Liquid fabric care composition comprising capsules

Abstract

The present disclosure provides liquid fabric care compositions comprising certain fabric treatment adjuncts and / or water, wherein the compositions further comprise a capsule characterized by a substantially inorganic shell, such as a silica-based shell. The present disclosure also relates to methods of making and using such compositions.

Description

Technical Field

[0001] The present disclosure relates to liquid fabric care compositions comprising certain fabric treatment aids and / or water and further comprising capsules characterized by a substantially inorganic shell, such as a silica-based shell. The present disclosure also relates to methods of making and using such compositions. Background Art

[0002] Many liquid fabric care products are formulated with fragranced core / shell capsules. Typically, the core of these capsules contains the fragrance, and the shell typically comprises a polymeric material such as an aminoplast, polyurea, or polyacrylate. These capsules can be used to deliver the benefit agent to a target surface, such as a fabric. The capsule then ruptures at various touch points, releasing the fragrance. However, fragrance capsules are known to leak into the liquid environment of a consumer product, reducing the efficiency of the fragrance delivery system.

[0003] Furthermore, fragrance capsules often encapsulate multiple fragrance raw materials ("PRMs"). The problem is that different PRMs can leak through the capsule wall at different rates. Over time, such as when the product is shipped or stored, the fragrance's characteristics can change because some PRMs leak more than others. This can lead to an olfactory experience that's less satisfying than the manufacturer's formulation, quality control issues, and even consumer dissatisfaction when the freshness profile provided by the first dose of the product differs from the freshness profile provided by the last dose.

[0004] There is a need for liquid fabric care products comprising perfume delivery systems having improved perfume leakage characteristics. Summary of the Invention

[0005] The present disclosure relates to liquid fabric care compositions comprising a population of capsules having a substantially inorganic shell.

[0006] For example, the present disclosure is directed to a liquid fabric care composition comprising a fabric treatment adjunct, wherein the fabric treatment adjunct is selected from a conditioning active, a surfactant, or a mixture thereof, wherein the conditioning active, if present, is selected from an alkyl quaternary ammonium compound ("alkyl quat"), an alkyl ester quat ("alkylester quat"), or a mixture thereof, and wherein the surfactant, if present, is selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant, an amphoteric surfactant, an ampholytic surfactant, or a mixture thereof; and a population of capsules comprising a core and a shell surrounding the core, wherein the core comprises a perfume raw material, wherein the shell comprises (a) a substantially inorganic first shell component comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer, and (b) an inorganic second shell component surrounding the first shell component, wherein the second shell component surrounds the nanoparticle layer.

[0007] The present disclosure also relates to a liquid fabric care composition comprising from about 5% to about 99.5% water, by weight of the composition, and a population of capsules comprising a core and a shell surrounding the core, wherein the core comprises a perfume raw material, wherein the shell comprises (a) a substantially inorganic first shell component comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer, and (b) an inorganic second shell component surrounding the first shell component, wherein the second shell component surrounds the nanoparticle layer.

[0008] The present disclosure also relates to a method for treating a surface, preferably a fabric, wherein the method comprises the step of contacting the surface with a liquid fabric care composition as described herein, optionally in the presence of water.

[0009] The present disclosure also relates to a method for treating a surface, wherein the method comprises providing a liquid base composition comprising a fabric treatment aid and / or water, wherein the fabric treatment aid is selected from a conditioning active, a surfactant or a mixture thereof, and providing a population of capsules to the base composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The drawings herein are illustrative in nature and are not intended to be limiting.

[0011] Figure 1A schematic diagram of a method for preparing a capsule having a first shell component, the capsule being prepared with a hydrophobic core is shown.

[0012] Figure 2 A schematic diagram of a capsule having a first shell part and a second shell part is shown.

[0013] Figure 3 Scanning electron microscope image of the capsule.

[0014] Figure 4 This is a graph showing the leakage results of Example 4.

[0015] Figure 5 This is a graph showing the leakage results of Example 10. DETAILED DESCRIPTION

[0016] The present disclosure relates to liquid fabric care compositions comprising certain fabric treatment actives (e.g., conditioning actives and / or surfactants) and a population of certain capsules. The capsules contain a fragrance raw material. In addition, the capsule shells contain an inorganic material selected to result in improved mechanical properties and low and / or consistent permeability.

