Water-soluble unit dose article containing core / shell capsule

Abstract

A water-soluble unit dose article containing a laundry detergent composition comprising a capsule having a core and a shell.

Description

[Technical Field]

[0001] A water-soluble unit-dose article containing a laundry detergent composition that includes capsules having a core and a shell. [Background technology]

[0002] Water-soluble unit-dose articles are favored by consumers because they are convenient and efficient to use. Such water-soluble unit-dose articles often include laundry detergent compositions. While not strictly theoretical, when a water-soluble unit-dose article is added to water, the film dissolves / disintegrates, releasing its internal contents into the surrounding water and creating a cleaning solution.

[0003] In many cases, encapsulated fragrance technology is incorporated into detergent compositions of water-soluble unit-dose articles to provide the benefit of a refreshing feeling on fabrics. These encapsulated fragrance technologies involve a core containing fragrance raw materials enclosed in a shell. This shell is typically made from petrochemical-derived technologies, such as melamine formaldehyde or polyacrylate-based technologies. In recent years, for environmental sustainability reasons, compounders have been exploring ways to reduce the petrochemical content in their formulations.

[0004] In this field, encapsulated fragrance technology, which includes shells mainly composed of inorganic materials, has been proposed as a non-petrochemical alternative to capsules. However, it has been found that their fabric freshening performance is inferior to that of conventional petrochemical-derived capsule technology in conventional detergent compositions. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, there is a need for a laundry detergent composition containing fragrance capsules, wherein the fragrance capsules have a shell in which the petrochemical content is significantly reduced, and the laundry detergent composition containing said capsules exhibits an improved fabric freshness effect compared to known laundry detergent compositions containing fragrance capsules having a shell in which the petrochemical content is significantly reduced.

[0006] Surprisingly, it was found that when a laundry detergent composition containing fragrance capsules with a significantly reduced petrochemical content, encapsulated within a polyvinyl alcohol water-soluble film, is incorporated, the fabric freshness performance is greatly improved when compared in a single variable manner with the same detergent composition without the polyvinyl alcohol water-soluble film. [Means for solving the problem]

[0007] One aspect of the present invention is a water-soluble unit-dose article comprising a water-soluble polyvinyl alcohol film and a laundry detergent composition, wherein the water-soluble film encloses the laundry detergent composition, the laundry detergent composition comprises a capsule, the capsule having a core and a shell, the shell surrounding the core, the core comprising a hydrophobic material, preferably the hydrophobic material comprising at least one fragrance ingredient, and the shell comprising 90% to 100% by weight of an inorganic material of the shell. [Brief explanation of the drawing]

[0008] [Figure 1] This is a water-soluble unit-dose article according to the present invention. [Modes for carrying out the invention]

[0009] Water-soluble unit dose articles 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 will be described in detail below.

[0010] A water-soluble unit-dose article includes a water-soluble film, i.e., a water-soluble polyvinyl alcohol film, shaped such that the unit-dose article contains at least one internal compartment surrounded by a water-soluble film. The unit-dose article may include a first water-soluble film and a second water-soluble film sealed together to define the internal compartment. The water-soluble unit-dose article is configured to prevent the detergent composition from leaking out of the compartment during storage. However, when the water-soluble unit-dose article is added to water, the water-soluble film dissolves, releasing the contents of the internal compartment into the cleaning solution.

[0011] A compartment should be understood as a sealed internal space within a unit-dose article that holds the detergent composition. During manufacturing, the first water-soluble film may be shaped to include an opening compartment into which the detergent composition is added. Next, the first film is covered with a second water-soluble film in a direction that closes the opening of the compartment. The first and second films are then sealed together along the sealing region.

[0012] A unit dose article may contain more than one compartment, more than two compartments, more than three compartments, or more than four compartments. The compartments may be arranged in an overlapping configuration, that is, one positioned on top of the other. In such an orientation, the unit dose article contains at least three films, one or more in the top, one in the middle, and one in the bottom. Alternatively, the compartments may be arranged in an adjacent configuration, that is, one adjacent to the other. The compartments may be oriented in a "tire and rim" configuration, that is, the first compartment is positioned adjacent to the second compartment, but the first compartment at least partially surrounds the second compartment but does not completely enclose it. Alternatively, one compartment may be completely enclosed within another compartment.

[0013] If the unit dose article contains at least two compartments, one of the compartments may be smaller than the other. If the unit dose article contains at least three compartments, two of the compartments may be smaller than a third compartment, preferably with the smaller compartments overlapping the larger compartment. The overlapping compartments are preferably oriented adjacent to each other. The unit dose article may contain at least four compartments, three of which may be smaller than a fourth compartment, preferably with the smaller compartments overlapping the larger compartment. The overlapping compartments are preferably oriented adjacent to each other.

[0014] In a multi-compartment orientation, the detergent composition according to the present invention may be contained in at least one of the compartments. For example, the detergent composition may be contained in only one compartment, or in two compartments, or even three compartments, or even four compartments.

[0015] Each section may contain the same composition or different compositions. The different compositions may all be in the same form or in different forms.

[0016] The water-soluble unit-dose article may include at least two internal compartments, with the liquid laundry detergent composition contained within at least one of these compartments; preferably, the unit-dose article includes at least three compartments, with the detergent composition contained within at least one of these compartments.

[0017] Figure 1 discloses a water-soluble unit-dose article (1) according to the present invention. The water-soluble unit-dose article (1) comprises a first water-soluble film (2) and a second water-soluble film (3), which are sealed together in a sealing region (4). A liquid laundry detergent composition (5) is contained within the water-soluble unit-dose article (1).

[0018] While we do not wish to be bound by theory, we believe there is a synergistic effect between polyvinyl alcohol and fragrance capsules having the inorganic shell material according to the present invention. This synergistic effect results in improved capsule adhesion and retention to fabrics during washing, and a corresponding improvement in the overall freshness performance of the fabric, compared to incorporating these fragrance capsules having the shell material according to the present invention into a detergent composition encapsulated in a non-water-soluble polyvinyl alcohol film.

[0019] This is even more surprising, considering that petrochemical-derived encapsulated fragrance technology has been found to negatively interact with polyvinyl alcohol, leading to a loss of freshness in fabrics, compared to incorporating capsules with a higher petrochemical content into detergent compositions that are not encapsulated in water-soluble polyvinyl alcohol film.

[0020] Water-soluble film The film of the present invention is water-soluble or water-dispersible. The water-soluble film preferably has a thickness of 20 to 150 micrometers, preferably 35 to 125 micrometers, more preferably 50 to 110 micrometers, and most preferably about 76 micrometers.

[0021] Preferably, the water solubility of the film is at least 50%, preferably at least 75%, or even more than 95%, when measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers. Add 5 grams ± 0.1 grams of film material to a pre-weighed 3 L beaker, and add 2 L ± 5 mL of distilled water. Stir vigorously with a magnetic stirrer (Labline model number 1250 or equivalent and a 5 cm magnetic stirrer) set to 600 rpm for 30 minutes at 30°C. Next, filter the mixture through a pleated qualitative calcined glass filter with the pore size defined above (maximum 20 micrometers). Dry the water from the recovered filtrate by any conventional method and determine the weight of the remaining material (this is the dissolved fraction or dispersed fraction). Then, the percentage of solubility or dispersion can be calculated.

[0022] A preferred film material is preferably a polymer material. The film material can be obtained by methods well known in the art, such as casting, blow molding, extrusion, or blow extrusion of polymer materials.

[0023] The water-soluble film contains polyvinyl alcohol. Preferably, the water-soluble film contains at least 50% by weight, preferably at least 60% by weight, of the water-soluble film's polyvinyl alcohol. The water-soluble film may also contain 50% to 100% by weight, or even more, 60% to 99% by weight, of the water-soluble film's polyvinyl alcohol.

[0024] Preferably, the water-soluble film comprises a polyvinyl alcohol homopolymer or copolymer, preferably a blend of polyvinyl alcohol homopolymer and / or polyvinyl alcohol copolymer, preferably selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymers, and most preferably a blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer. Preferably, the water-soluble film comprises a polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer, preferably anionic polyvinyl alcohol copolymer, or a blend of polyvinyl alcohol homopolymer and / or polyvinyl alcohol copolymer, preferably anionic polyvinyl alcohol copolymer. More preferably, the water-soluble film comprises anionic polyvinyl alcohol copolymer, and even more preferably anionic polyvinyl alcohol copolymer selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymer, and most preferably, the water-soluble film comprises a blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer.

[0025] A preferred film is one that exhibits good solubility in cold water, i.e., unheated distilled water. Preferably, such a film exhibits good solubility at a temperature of 24°C, and more preferably at 10°C. Good solubility means that the film exhibits water solubility of at least 50%, preferably at least 75%, or even more preferably at least 95%, when measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers as described above.

[0026] Preferred films include those supplied by Monosol under product reference numbers M8630, M8900, M8779, and M8310.

[0027] The film may be opaque, transparent, or translucent. The film may include printed areas.

[0028] The printing area can be obtained using standard technologies such as flexographic printing or inkjet printing.

[0029] The film may 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 concentration of the aversive agent may be used in the film. Suitable concentrations include, but are not limited to, 1 to 5000 ppm, or even 100 to 2500 ppm, or even 250 to 2000 rpm.

[0030] Preferably, a water-soluble film, or a water-soluble unit-dose article, or both, is coated with a lubricant, preferably 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.