[0017] For example, it has been found that the capsules of the present disclosure work surprisingly well in controlling the leakage of fragrance raw materials in the compositions of the present disclosure, resulting in relatively low and consistent fragrance leakage. Without wishing to be bound by theory, it is believed that a completely different mechanism drives the leakage of fragrance raw materials for shells containing highly cross-linked inorganic materials compared to shells containing organic polymer materials. Specifically, the diffusion of small molecules such as fragrance raw materials ("PRMs") through homogeneous organic polymer shells is similar to the diffusion mechanism through homogeneous polymer membranes. In this case, the permeability of the polymer membrane to a given solute depends on the polymer free volume (affected by crystallinity and crosslink density) and the relative solubility of the solute to the polymer. Since different PRMs will have different ranges of relevant physical and chemical properties (e.g., molecular weight and polarity), when the physical and chemical properties are also uniform, the diffusion rate for a given group of PRMs will be non-uniform.

[0018] On the other hand, it is believed that the diffusion of small molecules through a highly cross-linked inorganic shell occurs primarily through microchannels formed by the percolation network of micropores present in the shell. As disclosed in the present disclosure, such a highly cross-linked inorganic shell can be obtained by using a second shell component in combination with the first shell component. In this case, it is believed that the permeability of the inorganic shell depends primarily on the number, density, and size of the microchannels that effectively connect the core and the continuous phase, which can result in relatively uniform or consistent, and relatively low, PRM leakage rates.

[0019] Because the various PRMs leak from the disclosed capsules in the disclosed compositions at relatively consistent rates, it is further believed that the desired characteristics of the fragrance are maintained, resulting in a more pleasing and consistent olfactory performance.

[0020] The components, compositions, and related methods are described in more detail below.

[0021] As used herein, the articles "a" and "an," when used in a claim, are understood to refer to one or more of the things protected or described in the claim. As used herein, the terms "comprising," "including," and "containing" are intended to be non-limiting. The compositions of the present disclosure may comprise, consist essentially of, or consist of the components of the present disclosure.

[0022] The term "substantially free of" or "substantially free from" may be used herein. This means that the referenced material is very small and not intentionally added to the composition to form part of the composition, or preferably, the referenced material is not present at analytically detectable levels. This includes compositions in which the referenced material is present only as an impurity in one of the other materials intentionally added. If present at all, the referenced material may be present at a level of less than 1%, or less than 0.1%, or less than 0.01%, or even 0% by weight of the composition.

[0023] As used herein, the phrase "fabric care composition" includes compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry pre-wash agents, laundry pre-treaters, laundry additives, spray-on products, dry cleaning agents or compositions, laundry rinse additives, washing additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents on or included in porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art based on the teachings herein. Such compositions can be used as laundry pre-treaters, laundry post-treaters, or can be added during the rinse cycle or wash cycle of a laundry operation.

[0024] Unless otherwise indicated, all component or composition levels are in reference to the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

[0025] Unless otherwise indicated, all temperatures herein are in degrees Celsius (° C.) Unless otherwise indicated, all measurements herein are made at 20° C. and atmospheric pressure.

[0026] In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specifically stated. All ratios are by weight unless otherwise specifically stated.

[0027] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range falling within such wider numerical range, as if such narrower numerical ranges were all expressly written herein.

[0028] Liquid fabric care compositions

[0029] The present disclosure relates to liquid fabric care compositions.The liquid fabric care composition can be a liquid fabric enhancer, a liquid detergent (eg, a heavy-duty liquid detergent), a sprayable fabric refresher composition, or a combination thereof.

[0030] The composition may comprise a fabric treatment aid and a population of capsules. The capsules contain fragrance and can provide fragrance / freshness benefits at various contact points. The fabric treatment aid can provide benefits to the target fabric, such as conditioning or cleaning benefits. For example, suitable fabric treatment aids may include conditioning actives such as ester quaternary ammonium compounds, and / or surfactants such as anionic or nonionic surfactants.

[0031] The composition may comprise water. The composition may be substantially aqueous. The composition may comprise at least 5% by weight water, preferably at least 25% by weight, preferably at least 50% by weight water, preferably at least 75% by weight, or even greater than 85% by weight water. The composition may comprise from about 5% to about 99.5%, or from about 50% to about 99.5%, preferably from about 50% to about 99.5%, more preferably from about 60% to about 95%, even more preferably from about 75% to about 90% water, based on the weight of the composition.

[0032] The liquid fabric care composition may be packaged in a pourable bottle, and in such case, the composition may preferably comprise from about 50% to about 99%, or from about 60% to about 95%, or from about 70% to about 90%, by weight of the composition, of water. As described in more detail below, the liquid fabric care composition may be packaged in a sprayable bottle, and in such case, it may be preferred that the composition comprise from about 75% to about 99.5%, preferably from about 80% to about 99%, or from about 90% to about 99%, or from about 95% to about 99%, by weight of the composition, of water.

[0033] The liquid fabric care composition may be in the form of a sprayable product. For example, the liquid fabric composition may be contained in a spray dispenser, which may include (a) a bottle for containing the liquid composition and (b) a spray engine.

[0034] The bottle may be configured as a container having a bottom and a sidewall terminating in an opening. The bottle may comprise a bag-in-bag or bag-in-can container.

[0035] The spray engine can be constructed in various ways, such as a direct compression trigger sprayer, a pre-compression trigger sprayer, or an aerosol spray dispenser. One suitable spray dispenser is the TS800 trigger sprayer (Exxon Mobil PP1063, material classification 10003913, manufacturer: Calmar). Another suitable spray engine includes a continuous action sprayer, such as the FLAIROSOL from Afa Dispensing Group. TM Dispenser. FLAIROSOL TM The dispenser includes a pre-compression spray engine and aerosol pressurization of the aqueous composition through the use of a pressure chamber or a buffer chamber. Suitable trigger sprayers or finger pump sprayers are readily available from suppliers such as Calmar, Inc., City of Industry, Calif.; CSI (Continental Sprayers, Inc.), St. Peters, Mo.; Berry Plastics Corp., Evansville, Ind. ( Distributor of sprayers); or Seaquest Dispensing, Cary, Ill (cylindrical Euromist If the spray dispenser is configured as an aerosol, the spray dispenser may be pressurized with a propellant. Any suitable propellant may be used.

[0036] The composition can be in the form of a combined dose article such as a pouch. Such pouches typically include a water-soluble film that at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition can be encapsulated in a single compartment pouch or a multi-compartment pouch. The multi-compartment pouch can have at least two, at least three, or at least four compartments. The multi-compartment pouch can include compartments arranged side by side and / or stacked. The composition contained in the pouch or its compartments can be a liquid, a solid (such as a powder), or a combination thereof. The bagged composition can have a relatively small amount of water, for example, less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water by weight of the detergent composition.

[0037] The composition may have a -1and a viscosity of 1 centipoise to 1500 centipoise (1 mPa*s to 1500 mPa*s), 100 centipoise to 1000 centipoise (100 mPa*s to 1000 mPa*s), or 200 centipoise to 500 centipoise (200 mPa*s to 500 mPa*s) at 21°C.

[0038] The compositions of the present disclosure may be characterized by a pH of from about 2 to about 12, or from about 2 to about 8.5, or from about 2 to about 7, or from about 2 to about 5. The compositions of the present disclosure may have a pH of from about 2 to about 4, preferably from about 2 to about 3.7, more preferably from about 2 to about 3.5, preferably in the form of an aqueous liquid. It is believed that such pH levels are beneficial to the stability of quaternary ammonium compounds, particularly quaternary ammonium ester compounds. The pH of the composition is determined by dissolving / dispersing the composition in deionized water at about 20° C. to form a 10% concentration solution.

[0039] Fabric treatment auxiliaries

[0040] The liquid fabric care compositions of the present disclosure may include a fabric treatment aid. The fabric treatment aid may be selected to provide a beneficial effect to the target fabric, such as a conditioning or cleaning benefit. For example, suitable fabric treatment aids may include conditioning actives such as ester quaternary ammonium compounds, and / or surfactants such as anionic or nonionic surfactants. Additionally or alternatively, the fabric treatment aid may be selected to provide processing and / or stability benefits to the fabric care composition. These materials are described in more detail below.

[0041] a. Conditioning active substances

[0042] The liquid fabric care compositions of the present disclosure may contain conditioning actives. These materials can provide conditioning or softening benefits to the target surface and are particularly useful when the composition is in the form of a fabric enhancer composition.