[0031] Preferably, the water-soluble film and each of its individual components independently contain 0 ppm to 20 ppm, preferably 0 ppm to 15 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, even more preferably 0 ppm to 1 ppm, even more preferably 0 ppb to 100 ppb, and most preferably 0 ppb of dioxane. Those skilled in the art will recognize known methods and techniques for determining the dioxane levels in the water-soluble film and its components.

[0032] Laundry detergent composition The laundry detergent composition may be any suitable composition. The composition may be in the form of solids, liquids, or mixtures thereof.

[0033] The solids may be in the form of fluid particles, compacted solids, or mixtures thereof. The solids may contain some water, but it should be understood that they are essentially water-free. In other words, water is not intentionally added except from the addition of various raw materials.

[0034] In relation to the laundry detergent compositions of the present invention, the term "liquid" encompasses forms such as dispersions, gels, and pastes. The liquid composition may also contain gases in preferably subdivided forms. The term "liquid laundry detergent composition" refers to any laundry detergent composition containing a liquid that can wet and treat fabrics in a household washing machine, for example, to clean clothes. A dispersion is, for example, a liquid containing solid or particulate matter.

[0035] The laundry detergent composition may be used as a fully formulated consumer product, or it may be added to one or more further ingredients to form a fully formulated consumer product. The laundry detergent composition may also be a “pre-treatment” composition added to the fabric, preferably to the stain on the fabric, before adding the fabric to the washing solution.

[0036] The laundry detergent composition includes capsules, which are described in more detail below.

[0037] 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 10% to 60% by weight, more preferably 20% to 55% by weight, of the non-soap surfactant.

[0038] Preferably, the anionic non-soap surfactant includes a linear alkylbenzene sulfonate, an alkyl sulfate, an alkoxylated alkyl sulfate, or a mixture thereof. Preferably, the alkoxylated alkyl sulfate is an ethoxylated alkyl sulfate.

[0039] Preferably, the laundry detergent composition contains 5% to 60% by weight, preferably 15% to 55% by weight, more preferably 25% to 50% by weight, and most preferably 30% to 45% by weight of a non-soap anionic surfactant.

[0040] Preferably, the non-soap anionic surfactant comprises a linear alkylbenzene sulfonate and an 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 1:10 to 10:1, preferably 6:1 to 1:6, more preferably 4:1 to 1:4, and even more preferably 3:1 to 1:1. Alternatively, the weight ratio of linear alkylbenzene sulfonate to ethoxylated alkyl sulfate is 1:2 to 1:4. The alkoxylated alkyl sulfate can be derived from synthetic alcohols or natural alcohols, or blends thereof, between desired mean alkyl carbon chain length and mean branching degree. Preferably, synthetic alcohols are prepared according to the Ziegler process, oxo process, modified oxo process, Fischer-Tropsch process, Guerbet process, or a mixture thereof. Preferably, the naturally derived alcohol is derived from natural oils, preferably coconut oil, palm kernel oil, or a mixture thereof.

[0041] Preferably, the laundry detergent composition contains 0% to 15% by weight, preferably 0.01% to 12% by weight, more preferably 0.1% to 10% by weight, and most preferably 0.15% to 7% by weight of a nonionic surfactant. 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 branching degree. The alcohol alkoxylate nonionic surfactant may be a primary or secondary alcohol alkoxylate nonionic surfactant, preferably a primary alcohol alkoxylate nonionic surfactant. Examples of synthetically derived alcohol alkoxylate nonionic surfactants include Ziegler synthetic alcohol alkoxylate, oxo synthetic alcohol alkoxylate, modified oxo process synthetic alcohol alkoxylate, Fischer-Tropsch synthetic alcohol alkoxylate, Guerbet alcohol alkoxylate, alkylphenol alcohol alkoxylate, or mixtures thereof. The alkoxylated chain may be a mixed alkoxylated chain containing ethoxy, propoxy, and / or butoxy units, or it may be a purely ethoxylated alkyl chain, preferably a purely ethoxylated alkyl chain.

[0042] Preferably, the laundry, preferably liquid laundry detergent composition, comprises 1.5% to 20% by weight, more preferably 2% to 15% by weight, even more preferably 3% to 10% by weight, and most preferably 4% to 8% by weight of soap, preferably fatty acid salt, more preferably amine neutralized fatty acid salt, wherein the amine is more preferably an alkanolamine selected from monoethanolamine, diethanolamine, triethanolamine, or a mixture thereof, and more preferably monoethanolamine.

[0043] Preferably, the laundry detergent composition contains a non-aqueous solvent, preferably selected from ethanol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, ethylene glycol, polyethylene glycol, polypropylene glycol, or a mixture thereof, preferably polypropylene glycol having a molecular weight of 400. Preferably, the liquid laundry detergent composition contains 10% to 40% by weight, preferably 15% to 30% by weight, of the non-aqueous solvent. While we do not wish to be bound by theory, the non-aqueous solvent ensures that the film is neither too brittle nor too "soft" so as to ensure an appropriate level of film plasticization. While we do not wish to be bound by theory, having the correct degree of plasticization also facilitates the dissolution of the film when exposed to water during the washing process.

[0044] Preferably, the liquid laundry detergent composition contains 1% to 20% by weight, preferably 5% to 15% by weight, of water.

[0045] Preferably, the laundry detergent composition contains components selected from the list including cationic polymers, polyester terephthalate polymers, amphiphilic graft copolymers, alkoxylated, preferably ethoxylated polyethyleneimine polymers, carboxymethylcellulose, enzymes, bleaching agents, or mixtures thereof.

[0046] Preferably, the laundry detergent composition contains non-encapsulated fragrances.

[0047] The laundry detergent composition may contain auxiliary components, which may be selected from hue dyes, aesthetic dyes, builders (preferably citric acid), chelating agents, cleaning polymers, dispersants, color transfer inhibitor polymers, fluorescent whitening agents, opaque agents, defoaming agents, preservatives, antioxidants, or mixtures thereof. Preferably, the chelating agent is selected from aminocarboxylate chelating agents, aminophosphonate chelating agents, or mixtures thereof.

[0048] Preferably, the laundry detergent composition has a pH of 6 to 10, more preferably 6.5 to 8.9, and most preferably 7 to 8, and the pH of the laundry detergent composition is measured as a 10% dilution in desalinated water at 20°C.

[0049] Liquid laundry detergent compositions may be Newtonian or non-Newtonian. Preferably, liquid laundry detergent compositions are non-Newtonian. While we do not wish to be bound by theory, non-Newtonian liquids have different properties from Newtonian liquids; more specifically, the viscosity of non-Newtonian liquids depends on the shear rate, whereas Newtonian liquids have a constant viscosity regardless of the shear rate applied. The decrease in viscosity of non-Newtonian liquids when shear is applied is thought to further promote the dissolution of the liquid detergent. The liquid laundry detergent compositions described herein may have any preferred viscosity depending on factors such as the components blended and the purpose of the composition. In the case of Newtonian compositions, according to the methods described herein, the compositions may have viscosity values ​​of 100 to 3,000 cP, or 200 to 2,000 cP, or 300 to 1,000 cP at a shear rate of 20 s⁻¹ and a temperature of 20°C. For non-Newtonian compositions, according to the methods described herein, the compositions may have high shear viscosity values ​​of 100–3,000 cP, or 300–2,000 cP, or 500–1,000 cP at a shear rate of 20 s⁻¹ and a temperature of 20°C, and low shear viscosity values ​​of 500–100,000 cP, or 1,000–10,000 cP, or 1,300–5,000 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 this disclosure, viscosity measurement is performed using a rotational rheometer, for example, TA Instrument's AR550. This instrument includes a 40 mm 2° or 1° cone fixture with a gap of about 50–60 μιη for isotropic liquids, or a 40 mm flat steel plate with a gap of 1,000 μιη for liquid-containing particles. This measurement is performed using a flow procedure that includes a tune-up step, peak hold, and continuous sloping step. The tune-up step includes a 10-second pre-shear at a shear rate of 10 s1, and a 60-second equilibrium at the selected temperature, with the measurement temperature set at 20°C. Peak hold involves sampling every 10 s and applying a shear rate of 0.05 s1 at 20°C for 3 minutes. The continuous sloping step is performed at shear rates from 0.1 to 1200 s1 at 20°C for 3 minutes to obtain the full flow profile.

[0050] capsule The laundry detergent composition contains capsules, each capsule having a core and a shell, the shell surrounding the core.

[0051] The laundry detergent composition preferably contains capsules in an amount of 0.05% to 20% by weight, more preferably 0.05% to 10% by weight, even more preferably 0.1% to 5% by weight, and most preferably 0.2% to 3% by weight of the laundry detergent composition.

[0052] The core contains a hydrophobic material, preferably containing at least one fragrance ingredient. The core is described in more detail below.

[0053] The laundry detergent composition may contain a fragrance containing capsules as the sole source of fragrance raw materials, or it may contain a fragrance containing capsules in combination with a fragrance that is freely added to the laundry detergent composition. The laundry detergent composition may contain a sufficient amount of capsules to provide the laundry detergent composition with fragrance raw materials in an amount of about 0.05% to about 10% by weight, or about 0.1% to about 5% by weight, or about 0.1% to about 3% by weight. In the context of this specification, the amount or weight percentage of capsules means the total of the shell material and the core material.

[0054] The capsule may have an average shell thickness of 10 nm to 10,000 nm, preferably 170 nm to 1,000 nm, and more preferably 300 nm to 500 nm.