[0043] When present, the conditioning active is selected from the group consisting of alkyl quaternary ammonium compounds, alkyl ester quaternary ammonium compounds and mixtures thereof.For environmental / biodegradability reasons it may be preferred that the conditioning active comprises an alkyl ester quaternary ammonium compound.

[0044] Conditioning actives may be present at a level of from about 0.1% to about 50%, or from about 2% to about 40%, or from about 3% to about 25%, preferably from 4% to 18%, more preferably from 5% to 15%, by weight of the composition. Conditioning actives may be present at a level greater than 0% to about 50%, or from about 1% to about 35%, or from about 1% to about 25%, or from about 3% to about 20%, or from about 4.0% to 18%, more preferably from 4.5% to 15%, even more preferably from 5.0% to 12%, by weight of the composition. Conditioning actives may be present at a level of from about 1% to about 8%, or from about 1.5% to about 5%, by weight of the composition. The level of conditioning actives may depend on the desired concentration of the total conditioning active in the composition (diluted or concentrated composition) and the presence or absence of other conditioning / softening materials. At very high levels of conditioning actives, viscosity may no longer be adequately controlled, which makes the product unsuitable for use. However, if the level of conditioning actives is too low, the benefits delivered may be suboptimal.

[0045] Conditioning actives can be derived from fatty acids (sometimes referred to as parent fatty acids). The fatty acids can include saturated fatty acids and / or unsaturated fatty acids. The fatty acids can be characterized by an iodine value (see methods). Preferably, the iodine value of the fatty acids forming the quaternary ammonium fabric compound is from 0 to 140, or from 0 to about 90, or from about 10 to about 70, or from about 15 to about 50, or from about 18 to about 30. The iodine value can be from about 25 to 50, preferably from 30 to 48, more preferably from 32 to 45. Without being bound by theory, when the fatty acid from which the quaternary ammonium compound is formed is at least partially unsaturated, a lower melting point is obtained that makes the FCA easier to process. In particular, it is believed that diunsaturated fatty acids enable easy processing of FCA.

[0046] The fatty acids may include alkyl moieties containing an average weight of from about 13 to about 22 carbon atoms, or from about 14 to about 20 carbon atoms, preferably from about 16 to about 18 carbon atoms.

[0047] Suitable fatty acids may include those derived from: (1) animal fats, and / or partially hydrogenated animal fats, such as tallow, lard, etc.; (2) vegetable oils, and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, sesame oil, rapeseed oil, cottonseed oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, palm kernel oil, coconut oil, other tropical palm oils, linseed oil, tung oil, etc.; (3) processed oils and / or polymerized oils, such as linseed oil or tung oil that have been treated with heat, pressure, alkali isomerization, and catalysis; (4) mixtures thereof to produce saturated (e.g., stearic acid), unsaturated (e.g., oleic acid), polyunsaturated (linoleic acid), branched (e.g., isostearic acid), or cyclic (e.g., saturated or unsaturated α-disubstituted cyclopentyl or cyclohexyl derivatives of the polyunsaturated acids) fatty acids.

[0048] Conditioning actives may include compounds formed from unsaturated fatty acids. The fatty acids may comprise an unsaturated C18 chain, which may contain a single double bond ("C18:1") or may be diunsaturated ("C18:2").

[0049] The conditioning active can be derived from a fatty acid and optionally triethanolamine, preferably an unsaturated fatty acid containing eighteen carbons ("C18 fatty acid"), more preferably a C18 fatty acid containing a single double bond ("C18:1 fatty acid"). The conditioning active can comprise from about 10% to about 40%, or from about 10% to about 30%, or from about 15% to about 30%, by weight of the conditioning active, of a compound derived from triethanolamine and a C18:1 fatty acid. Such levels of fatty acids can facilitate handling of the resulting esterquat material.

[0050] The fatty acids forming the conditioning active may comprise from 1.0% to 20.0%, preferably from 1.5% to 18.0%, or from 3.0% to 15.0%, more preferably from 4.0% to 15.0% of diunsaturated C18 chains ("C18:2") by weight of the total fatty acid chains. From about 2% to about 10%, or from about 2% to about 8%, or from about 2% to about 6% by weight of the total fatty acids used to form the conditioning active may be C18:2 fatty acids.

[0051] On the other hand, very high levels of unsaturated fatty acid chains should be avoided in order to minimize malodor development due to oxidation of the fabric softener composition over time.