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

[0056] The average volume-loaded diameter of the capsule may be 1 to 200 micrometers, preferably 1 to 10 micrometers, and more preferably 2 to 8 micrometers. The shell thickness may be 1 to 10,000 nm, 1 to 1,000 nm, or 10 to 200 nm. The capsule may have an average volume-loaded diameter of 1 to 10 micrometers and a shell thickness of 1 to 200 nm. Capsules having an average volume-loaded diameter of 1 to 10 micrometers and a shell thickness of 1 to 200 nm have been found to have higher fracture strength.

[0057] While not bound by theory, it is thought that higher fracture strength leads to better persistence during the washing process, and the washing process can cause mechanically weak capsules to rupture prematurely due to mechanical constraints in the washing machine.

[0058] Capsules having an average volume-weighted diameter of 1 to 10 micrometers and a shell thickness of 10 to 200 nm will only be resistant to mechanical constraints if the silica precursor used is carefully selected and prepared. The precursor may have a molecular weight of 2 to 5 kDa, more preferably 2.5 to 4 kDa. In addition, the concentration of the precursor must be carefully selected, and the concentration should be 20 to 60% by weight, preferably 40 to 60% by weight, of the oil phase used during encapsulation.

[0059] While not bound by theory, it is believed that high molecular weight precursors have a much slower migration time from the oil phase to the water phase. This slower migration time is thought to result from a combination of three phenomena: diffusion, distribution, and reaction kinetics. This phenomenon is important in the context of small-sized capsules due to the fact that the total surface area between the oil and water in the system increases as the capsule diameter decreases. A larger surface area leads to greater migration of the precursor from the oil phase to the water phase, which in turn reduces the polymerization yield at the interface. Therefore, a higher molecular weight precursor is required to mitigate the effects caused by the increased surface area and to obtain the capsule according to the present invention.

[0060] Surprisingly, it was found that, in addition to the inorganic shell, the volume-to-core-to-shell ratio can also play a role in ensuring the physical integrity of the capsule. Shells that are too thin relative to the overall size of the capsule (core-to-shell ratio > 98:2) tend to suffer from a lack of self-integration. On the other hand, shells that are extremely thick relative to the diameter of the capsule (core-to-shell ratio < 80:20) tend to have higher shell permeability in surfactant-rich matrices. While it would intuitively be expected that a thicker shell would result in lower shell permeability (because this parameter affects the average diffusion pathway of the active substance across the shell), surprisingly, it was found that capsules of the present invention having shells with thicknesses exceeding a threshold exhibited higher shell permeability. This upper threshold is thought to depend to some extent on the capsule diameter. The volume-to-core-to-shell ratio is determined according to the method provided in the Test Methods section below.

[0061] The capsule may have a volume core-to-shell ratio of 50:50 to 99:1, preferably 60:40 to 99:1, preferably 70:30 to 98:2, and more preferably 80:20 to 96:4.

[0062] It may be desirable to have a specific combination of these capsule characteristics. For example, a capsule may have a volume-core-to-shell ratio of approximately 99:1 to approximately 50:50, an average volume-weighted capsule diameter of approximately 0.1 μm to approximately 200 μm, and an average shell thickness of approximately 10 nm to approximately 10,000 nm. A capsule may have a volume-core-to-shell ratio of approximately 99:1 to approximately 50:50, an average volume-weighted capsule diameter of approximately 10 μm to approximately 200 μm, and an average shell thickness of approximately 170 nm to approximately 10,000 nm. A capsule may have a volume-core-to-shell ratio of approximately 98:2 to approximately 70:30, an average volume-weighted capsule diameter of approximately 10 μm to approximately 100 μm, and an average shell thickness of approximately 300 nm to approximately 1000 nm.

[0063] The method according to this disclosure can produce capsules with a low coefficient of variation of capsule diameter. By controlling the size distribution of the capsules, it is possible to improve the fracture strength of the group and enable the group to have a more uniform fracture strength. The capsule group can have a coefficient of variation of capsule diameter of 40% or less, preferably 30% or less, and more preferably 20% or less.

[0064] For capsules containing a cost-effective core material that works in consumer goods applications such as liquid detergents or liquid fabric softeners, the capsule should i) be resistant to core diffusion during the shelf life of the liquid product (e.g., low leakage or permeability), ii) be able to deposit on a targeted surface during application (e.g., during a washing machine cycle), and iii) be able to release the core material by mechanically rupturing the shell at the correct time and place, thereby providing the intended benefit to the end consumer.

[0065] The capsules described herein can have an average fracture strength of 0.1 MPa to 10 MPa, preferably 0.25 MPa to 5 MPa, and more preferably 0.25 MPa to 3 MPa. While conventionally, completely inorganic capsules have inferior fracture strength, the capsules described herein can have a fracture strength exceeding 0.25 MPa, improving stability and allowing them to induce the release of beneficial agents upon receiving a bursting stress of a specified magnitude.

[0066] The core may be oil-based or water-based. Preferably, the core is oil-based. In embodiments, the core may be liquid at the temperature in which it is used in the compound product. The core may be liquid at or near room temperature.

[0067] The core preferably contains fragrance ingredients. The core may contain about 1% to 100% by weight of fragrance based on the total weight of the core. Preferably, the core may contain about 50% to 100% by weight of fragrance based on the total weight of the core, or about 80% to 100% by weight of fragrance based on the total weight of the core. Typically, higher levels of fragrance are preferred for improved delivery efficiency.

[0068] The fragrance raw material may contain one or more, preferably two or more, fragrance raw materials. The term "fragrance raw material" (or "PRM") as used herein means a compound having a molecular weight of at least about 100 g / mol and useful for imparting odor, fragrance, essence, or scent, either alone or in combination with other fragrance raw materials. Typical PRMs include alcohols, ketones, aldehydes, esters, ethers, nitrides, and alkenes such as terpenes.

[0069] PRMs may be characterized by their boiling point (BP), measured at atmospheric pressure (760 mmHg), and their octanol / water partition coefficient (P), which can be described in relation to logP, determined according to the test method described in the Test Methods section. Based on these characteristics, PRMs may be classified as fragrances of Quadrant I, Quadrant II, Quadrant III, and Quadrant IV, as described in more detail below. Fragrances with various PRMs from different quadrants may be desirable, for example, to provide aromatic effects at different touchpoints during normal use.

[0070] Fragrance raw materials having a boiling point BP lower than approximately 250°C and a logP lower than approximately 3 are known as Quadrant I fragrance raw materials. It is preferable that Quadrant I fragrance raw materials be limited to less than 30% of the fragrance composition. Fragrance raw materials having a BP higher than approximately 250°C and a logP higher than approximately 3 are known as Quadrant IV fragrance raw materials, fragrance raw materials having a BP higher than approximately 250°C and a logP lower than approximately 3 are known as Quadrant II fragrance raw materials, and fragrance raw materials having a BP lower than approximately 250°C and a logP higher than approximately 3 are known as Quadrant III fragrance raw materials.

[0071] Preferably, the capsule contains a fragrance. Preferably, the fragrance in the capsule contains a mixture of at least three, or more precisely, at least five, or at least seven fragrance ingredients. The fragrance in the capsule may also contain at least ten or at least fifteen fragrance ingredients. The mixture of fragrance ingredients may provide a more complex and desirable aesthetic, and / or better fragrance performance or longevity, for example, at various touchpoints. However, it may be desirable to limit the number of fragrance ingredients in the fragrance in order to reduce or limit the complexity and / or cost of the formulation.

[0072] The fragrance may contain at least one naturally derived fragrance ingredient. Such ingredients may be desirable for sustainability / environmental reasons. The naturally derived fragrance ingredient may contain natural extracts or essences that may contain a mixture of PRMs. Examples of such natural extracts or essences include orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, sandalwood oil, pine root oil, and cedar.

[0073] The core may include, in addition to fragrance raw materials, pro-fragrances that can contribute to improving the duration of the refreshing effect. The pro-fragrances may include, for example, non-volatile substances that release or convert fragrance substances as a result of simple hydrolysis, or pH-change induced pro-fragrances (e.g., induced by a decrease in pH), or enzyme-releaseable pro-fragrances, or photo-induced pro-fragrances. Depending on the selected pro-fragrances, the pro-fragrances may exhibit a variety of release rates.

[0074] The core of the inclusions of this disclosure may contain core modifiers such as distribution modifiers and / or density modifiers. In addition to the fragrance, the core may contain distribution modifiers in an amount of more than 0% to about 80%, preferably more than 0% to about 50%, more preferably more than 0% to about 30%, based on the total weight of the core. The distribution modifiers include vegetable oils, modified vegetable oils, C4-C 24The material may include a selection of materials from the group consisting of mono-, di-, and tri-esters of fatty acids, isopropyl myristate, dodecanophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partitioning regulator may preferably contain isopropyl myristate or consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably contain castor oil and / or soybean oil.

[0075] The shell contains 90% to 100% by weight, preferably 95% to 100% by weight, and more preferably 99% to 100% by weight of inorganic material. Preferably, the inorganic material in the shell includes materials selected from metal oxides, metalloid oxides, metals, minerals, or mixtures thereof. Preferably, the inorganic material in the shell includes materials 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 materials selected from SiO2, TiO2, Al2O3, CaCO3, or mixtures thereof, most preferably SiO2.