[0052] Suitable conditioning active alkyl ester quats are selected from the group consisting of monoester quat materials ("monoester quats"), diester quat materials ("diester quats"), triester quat materials ("triester quats"), and mixtures thereof. Based on the weight of the total conditioning active, the level of monoester quats may be from 2.0% to 40.0%, the level of diester quats may be from 40.0% to 98.0%, and the level of triester quats may be from 0.0% to 30.0%. Based on the weight of the total conditioning active, the level of monoester quats may be from 2.0% to 40.0%, the level of diester quats may be from 40.0% to 98.0%, and the level of triester quats may be less than 5.0%, or less than 1.0%, or even 0.0%. Based on the weight of the total conditioning active, the level of monoester quats may be from 15.0% to 35.0%, the level of diester quats may be from 40.0% to 60.0%, and the level of triester quats may be from 15% to 38.0%. The quaternary ammonium ester compound may comprise a triester quat material ("triester quat").

[0053] Suitable alkyl ester quaternary ammonium compounds can be derived from alkanolamines, such as C1-C4 alkanolamines, preferably C2 alkanolamines (e.g., ethanolamine). The alkyl ester quaternary ammonium compounds can be derived from monoalkanolamines, dialkanolamines, trialkanolamines, or mixtures thereof, preferably monoethanolamine, diethanolamine, diisopropanolamine, triethanolamine, or mixtures thereof. The alkyl ester quaternary ammonium compounds can be derived from diethanolamine. The alkyl ester quaternary ammonium compounds can be derived from diisopropanolamine. The alkyl ester quaternary ammonium compounds can be derived from triethanolamine. The alkanolamine from which the alkyl ester quaternary ammonium compounds are derived can be an alkylated monoalkanolamine or dialkanolamine, such as a C1-C4 alkylated alkanolamine, preferably a C1 alkylated alkanolamine (e.g., N-methyldiethanolamine).

[0054] The conditioning active may comprise an at least partially substituted quaternized nitrogen atom. The quaternized nitrogen atom may be at least partially substituted with one or more C1-C3 alkyl or C1-C3 hydroxyalkyl groups. The quaternized nitrogen atom may be at least partially substituted with a moiety selected from the group consisting of methyl, ethyl, propyl, hydroxyethyl, 2-hydroxypropyl, 1-methyl-2-hydroxyethyl, poly(C2-C3-alkoxy), polyethoxy, benzyl, more preferably methyl or hydroxyethyl.

[0055] The conditioning active may comprise a compound according to formula (1):

[0056] {R 2 (4-m) -N+-[XYR 1 ] m}A - Formula (1)

[0057] in:

[0058] m is 1, 2, or 3, provided that in a given molecule, the value of each m is the same;

[0059] Each R may contain from 13 to 22 carbon atoms 1 are independently straight chain or branched chain hydrocarbon groups, preferably R 1 is a straight chain, more preferably R 1 is a partially unsaturated straight alkyl chain;

[0060] Each R 2 is independently a C1-C3 alkyl or hydroxyalkyl group, and / or each R 2 Selected from methyl, ethyl, propyl, hydroxyethyl, 2-hydroxypropyl, 1-methyl-2-hydroxyethyl, poly(C2-C3-alkoxy), polyethoxy, benzyl, more preferably methyl or hydroxyethyl;

[0061] Each X is independently -(CH2)n-, -CH2-CH(CH3)- or -CH(CH3)-CH2-, wherein each n is independently 1, 2, 3 or 4, preferably each n is 2;

[0062] each Y is independently -O-(O)C- or -C(O)-O-; and

[0063] A- is independently selected from the group consisting of chloride, bromide, methylsulfate, ethylsulfate, sulfate and nitrate, preferably A- is selected from the group consisting of chloride and methylsulfate, more preferably A- is methylsulfate.

[0064] At least one X, preferably each X, may be independently selected from -CH2-CH(CH3)- or -CH(CH3)-CH2-. When m is 2, X may be selected from *-CH2-CH(CH3)-, *-CH(CH3)-CH2-, or a mixture thereof, wherein * indicates the end closest to the nitrogen of the alkyl ester quat. When two or more X groups are present in a single compound, at least two of the X groups may be different from each other. For example, when m is 2, one X (e.g., the first X) may be *-CH2-CH(CH3)-, and another X (e.g., the second X) may be *-CH(CH3)-CH2-, wherein * indicates the end closest to the nitrogen of the alkyl ester quat. It has been found that such selection of the m index and the X groups can improve the hydrolytic stability of the alkyl ester quat, and thus further improve the stability of the composition.