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

[0077] The inorganic shell may include a first shell component including a condensation layer surrounding the core, and may further include a nanoparticle layer surrounding the condensation layer. The inorganic shell may further include a second shell component surrounding the first shell component. The first shell component includes an inorganic material, preferably a metal / semimetal oxide, more preferably SiO2, TiO2, and Al2O3, or a mixture thereof, even more preferably SiO2. The second shell component includes an inorganic material, preferably a material from the group of metal / semimetal oxides, metals, and minerals, more preferably a material selected from the list of SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, clay, gold, silver, iron, nickel, and copper, or a mixture thereof, even more preferably a material selected from SiO2 and CaCO3 or a mixture thereof. Preferably, the material of the second shell component is the same type of chemical substance as the first shell component in order to maximize chemical compatibility.

[0078] The first shell component may include a condensation layer surrounding the core. The condensation layer may be a condensation product of one or more precursors. The one or more precursors may include at least one compound from the group consisting of formula (I), formula (II), and mixtures thereof, where formula (I) is (M v O z Y n ) w and formula (II) is (M v O z Y n R<​​​​​​​​​​​​​​​​​​​(Equation I) (In the formula, M is one or more of silicon, titanium, and aluminum; v is the valence of M, which is 3 or 4; z is 0.5 to 1.6, preferably 0.5 to 1.5; and each Y is -OH, -OR) 2 -NH2, -NHR 2 , -N(R 2 ) Selected from 2, R 2 C1~C 20 Alkyl, C1-C 20 Alkylene, C6~C 22 Independently selected from aryl or 5-12 membered heteroaryls containing 1-3 ring heteroatoms selected from O, N, and S, R 3 H, C1~C 20 Alkyl, C1-C 20 Alkylene, C6~C 22 A 5-12 membered heteroaryl compound containing an aryl or 1-3 ring heteroatoms selected from O, N, and S, where n is 0.7-(v-1) and w is 2-2000.

[0080] One or more precursors may be of formula (I), where M is silicon and Y is -OR 2 It may also be n can be 1 to 3. Y is -OR 2 And it is preferable that n is 1 to 3. n is at least 2, and one or more of Y are -OR 2 In this case, it is preferable that one or more of the Y components be -OH.

[0081] R 2 C1~C 20 Alkyl may also be used. 2 C6~C 22 It could also be aryl. 2 This may be one or more of C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, and C8 alkyl. 2 R may be a C1 alkyl group. 2 R may be a C2 alkyl group. 2R may be a C3 alkyl group. 2 This may be a C4 alkyl group.

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

[0083] M is silicon, v is 4, and each Y is -OR 2 n is 2 and / or 3, and each R 2 It may be a C2 alkyl group.

[0084] The precursor may include polyalkoxysilane (PAOS). The precursor may include polyalkoxysilane (PAOS) ​​synthesized via a non-hydrolysis process.

[0085] The precursor may, alternatively or further, comprise one or more compounds of formula (II): (M v O z Y n R 1 p ) w (Formula II) (In the formula, M is one or more of silicon, titanium, and aluminum; v is the valence of M, which is 3 or 4; z is 0.5 to 1.6, preferably 0.5 to 1.5; and each Y is -OH, -OR) 2 -NH2, -NHR 2 , -N(R 2 ) Selected from 2, R 2 C1~C 20 Alkyl, C1-C 20 Alkylene, C6~C 22 Independently selected from aryl or 5-12 membered heteroaryls containing 1-3 ring heteroatoms selected from O, N, and S, R 3 H, C1~C 20 Alkyl, C1-C 20 Alkylene, C6~C 22An aryl or 5-12 membered heteroaryl containing 1-3 ring heteroatoms selected from O, N, and S, where n is 0-(v-1), and each R 1 C1~C 30 Alkyl; C1~C 30 Alkylene; C1-C substituted with members (e.g., one or more) selected from the group consisting of halogens, -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. 30 C1-C1 are substituted with members selected from the group consisting of alkyl, 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 Independently selected from the group consisting of alkylenes; p is a number greater than 0 up to pmax, where pmax = 60 / [9 * Mw(R 1 )+8] and Mw(R 1 ) is R 1 This is the molecular weight of the group, where w is between 2 and 2000.

[0086] R 1 C1-C1 is substituted with 1-4 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 groups. 30 It may be alkyl. 1 C1-C1 is substituted with 1-4 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 groups. 30It could be alkylene.

[0087] As described above, it may be preferable to reduce or eliminate the presence of the compound according to formula (II) having an R1 group in order to reduce or even eliminate the organic content in the first shell component. The precursor, condensation layer, first shell component, and / or shell do not have to contain the compound according to formula (II).

[0088] The precursors of formula (I) and / or (II) may be characterized by one or more physical properties, namely molecular weight (Mw), degree of branching (DB), and polydispersity index (PDI) of the molecular weight distribution. Selecting a specific Mw and / or DB is considered useful in obtaining capsules that retain their mechanical integrity when dried on a surface and have low shell permeability in a surfactant matrix. The precursors 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 1,000 Da to 30,000 Da. These characteristics provide useful properties for the precursors in order to obtain the capsules of the present invention. The precursors of formula (I) and / or (II) may have a PDI of 1 to 50.

[0089] The condensation layer containing a metal / metalloid oxide may be formed from a condensation product of a precursor containing at least one compound of formula (I) and / or at least one compound of formula (II), optionally combined with one or more monomer precursors of the metal / metalloid oxide, wherein the metal / metalloid oxide includes TiO2, Al2O3, and SiO2, preferably SiO2. Examples of monomer precursors of the metal / metalloid oxide include those of formula M(Y) V-n R n Compounds of the form (wherein M, Y, and R are as defined in formula (II), and n may be an integer from 0 to 3) may also be given. The monomer precursor of the metal / metallic oxide is preferably one in which M is silicon and the compound has the general formula Si(Y) 4-n R nThe monomers may be in a form having (wherein Y and R are defined as in formula (II), and n may be an integer from 0 to 3). Examples of such monomers are TEOS (tetraethoxyorthosilicate), TMOS (tetramethoxyorthosilicate), TBOS (tetrabutoxyorthosilicate), triethoxymethylsilane (TEMS), diethoxydimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). These are not intended to limit the range of monomers that can be used, and suitable monomers that can be used in combination as described herein will be obvious to those skilled in the art.

[0090] In embodiments, the first shell component may include an arbitrary nanoparticle layer. The nanoparticle layer contains nanoparticles. The nanoparticles in the nanoparticle layer may be one or more of SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, clay, silver, gold, and copper. Preferably, the nanoparticle layer may contain SiO2 nanoparticles.

[0091] The nanoparticles can have an average diameter of 1 nm to 500 nm, preferably 50 nm to 400 nm.

[0092] The pore size of the capsule can be adjusted by changing the shape of the nanoparticles and / or by using a combination of nanoparticles of different sizes. For example, non-spherical and irregular nanoparticles can be used because they may improve packing when forming a nanoparticle layer, thereby resulting in a higher density shell structure. This may be advantageous when it is necessary to limit permeability. The nanoparticles used may have more regular shapes, such as spherical ones. Any conceivable nanoparticle shape can be used herein.

[0093] Nanoparticles may not contain substantially hydrophobic modifications. Nanoparticles may not contain substantially organic compound modifications. Nanoparticles may contain organic compound modifications. Nanoparticles may be hydrophilic.

[0094] Nanoparticles may include surface modifications, such as linear or branched C1-C 20 Examples of surface modifications include, but are not limited to, alkyl groups, surface amino groups, surface methacrylic groups, surface halogens, or surface thiols. These surface modifications enable the nanoparticle surface to covalently bond organic molecules to itself. Where inorganic nanoparticles are disclosed herein, this means that any or none of the aforementioned surface modifications are included, although not explicitly stated.

[0095] The capsule of the present invention may be defined as comprising a substantially inorganic shell comprising a first shell component and a second shell component. Substantially inorganic means that the first shell component may contain up to 10% by weight or up to 5% by weight of organic content, preferably up to 1% by weight, as defined later in the calculation of organic content. It may be preferable that the first shell component, the second shell component, or both contain an organic content of about 5% by weight or less, preferably about 2% by weight or less, and more preferably about 0% by weight, relative to the weight of the first or shell component.

[0096] The first shell component is useful for constructing a mechanically robust scaffold or skeleton, but can also provide low shell permeability in liquid products containing surfactants, such as laundry detergents, shower gels, and cleansers (see Surfactants in Consumer Products, J. Falbe, Springer-Verlag). The second shell component can significantly reduce shell permeability, improving capsule impermeability in surfactant-based matrices. The second shell component can also significantly improve the mechanical properties of the capsule, such as burst force and fracture strength. While not theoretically bound, the second shell component is thought to contribute to the overall density of the shell by depositing precursors in the pores remaining within 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 arise only when used in combination with the first shell component as defined in this invention.

[0097] The capsules of this disclosure may first be formed by mixing a hydrophobic material with one of the condensation layer precursors defined above, thereby forming an oil phase, the oil phase may include oil-based and / or oil-soluble precursors. The mixture of the precursor and the hydrophobic material is then used with the aqueous phase as a dispersed phase or as a continuous phase. When the two phases are mixed and homogenized by methods known to those skilled in the art, an O / W (oil in water) emulsion is formed in the former case, and a W / O (water in oil) emulsion is formed in the latter case. Preferably, an O / W emulsion is formed. Nanoparticles can be present in the aqueous phase and / or oil phase regardless of the desired emulsion type. The oil phase may include an oily core modifier and / or an oil-soluble beneficial agent and a condensation layer precursor. Suitable core materials used in the oil phase are described earlier herein.