[0065] For similar stability reasons, conditioning actives may include a mixture of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester; (2-hydroxypropyl)-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid ester; and bis-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid ester; wherein the fatty acid esters are derived from a mixture of C12-C18 fatty acids. Conditioning actives may include any of the fatty acid esters listed in this paragraph, either individually or as a mixture.

[0066] Each X may be -(CH2)n-, wherein each n is independently 1, 2, 3 or 4, preferably each n is 2.

[0067] Each R 1 The groups may correspond to and / or be derived from the alkyl portion of any of the parent fatty acids provided above. 1 The group may contain from about 13 to about 22 carbon atoms or from about 14 to about 20 carbon atoms, preferably from about 16 to about 18 carbon atoms. It is possible that when Y is *-O-(O)C- (where * indicates the end closest to the X moiety), each R 1The sum of carbon atoms in the is 13 to 21, preferably 13 to 19.

[0068] Conditioning actives of the present disclosure may include mixtures of quaternary ammonium compounds according to formula (1), for example, having some compounds where m = 1 (e.g., monoesters) and some compounds where m = 2 (e.g., diesters). Some mixtures may even contain compounds where m = 3 (e.g., triesters). Quaternary ammonium compounds may include compounds according to formula (1) where m is 1 or 2, but not 3 (e.g., substantially free of triesters).

[0069] The conditioning actives of the present disclosure may include compounds according to formula (1), wherein each R 2 The conditioning actives of the present disclosure may include compounds according to formula (1) wherein at least one R 2 , preferably wherein at least one R 2 is a hydroxyethyl group and at least one R 2 For compounds according to formula (1), m may be equal to 1, and only one R 2 It may be a hydroxyethyl group.

[0070] The conditioning actives of the present disclosure may include methylsulfate as a counterion. When the conditioning actives of the present disclosure include a compound according to formula (1), A- may preferably be methylsulfate. Without wishing to be bound by theory, it is believed that esterquats having methylsulfate as a counterion have lower electrostatic repulsion than esterquats having chloride ions because the methylsulfate counterion is more tightly bound than the chloride ion, which may result in more efficient deposition on a target surface such as a fabric.

[0071] The conditioning actives of the present disclosure may include one or more members selected from the group consisting of:

[0072] (A) bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester and isomers of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester and / or mixtures thereof; N,N-bis-(2-

[0073] (Acyl-oxy)-propyl)-N,N-dimethylammonium methylsulfate and / or N-(2-(acyl-oxy)-propyl)-N-(2-(acyl-oxy)-1-methyl-ethyl)-N,N-dimethylammonium methylsulfate and / or

[0074] or mixtures thereof, wherein the acyl moiety is derived from a C12-C22 fatty acid such as palm, tallow, canola and / or other suitable fatty acids (which may be fractionated and / or hydrogenated), and / or mixtures thereof;

[0075] (B) 1,2-di(acyloxy)-3-trimethylammonium propane chloride, wherein the acyl moiety is derived from c12-

[0076] C22 fatty acids such as palm, tallow, canola and / or other suitable fatty acids (which may be fractionated and / or hydrogenated), and / or mixtures thereof;

[0077] (C) N,N-bis(hydroxyethyl)-N,N-dimethylammonium chloride fatty acid esters; N,N-bis(acyl-oxy-ethyl)-N,N-dimethylammonium chloride, wherein the acyl moiety is derived from a C12-C22 fatty acid such as palm, tallow, canola and / or other suitable fatty acids (which may be fractionated and / or hydrogenated), and / or mixtures thereof, such as N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethylammonium chloride;

[0078] (D) esterification products of fatty acids with triethanolamine, quaternized with dimethyl sulfate; N,N-bis(acyl-oxy-ethyl) N-(2-hydroxyethyl)-N-methylammonium methylsulfate, wherein the acyl moiety is derived from a C12-C22 fatty acid such as palm, tallow, canola and / or other suitable fatty acids (which may be fractionated and / or hydrogenated), and / or mixtures thereof, such as N,N-bis(tallowoyl-oxy-ethyl) N-(2-hydroxyethyl)-N-methylammonium methylsulfate;

[0079] (E) dicanola dimethyl ammonium chloride; di(hard) tallow dimethyl ammonium chloride; dicanola dimethyl ammonium methyl sulfate; 1-methyl-1-stearoylaminoethyl-2-stearoyl imidazoline methyl sulfate; 1-tallowylamidoethyl-2-tallowyl imidazoline; dipalmitylmethyl hydroxyethyl ammonium methyl sulfate; and / or

[0080] (F) A mixture thereof.