[0098] Once either emulsion is formed, the following occurs: (a) A step in which nanoparticles move to the oil / water interface and thereby form a nanoparticle layer, (b) The precursor of the condensation layer, which contains a metal / metallic oxide precursor, may begin to undergo hydrolysis / condensation reactions with water at the oil / water interface, thereby forming a condensation layer surrounded by a nanoparticle layer. The precursor of the condensation layer may further react with the nanoparticles in the nanoparticle layer.

[0099] The precursor that forms the condensation layer can be present in an amount of 1% to 50% by weight, preferably 10% to 40% by weight, based on the total weight of the oil phase.

[0100] The oil phase composition may contain any of the compounds defined in the Core section above. The oil phase may contain 10% to about 99% by weight of beneficial agents before emulsification.

[0101] In the method for preparing capsules according to this disclosure, the oil phase may be a dispersed phase, and the continuous aqueous (or water) phase may include water, an acid or base, and nanoparticles. The aqueous (or water) phase may have a pH of 1 to 11, preferably 1 to 7, at least when both the oil and aqueous phases are mixed together. 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. The acid may be a weak acid. The weak acid may be acetic acid or HF. The concentration of the acid in the continuous aqueous phase is 10 -7 The concentration can be 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 inorganic base may be about 10⁻⁵ M to 0.01 M NaOH, or about 10⁻⁵ M to about 1 M ammonia. The list of acids and bases exemplified above and their concentration ranges is not intended to limit the scope of the present invention, and other suitable acids and bases that enable control of the pH of the continuous phase are conceived herein.

[0102] In the method for preparing capsules according to this disclosure, the pH can be varied throughout the process by adding acids and / or bases. For example, the method can be started with an aqueous phase of acidic or neutral pH, and later, a base can be added during the process to increase the pH. Alternatively, the method can be started with an aqueous phase of basic or neutral pH, and later, an acid can be added during the process to decrease the pH. Furthermore, the method can be started with an aqueous phase of acidic or neutral pH, and an acid can be added during the process to further decrease the pH. Furthermore, the method can be started with an aqueous phase of basic or neutral pH, and a base can be added during the process to further increase the pH. Any suitable pH shift may be used. In addition, any suitable combination of acids and bases can be used at any point to achieve the desired pH. Any of the nanoparticles described above can be used in the aqueous phase. The nanoparticles may be present in an amount of about 0.01% to about 10% by weight, based on the total weight of the aqueous phase.

[0103] This method may include mixing the oil phase and the aqueous phase in an oil-to-aqueous water phase ratio of approximately 1:10 to approximately 1:1.

[0104] A second shell component can be formed by mixing a capsule having a first shell component with a solution of a second shell component precursor. The solution of the second shell component precursor may contain a water-soluble or oil-soluble second shell component precursor. The second shell component precursor may be one or more of the compounds of formula (I) defined above, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS), triethoxymethylsilane (TEMS), diethoxydimethylsilane (DEDMS), trimethylethoxysilane (TMES), and tetraacetoxysilane (TAcS). The second shell component precursor is Si(Y) 4-n R nThe second shell component precursor may also include one or more silane monomers of type 1 (wherein Y is a hydrolyzable group, R is a non-hydrolyzable group, and n can be an integer from 0 to 3). Examples of such monomers have been previously described in this paragraph, but this does not mean to limit the range of monomers that can be used. The second shell component precursor may include silicates, titanates, aluminates, zirconates, and / or zincates. The second shell component precursor may include carbonates and calcium salts. The second shell component precursor may include salts of iron, silver, copper, nickel, and / or gold. The second shell component precursor may include alkoxides of zinc, zirconium, silicon, titanium, and / or aluminum. The second shell component precursor may include one or more of the following: silicate solutions such as sodium silicate, silicon tetraalkoxide solutions, iron sulfates and iron nitrates, titanium alkoxide solutions, aluminum trialkoxide solutions, zinc dialkoxide solutions, zirconium alkoxide solutions, calcium salt solutions, and carbonate solutions. A second shell component containing CaCO3 can be obtained by using a combination of calcium salt and carbonate. While a second shell component containing CaCO3 can be obtained from calcium salt without adding carbonate, this requires the situ generation of carbonate ions from CO2.

[0105] The second shell component precursor may include any preferred combination of any of the aforementioned compounds.

[0106] A solution of the second shell component precursor can be added dropwise to a capsule containing the first shell component. The solution of the second shell component precursor and the capsule can be mixed together within 1 minute to 24 hours. The solution of the second shell component precursor and the capsule can be mixed together at room temperature or at a high temperature, for example, between 20°C and 100°C.

[0107] The second shell component precursor solution may contain the second shell component precursor in an amount of 1% to 50% by weight relative to the total weight of the second shell component precursor solution.

[0108] A capsule having a first shell component can be mixed with a solution of a 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 contain one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4, and HClO3, preferably HCl. In other embodiments, the acid may be a weak acid. In embodiments, the weak acid may be acetic acid or HF. The concentration of the acid in the solution of the second shell component precursor is 10 -7 The concentration can be 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 inorganic base may be about 10 -5 M~0.01M NaOH, or about 10 -5 This can be M to about 1M ammonia. The list of acids and bases exemplified above is not intended to limit the scope of the present invention, and other suitable acids and bases that enable control of the pH of the second shell component precursor solution are intended herein.

[0109] The process of forming the second shell component may include changing the pH during the process. For example, the process of forming the second shell component may start at an acidic or neutral pH and later increase the pH by adding a base during the process. Alternatively, the process of forming the second shell component may start at a basic or neutral pH and later decrease the pH by adding an acid during the process. Furthermore, the process of forming the second shell component may start at an acidic or neutral pH and further decrease the pH by adding an acid during the process. Furthermore, the process of forming the second shell component may start at a basic or neutral pH and further increase the pH by adding a base during the process. Any suitable pH shift may be used. In addition, any suitable combination of acid and base can be used at any point in the solution of the second shell component precursor to achieve the desired pH. The process of forming the second shell component may include maintaining a stable pH during the process with a deviation of up to ±0.5 pH units. For example, the process of forming the second shell component may be maintained at a basic, acidic, or neutral pH. Alternatively, the process of forming the second shell component can be maintained within a specific pH range by controlling the pH using an acid or base. Any suitable pH range may be used. Furthermore, any suitable combination of acid and base can be used at any point in the solution of the second shell component precursor to maintain a stable pH within a desired range.

[0110] Whether an oil-based or aqueous core is prepared, the emulsion can be cured under conditions that solidify the precursor, thereby forming a shell that surrounds the core.

[0111] The reaction temperature for curing can be increased to accelerate the rate at which solidified capsules are obtained. The curing process can induce the condensation of precursors. The curing process can be carried out at room temperature or a temperature higher than room temperature. The curing process can be carried out at a temperature of 30°C to 150°C, preferably 50°C to 120°C, more preferably 80°C to 100°C. The curing process can be carried out over any suitable period of time to allow the capsule shell to be strengthened through the condensation of the precursor material. The curing process can be carried out over a period of 1 minute to 45 days, preferably 1 hour to 7 days, more preferably 1 hour to 24 hours. A capsule is considered cured when it no longer disintegrates. The determination of capsule disintegration is described in detail below. During the curing step, hydrolysis of the Y moiety (from formulas (I) and / or (II)) is thought to occur, followed by subsequent condensation of either the -OH group with another -OH group, or the -OH group with another Y-type moiety (wherein the formulas the two Ys are not necessarily the same). The hydrolyzed portion of the precursor initially condenses with the surface portion of the nanoparticle (if the nanoparticle contains such a portion). As shell formation progresses, the precursor portion begins to react with the previously formed shell.

[0112] The emulsion can be cured so that the shell precursor condenses. The emulsion can be cured so that the shell precursor reacts with nanoparticles and condenses. Below are examples of the hydrolysis and condensation steps described herein for silica-based shells. Hydrolysis:≡Si-OR+H2O → ≡Si-OH+ROH Condensation: ≡Si-OH+≡Si-OR → ≡Si-O-Si≡+ROH ≡Si-OH+≡Si-OH → ≡Si-O-Si≡+H2O.

[0113] For example, when a precursor of formula (I) or (II) is used, the following describes the hydrolysis step and the condensation step. Hydrolysis:≡M-Y+H2O → ≡M-OH+YH Condensation: ≡M-OH+≡MY → ≡MOM≡+YH ≡M-OH+≡M-OH → ≡MOM≡+H2O.

[0114] The capsules may be provided as a slurry composition (or simply "slurry" as used herein). The results of the methods described herein may be a slurry containing the capsules. The slurry can be formulated into products, such as consumer products.

[0115] Method for preparing water-soluble unit-dose articles Those skilled in the art will recognize known techniques and methods for producing liquid laundry detergent compositions and water-soluble unit-dose articles.

[0116] How to use A further aspect of the present invention is a method for washing fabric, comprising the steps of: preparing a washing solution by diluting a water-soluble unit-dose article according to the present invention with water 200 to 3000 times, preferably 300 to 2000 times; and bringing the fabric to be treated into contact with the washing solution.

[0117] The cleaning solution may preferably contain water of any hardness ranging from 0 gpg to 40 gpg.

[0118] Preferably, the washing solution contains 0.01 to 100 ppm, preferably 0.1 to 10 ppm, of polyvinyl alcohol and 1 to 1000 ppm, preferably 10 to 100 ppm, of capsules. The weight ratio of capsules and polyvinyl alcohol in the washing solution is preferably 1:1 to 100:1, preferably 10:1 to 50:1.

[0119] Test method It will be understood that the values ​​of each parameter of the applicant's claimed subject matter, as claimed and described herein, should be measured using the test methods disclosed in the section on test methods of this application.

[0120] How to determine logP For each PRM in the fragrance mixture under test, calculate the log value (logP) of the octanol / water partition coefficient. The logP values ​​for individual PRMs are calculated using the Consensus logP Computational Model, version 14.02 (Linux®), available from Advanced Chemistry Development Inc. (ACD / Lab) (Toronto, Canada), yielding dimensionless logP values. The ACD / Labs Consensus logP Computational Model is part of the ACD / Labs model suite.

[0121] Average shell thickness measurement The capsule shell, including the first shell component and, if present, the second shell component, is measured in nanometer units for 20 delivery capsules containing the beneficial agent, using a focused ion beam scanning electron microscope (FIB-SEM, Helios Nanolab 650, FEI) or equivalent instrument. A sample is prepared by diluting a small amount of liquid capsule dispersion (20 μL) with distilled water (1:10). The suspension is then deposited onto an ethanol-washed aluminum stub and transferred to a carbon coating apparatus (Leica EM ACE600 or equivalent instrument). The sample is dried in the coating apparatus under vacuum (vacuum level: 10 -5 (mbar). Next, a conductive carbon layer is deposited on the sample by flash deposition of 25nm to 50nm carbon. Then, the aluminum stub is transferred to the FIB-SEM to prepare the capsule cross section. The cross section is prepared by ionic grinding using a cross section cleaning pattern with an acceleration voltage of 30kV and an emission current of 2.5nA. Images are acquired at 5.0kV and 100pA in immersion mode (dwell time: approximately 10 microseconds) at a magnification of approximately 10,000x.

[0122] From 20 randomly selected beneficial drug delivery capsules with no size bias, cross-sectional images of the fractured shells are obtained to create a representative sample of the size distribution of the capsules present. The shell thickness of each of the 20 inclusions is measured at three different randomly selected locations using calibrated microscopy software by drawing measurement lines perpendicular to the contact surface of the outer surface of the capsule shell. Sixty independent thickness measurements are recorded and used to calculate the average thickness.

[0123] Mean and coefficient of variation of volume-weighted capsule diameter The capsule size distribution is determined by single-particle optical detection (SPOS), also known as optical particle counting (OPC), using an AccuSizer 780 AD instrument or equivalent, and accompanying software CW788 version 1.82 (Particle Sizing Systems, Inc., Santa Barbara, California, USA) or equivalent software. The instrument is configured with the following conditions and options: flow rate = 1 mL / sec; small diameter threshold = 0.50 μm; sensor model number = LE400-05SE or equivalent; auto-dilution = on; collection time: 60 seconds; number of channels = 512; fluid volume in container = 50 ml; maximum simultaneous count = 9200. The measurement is initiated by cooling the sensor by flushing it with water until the background count is less than 100. A sample of delivery capsules in suspension is introduced, and the capsule density is adjusted as needed via auto-dilution with deionized water so that the capsule count is a maximum of 9200 per mL. The suspension is analyzed over 60 seconds. The size range used was 1 μm to 493.3 μm.

[0124] Volume distribution:

[0125]

number

[0126]

number

[0127] Evaluation of the volumetric core-to-shell ratio The volume-core-to-shell ratio is determined as follows and depends on the average shell thickness measured by the shell thickness test method. For capsules with a measured average shell thickness, the volume-core-to-shell ratio is calculated using the following equation:

[0128]

number

[0129] This ratio can be converted to a core-to-shell fraction value by calculating the core weight percentage using the following formula.

[0130]

number

[0131] Method for determining branching degree The degree of branching of the precursor was determined as follows: The degree of branching is measured using (29Si) nuclear magnetic resonance spectroscopy (NMR).

[0132] Sample preparation Dilute each sample to a 25% solution using deuterated benzene (Benzene-D6"100%" (D, 99.96%, available from Cambridge Isotope Laboratories Inc., Tewksbury, Massachusetts) or an equivalent. Add 0.015 M chromium(III) acetylacetonate (99.99% purity, available from Sigma-Aldrich, St. Louis, Missouri, or an equivalent) as a paramagnetic relaxation agent. If using glass NMR tubes (Wilmed-LabGlass, Vineland, New Jersey, or an equivalent) for analysis, a blank sample must also be prepared by filling the NMR tube with the same type of deuterated solvent used to dissolve the sample. The same glass tube must be used for analyzing both the blank and the sample.

[0133] Sample analysis The branching degree is determined using a Bruker 400 MHz nuclear magnetic resonance (NMR) spectrometer or equivalent instrument. A standard silicon (29Si) method (e.g., from Bruker) is used with default parameter settings, involving a minimum of 1000 scans and a 30-second relaxation time.

[0134] Sample processing The samples are stored and processed using appropriate system software for NMR spectroscopy, such as MestReNova version 12.0.4-22023 (available from Mestrelab Research) or an equivalent. Phase adjustment and background correction are applied. A large, broad signal extending from -70 to -136 ppm exists, which is a result of using the glass present in the glass NMR tube and probe housing. This signal is suppressed by subtracting the spectrum of the blank sample from the spectrum of the synthesized sample, provided that the same tube and method parameters are used to analyze the blank and sample. To further account for slight differences in data acquisition, tubes, etc., the region outside the peak of the region of interest should be integrated and normalized to a consistent value. For example, integrate -117 to -115 ppm and set the integrated value to 4 for all blanks and samples.

[0135] The resulting spectrum generates up to five main peak regions. The first peak (Q0) corresponds to unreacted TAOS. The second set of peaks (Q1) corresponds to terminal groups. The next set of peaks (Q2) corresponds to linear groups. The next broad set of peaks (Q3) represents semi-dendritic units. The final broad set of peaks (Q4) represents dendritic units. When PAOS and PBOS are analyzed, each group falls within a defined ppm range. Typical ranges are shown in the table below.

[0136] [Table 1]

[0137] Polymethoxysilanes have different chemical shifts for Q0 and Q1, overlapping signals for Q2, and remain unchanged for Q3 and Q4, as shown in the table below:

[0138] [Table 2]

[0139] The ppm ranges shown in the table above do not necessarily apply to all monomers. However, other monomers may cause different chemical shifts, but the proper assignment of Q0 to Q4 should not be affected.

[0140] Using MestReNova, we can integrate each peak group and calculate the degree of branching using the following formula:

[0141]

number

[0142] Method for determining molecular weight and polydispersity index The molecular weight (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.

[0143] Sample preparation The sample is weighed and then diluted to a target concentration of 10 mg / mL with the solvent used in the instrument system. For example, 50 mg of polyalkoxysilane is weighed into a 5 mL volumetric flask, dissolved, and diluted to the desired volume with toluene. After the sample is dissolved in the solvent, it is passed through a 0.45 μm nylon filter and loaded into the instrument's automatic sampler.

[0144] Sample analysis An HPLC system using an automated sampler (e.g., Waters 2695 HPLC separation module, Waters Corporation, Milford, Massachusetts) connected to a refractive index detector (e.g., Wyatt 2414 refractive index detector, or equivalent) is used for polymer analysis. Separation is performed using three columns, each with an inner diameter of 7.8 mm and a length of 300 mm, packed with 5 μm of polystyrene-divinylbenzene medium, and cutoffs at molecular weights of 1, 10, and 60 kDA, respectively. Preferred columns are TSKGel G1000HHR, G2000HHR, and G3000HHR columns (available from TOSOH Bioscience, King of Prussia, Pennsylvania) or equivalents. The analytical column is protected using a 6 mm inner diameter x 40 mm length, 5 μm polystyrene-divinylbenzene guard column (e.g., TSKgel Guardcolumn HHR-L (TOSOH Bioscience), or equivalent). Toluene (HPLC grade or equivalent) is pumped at a uniform rate of 1.0 mL / min while both the column and detector are maintained at 25°C. 100 μL of the prepared sample is injected for analysis. Sample data is stored and processed using software with GPC computing capabilities (e.g., ASTRA Version 6.1.7.17 software or equivalent, available from Wyatt Technologies (Santa Barbara, California)).

[0145] The system is calibrated using a cubic fit to an Mp-versus-residence time curve, using more than 10 narrowly dispersed polystyrene standards (e.g., Standard ReadyCal Set (e.g., Sigma-Aldrich, PN76552, or equivalent)) with known molecular weights in the range of approximately 0.250–70 kDa.

[0146] The system software is used to calculate and report the weight-average molecular weight (Mw) and polydispersity index (Mw / Mn).

[0147] Method for calculating the organic content in the first shell component As used herein, definition of the organic portion in the inorganic shell of the capsules according to the present disclosure: Any portion X that cannot be cleaved from the metal precursor carrying the metal M under specified reaction conditions via hydrolysis of the M-X bond (where M belongs to the group of metals and metalloids, X belongs to the group of non-metals, and this portion is linked to the inorganic precursor of the metal or metalloid M) is considered an organic portion. It is set as the above reaction condition that it has a hydrolysis degree of at least 1% when exposed to distilled water having a neutral pH without stirring for 24 hours.

[0148] This method makes it possible to calculate the theoretical organic content assuming complete conversion of all hydrolyzable groups. Therefore, it becomes possible to evaluate the theoretical proportion of the organic component for any mixture of silanes, and the result indicates only the organic component content of this precursor mixture itself, not the actual organic content in the first shell component. Thus, if a specific proportion for the organic content of the first shell component is disclosed anywhere in this document, that proportion should be understood as being for any mixture of unhydrolyzed or pre-polymerized precursors that gives a theoretical organic content smaller than the disclosed number according to the following calculation.

[0149] Examples of silanes (however, not limited thereto. Refer to the general formula at the end of this item): Each molar fraction Y i Consider a mixture of silanes having. Here, i is the identification number of each silane. This mixture can be represented as follows. Si(XR) 4-n R n where XR is a hydrolyzable group under the conditions described in the above definition, and R i ni is non-hydrolyzable under the above conditions, and n i = 0, 1, 2, or 3. <A <0A

[0150] Such a mixture of silanes yields a shell having the following general formula:

[0151]

number

[0152] Next, the weight percentage of the organic portion, as defined earlier, can be calculated as follows. 1) Find the mole fraction of each precursor (containing nanoparticles). 2) Determine the general formula for each precursor (including nanoparticles). 3) Based on the mole fraction, calculate the general formula for the mixture of the precursor and nanoparticles. 4) Convert to the reacted silane (convert all hydrolyzable groups to oxygen groups). 5) Calculate the weight ratio of the organic portion to the total mass (assuming 1 mole of Si relative to the framework).

[0153] Examples:

[0154] [Table 3]

[0155] To calculate the general formula for a mixture, the exponents of each atom in the individual formula are multiplied by their respective mole fractions. Then, in the case of a mixture, where similar exponents arise, the sum of the fractional exponents is adopted (typically for ethoxy groups).

[0156] Note: The sum of all Si fractions is always 1 in the general formula for the mixture, according to the calculation method (the sum of the total mole fractions of Si is 1).

[0157]

number

[0158] To convert the unreacted formula to the post-reaction formula, simply divide the exponent of all hydrolyzable groups by 2, then sum them together (along with any existing oxygen groups if applicable) to obtain the fully reacted silane. SiO 1.88 Me 0.20

[0159] In this case, the expected result is that since the sum of all exponents must follow the following formula, for SiO 1.9 Me 0.2 it is: A + B / 2 = 2, (where A is the exponent of the oxygen atom and B is the sum of all non-hydrolyzable exponents.) Small errors occur from taking approximate numbers during calculation, but they should be corrected. Then, readjust the exponent of the oxygen atom to satisfy this formula.

[0160] Thus, the final formula is SiO 1.9 Me 0.2 and the weight ratio of the organic component is calculated as follows: Weight ratio = (0.20 * × 15) / (28 + 1.9 * × 16 + 0.20 * × 15) = 4.9%

[0161] General case: The above formula can be generalized by considering the valence of the metal or metalloid M, and thus the following modified formula can be obtained: M(XR) V-ni R i ni The same method is used, but the valence V of each metal is considered.

[0162] <0The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise indicated, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm." [Examples]

[0163] In accordance with the test methods described herein, the effect of the presence or absence of a polyvinyl alcohol water-soluble film on the wet fabric fragrance headspace performance (nmol / L) of cotton and polyester fabrics was evaluated for liquid laundry detergent compositions suitable for use in water-soluble unit-dose articles, which contain silica shell-based fragrance capsules according to the present invention. This effect was compared with that of a liquid laundry detergent composition containing polyacrylate shell-based fragrance capsules, which are outside the scope of the present invention, in a single variable manner.

[0164] Starting materials: Liquid detergent composition Liquid detergent compositions having the formulations provided in Table 1 were prepared on a laboratory scale by typically mixing the individual starting materials at room temperature under a batch process. Example 1 of the present invention includes silica shell-based fragrance capsules according to the present invention, while Comparative Example 1 includes polyacrylate shell-based fragrance capsules outside the scope of the present invention.

[0165] [Table 4] (1) Lutensit Z96: A zwitterionic ethoxylated quaternary sulfated hexamethylenediamine manufactured by BASF. (2) Details: See the section on fragrance capsules below. (3) As encapsulated fragrance %.

[0166] Fragrance capsules The two types of fragrance capsules added to each liquid detergent composition in Table 1 were synthesized according to the following synthesis route.

[0167] Silica shell-based fragrance capsules The oil phase is prepared by mixing and homogenizing (or dissolving, if all compounds are miscible) the non-hydrolyzable precursor with the fragrance composition (2 parts fragrance composition to 1 part non-hydrolyzable precursor). The aqueous phase is prepared by adding 1.25 wt% Aerosil 300 (available from Evonik) to a 0.1 M aqueous HCl solution and dispersing it in an ultrasonic bath for at least 30 minutes. After each phase is prepared separately, they are combined (1 part oil phase to 4 parts water), and the oil phase is dispersed into the aqueous phase at 13400 RPM / min using an IKA ultraturrax S25N-10G mixing tool. Once the emulsification process is complete, the resulting emulsion is cured at the following temperature profiles: 22°C for 4 hours, 50°C for 16 hours, and 70°C for 96 hours. To deposit the second shell component, the capsules are subjected to post-treatment with a solution of the second shell component: the slurry is diluted 2-fold with 0.1 M HCl and treated with controlled addition of a 10 wt% sodium silicate aqueous solution (40 μl per minute, 0.16 ml per g of slurry) using a suspension magnetic stirring reactor at 22°C and 250 RPM. The pH is kept constant at pH 7 using 1 M HCl (aqueous solution). After the injection of the second shell component solution is complete, the capsules are centrifuged at 2500 RPM for 10 minutes to redisperse them in deionized water. The resulting capsules contain the silica-based first shell component and the second shell component according to this disclosure, have an average size of 29.22 μm, and a CoV of 38%.

[0168] Synthesis of non-hydrolyzable precursors 1000 g of tetraethoxysilane (TEOS, available from Sigma Aldrich) is added to a clean, dry round-bottom flask equipped with a stirring rod and distillation apparatus under a nitrogen atmosphere. 490 ml of acetic anhydride (available from Sigma Aldrich) and 5.8 g of tetrakis(trimethylsiloxy)titanium (available from Gelest) are added, and the contents of the flask are stirred at 135°C for 28 hours. During this time, ethyl acetate produced by the reaction of the ethoxysilane group with acetic anhydride is removed by distillation. The reaction flask is cooled to room temperature and placed on a rotary evaporator (Rotovapor R110, Buchi), and this rotary evaporator is used with a water bath and a vacuum pump (Welch 1402 DuoSeal) to remove all remaining solvent and volatile compounds. The resulting polyethoxysilane (PEOS) is a yellow, viscous liquid with the following specifications as shown in Table 2. The ratio of TEOS to acetic anhydride can be varied to control the parameters shown in Table 2.

[0169] [Table 5]

[0170] Polyacrylate shell fragrance capsules A group of fragrance capsules containing polyacrylate shells that encapsulate the same fragrance composition as the silica shell-based fragrance capsules described above was prepared according to encapsulations made according to the process disclosed in U.S. Patent Application Publication No. 2011 / 0268802.

[0171] Non-hydrolyzable PEOS synthesis: 1000 g of TEOS (available from Sigma Aldrich) was added to a clean, dry, round-bottom flask equipped with a stirring rod and distillation apparatus under a nitrogen atmosphere. Next, 564 g of acetic anhydride (available from Sigma Aldrich) and 5.9 g of tetrakis(trimethylsiloxide)titanium (Gelest, available from Sigma Aldrich) were added, and the contents of the flask were heated to 135°C while stirring. The reaction temperature was maintained at 135°C for 30 hours with vigorous stirring, during which time the organic ester produced by the reaction of the alkoxysilane group with acetic anhydride was removed by distillation along with any further organic esters produced by the condensation of the silyl acetate group with other alkoxysilane groups generated during the formation of polyethoxysilane (PEOS). The reaction flask was cooled to room temperature and placed on a rotary evaporator (Rotovapor R110, Buchi). This rotary evaporator, along with a water bath and a vacuum pump (Welch 1402 DuoSeal), was used to remove all remaining solvent. The degree of branching (DB), molecular weight (Mw), and polydispersity index (PDI) of the synthesized PEOS polymer were 0.42, 2.99, and 2.70, respectively.

[0172] Capsule synthesis: Five batches were prepared according to the following procedure, and after the curing process, the five batches were combined to obtain a combined slurry. The oil phase was prepared by mixing 3 g of the PEOS precursor synthesized above with 2 g of beneficial agents and / or core modifiers and homogenizing (or, if all compounds are miscible, dissolving them). 100 g of the aqueous phase was prepared by mixing 0.5 g of NaCl, 3.5 g of Evonik Aerosil 300 fumed silica, and 96 g of DI water. The fumed silica was dispersed in the aqueous phase at 20,000 RPM for 15 minutes using an IKA ultra-turrax (S25N).

[0173] After preparing each phase separately, 5g of the oil phase was dispersed in 16g of the aqueous phase at 25,000 RPM for 5 minutes using an IKA Ultra-Turrax mixer (S25N-10g) to reach the desired average oil droplet diameter. Next, 0.1M HCl was added dropwise to adjust the pH. of The ratio was set to 1. After the emulsification process was completed, the resulting emulsion was left to stand at room temperature for 4 hours without stirring, and then left to stand at 90°C for 16 hours until sufficient curing occurred so that the capsules would not collapse. After the curing process, the five batches were combined to obtain a combined capsule slurry.

[0174] To deposit the second shell component, the combined capsule slurry was post-treated with the second shell component solution. 50 g of the combined slurry was diluted with 50 g of 0.1 M HCl (aqueous solution). 1 M NaOH (aqueous solution) was added dropwise to adjust the pH to 7. Next, the diluted slurry was treated with controlled addition (40 μl per minute) of the second shell component precursor solution (20 ml of 15 wt% sodium silicate (aqueous solution)) using a suspension magnetic stirring reactor at 300 RPM at room temperature. The pH was kept constant at pH 7 by continuously injecting 1.6 M HCl (aqueous solution) and 1 M NaOH (aqueous solution). The capsules were then centrifuged every 10 minutes at 2500 RPM. The supernatant was discarded, and the capsules were redispersed in deionized water.

[0175] To test whether the capsules would disintegrate, the slurry was diluted 10-fold with deionized water. Droplets of the resulting dilution were added to a microscope microslide and dried overnight at room temperature. The following day, the dried capsules were observed under an optical microscope by light transmission to evaluate whether they maintained their spherical shape (no coverslides were used). The capsules withstood drying and did not disintegrate. The average volume-weighted diameter of the measured capsules was 5.3 μm, and the CoV was 46.2%. The organic content in the shell was 0%.

[0176] Polyvinyl alcohol film The polyvinyl alcohol used was the same polyvinyl alcohol homopolymer / anionic polyvinyl alcohol copolymer blend that was used in Ariel 3-in-1 Pods, which were commercially available in the UK in July 2020, as received from MonoSol.

[0177] Test method for headspace performance of fragrance on damp fabric: The compositions of the present invention and comparative examples shown in Table 1 were tested for wet fabric fragrance headspace performance both in the presence and absence of a polyvinyl alcohol-based film. Washed fabrics were analyzed by GC-MS at the wet stage to obtain the wet fabric headspace (WFHS) for each fragrance ingredient.

[0178] Preparation of fabric samples The method of processing the fabrics includes the use of a commercially available washing machine such as the Miele Honeycomb Care W1724, or a similar machine using standard machine settings (using water with a hardness of 2.5 mmol / L, 40°C, and a cotton short cycle for 1 hour and 14 minutes at 1200 RPM). The fabric composition in the washing machine consists of terry cotton and polyester test cloths, as well as a standard ballast load of a mixture of polycotton and cotton, totaling 3 kilograms. The water-soluble polyvinyl alcohol polymer and detergent treatment agent are delivered to the machine drum at the specified level, with and without the water-soluble polyvinyl alcohol film: 22.6 g of the detergent composition, and the water-soluble polyvinyl alcohol film (0.03 g) is administered as an empty 3-compartment unit dose article similar to the unit dose article design similar to that commercially available in the UK in July 2020, for example, as shown in Figure 1.

[0179] Headspace Analysis Immediately after the washing cycle, wet fabric tracers were subjected to fragrance headspace analysis. Six replicas of each type of tracer were analyzed by high-speed headspace GC / MS for each washing test. 4cm × 4cm aliquots of the fabric tracer were transferred to a 25mL headspace vial. The fabric samples were equilibrated at 65°C for 10 minutes. The headspace above the fabric was sampled for 5 minutes using the SPME (50 / 30μm DVB / Carboxen / PDMS) method. Subsequently, the SPME fibers were thermally desorbed online in the GC. The samples were analyzed in full scan mode on the high-speed GC / MS. The total headspace reaction (expressed in nmol / l) on the above specimens was determined by ion extraction of a specific mass of fragrance raw materials.

[0180] Test results: Table 3 summarizes the total fragrance headspace reaction to a wet terry cotton tracer, as well as the single variable headspace loss / gain effect of polyvinyl alcohol addition, for 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 reaction to a wet polyester fabric tracer, as well as the single variable headspace loss / gain effect of polyvinyl alcohol addition, for silica shell capsules according to the present invention and polyacrylate shell capsules outside the scope of the present invention.

[0181] The data clearly show a positive effect of the polyvinyl alcohol film's fragrance headspace on the terry cotton fabric tracer headspace when combined with silica shell capsules (+56% total headspace), but a negative effect of the polyvinyl alcohol film when combined with polyacrylate shell capsules (-16% total headspace). On the polyester fabric tracer, the neutral effect of the polyvinyl alcohol film is observed when combined with silica shell capsules (+1% total headspace), but the negative effect of the polyvinyl alcohol film is again observed when combined with polyacrylate shell capsules (-23% total headspace). As a final result, the silica-based fragrance capsules according to the present invention, when considering the wet-stage fragrance headspace, inherently perform worse than polyacrylate-based fragrance capsules due to the surprisingly opposite synergistic effect of the polyvinyl alcohol wet-stage fragrance headspace. However, when these fragrance capsules according to the present invention are incorporated into a water-soluble polyvinyl alcohol film containing a unit dose article, this inherent wet-stage fragrance headspace performance gap is significantly reduced (-27% vs. -61% for cotton, and -8% vs. -31% for polyester).

[0182] [Table 6]

[0183] [Table 7]

Claims

1. A water-soluble unit dose article comprising a water-soluble polyvinyl alcohol film and a laundry detergent composition, wherein the water-soluble film encloses the laundry detergent composition, the laundry detergent composition comprises a capsule, the capsule having a core and a shell, the shell surrounding the core, The core comprises a hydrophobic material, and the hydrophobic material comprises at least one fragrance ingredient. The shell comprises 90% to 100% by weight of an inorganic material, and the inorganic material is SiO ２ It is a water-soluble unit dose product.

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

3. The aforementioned capsule is as follows: (a) Average volume-weighted capsule diameter of 10 μm to 200 μm; (b) Average shell thickness of 170 nm to 1000 nm; (c) Volume core / shell ratio of approximately 50:50 to 99:1; (d) The first shell component contains an organic content of 5% by weight or less relative to the weight of the first shell component; or (e) These mixtures, A water-soluble unit-dose article according to claim 1 or 2, characterized by one or more of the following.

4. The precursor comprises at least one compound selected from the group consisting of formula (I), formula (II), or mixtures thereof. Equation (I) is (M ｖ O ｚ Y ｎ ) ｗ and Formula (II) is (M ｖ O ｚ Y ｎ R １ ｐ ), ｗ where For formula (I), formula (II), or mixtures thereof: Each M is silicon, v is the valence of M, and is either 3 or 4. z is between 0.5 and 1.

6. Each Y is -OH, -OR ２ ,halogen, 【Chemistry 1】 -NH ２ , - NHR ２ , -N(R ２ ) ２ , and 【Chemistry 2】 Selected independently from, R ２ C １ ~C ２０ Alkyl, C １ ~C ２０ Alkylene, C ６ ~C ２２ A 5-12 membered heteroaryl containing an aryl or 1-3 ring heteroatoms selected from O, N, and S, R ３ H, C １ ~C ２０ Alkyl, C １ ~C ２０ Alkylene, C ６ ~C ２２ A 5-12 membered heteroaryl containing an aryl or 1-3 ring heteroatoms selected from O, N, and S, w is between 2 and 2000. For equation (I), n is between 0.7 and (v-1), For equation (II), n is between 0 and (v-1), Each R １ C １ ~C ３０ Alkyl; C １ ~C ３０ Alkylene; halogen, -OCF ３ , -NO ２ -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -CO ２ C substituted with a member selected from the group consisting of H, -C(O)-alkyl, -C(O)O-aryl, and -C(O)O-heteroaryl. １ ~C ３０ Alkyl; and halogen, -OCF ３ , -NO ２ C substituted with a member selected from the group consisting of -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. １ ~C ３０ Independently selected from the group consisting of alkylenes, p is a number greater than 0 and up to pmax. pmax=60 / [9 ＊ Mw(R １ ) + 8], Mw(R １ ) is R １ The water-soluble unit dose article according to claim 2, wherein the molecular weight of the group is...

5. The aforementioned precursor, a. comprising at least one compound according to formula (I); or b. The water-soluble unit-dose article according to claim 4, comprising at least one compound according to formula (II).

6. One or both of the compounds of formula (I) and formula (II) are: (a) Weight-average molecular weight (Mw) on a polystyrene basis as defined herein, ranging from approximately 700 Da to approximately 30,000 Da; (b) branching degrees as defined herein, 0.2 to 0.6; (c) Molecular weight polydispersity index as defined herein in 1 to 20; or (d) These mixtures, A water-soluble unit-dose article according to claim 4 or 5, characterized by one or more of the following.

7. A water-soluble unit dose article according to any one of claims 4 to 6, wherein Y is OR and R is selected from a methyl group, an ethyl group, a propyl group, or a butyl group, for formula (I), formula (II), or both thereof.

8. The water-soluble unit-dose article according to any one of claims 2 to 7, wherein the inorganic nanoparticles of the first shell component include at least one of metal nanoparticles, mineral nanoparticles, metal oxide nanoparticles, or metalloid oxide nanoparticles, or a mixture thereof.

9. The inorganic second shell component is SiO ２ The water-soluble unit dose article according to any one of claims 2 to 7.

10. The water-soluble unit dose article according to any one of claims 1 to 9, wherein the laundry detergent composition contains the capsule in an amount of 0.05% to 20% by weight of the laundry detergent composition.

11. The water-soluble unit dose article according to any one of claims 1 to 10, wherein the laundry detergent composition is a liquid laundry detergent composition comprising 1% to 20% by weight of water in the liquid laundry detergent composition.

12. The water-soluble unit-dose article according to any one of claims 1 to 11, wherein the laundry detergent composition comprises a non-encapsulated fragrance.

13. The water-soluble unit dose article according to any one of claims 1 to 12, wherein the water-soluble film comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer.

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