[0081] Examples of suitable conditioning actives are commercially available from Evonik under the tradenames Rewoquat WE18 and / or Rewoquat WE20 and from Stepan under the tradenames Stepantex GA90, Stepantex VK90 and / or Stepantex VL90A.

[0082] It will be appreciated that compositions comprising conditioning actives as fabric conditioning actives may also comprise non-quaternised derivatives of such compounds, as well as unreacted reactants (eg free fatty acids).

[0083] The liquid fabric care composition of the present disclosure may include, for example, other conditioning materials in addition to alkyl quaternary ammonium compounds and / or alkyl ester quaternary ammonium compounds. Such materials may include silicones, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof, preferably silicones. The total amount of the combination of conditioning actives (as described above) and silicones may be from about 5% to about 70%, or from about 6% to about 50%, or from about 7% to about 40%, or from about 10% to about 30%, or from about 15% to about 25% by weight of the composition. The composition may include conditioning actives (as described above) and silicones in a weight ratio of from about 1:10 to about 10:1, or from about 1:5 to about 5:1, or from about 1:3 to about 1:3, or from about 1:2 to about 2:1, or from about 1:1.5 to about 1.5:1, or from about 1:1.

[0084] b. Surfactants

[0085] The liquid fabric care compositions of the present disclosure may contain surfactants as fabric treatment aids. These materials can provide cleaning benefits to the target surface and are particularly useful when the composition is in the form of a liquid detergent composition, such as a heavy-duty liquid ("HDL") detergent composition. Additionally or alternatively, surfactants can be used as processing aids and / or stability aids.

[0086] The surfactant may comprise one or more surfactants, preferably two or more. When more than one surfactant is present, it can be considered a surfactant system.

[0087] When present, surfactant can be selected from the group consisting of: anionic surfactant, nonionic surfactant, cationic surfactant, zwitterionic surfactant, amphoteric surfactant, amphoteric surfactant and their mixture. Preferably, surfactant comprises anionic surfactant, nonionic surfactant, zwitterionic surfactant or their mixture. More preferably, surfactant can comprise at least one anionic surfactant, even more preferably at least two anionic surfactants, because such system can provide effective cleaning benefit. Surfactant can comprise the combination of anionic surfactant and nonionic surfactant, optionally further combined with zwitterionic surfactant.

[0088] The composition may comprise from about 1%, or about 5%, or about 10%, or about 15%, or about 20%, or about 30%, to about 80%, or to about 65%, or to about 50%, or to about 45%, or to about 35%, or to about 25% surfactant by weight of the composition. The composition may comprise from about 1% to about 50%, preferably from about 5% to about 45%, more preferably from about 10% to about 40% surfactant by weight of the composition.

[0089] Typical HDL detergents may comprise from about 5% to about 50%, preferably from about 7% to about 40%, more preferably from about 10% to about 35%, by weight of the composition, of a surfactant, preferably an anionic surfactant. Compacted liquid detergents, such as those that may be encapsulated in a water-soluble film, may comprise from about 15% to about 50%, or from about 15% to about 45%, or from about 20% to about 40%, by weight of the composition, of a surfactant, preferably an anionic surfactant.

[0090] The composition may include anionic surfactants. Anionic surfactants can be particularly useful for providing cleaning or decontamination benefits. Suitable anionic surfactants include alkoxylated alkyl sulfates, non-alkoxylated alkyl sulfates, alkylbenzene sulfonates, and mixtures thereof. Anionic surfactants can be linear, branched (e.g., mid-chain branched) or combinations thereof. Other suitable anionic surfactants can include methyl ester sulfonates, alkane sulfonates, α-olefin sulfonates, internal olefin sulfonates, and mixtures thereof. Yet other suitable anionic surfactants can include alkyl ether carboxylates, including C10-C26 linear or branched, preferably C10-C20 linear, most preferably C16-C18 linear alkyl alcohols, and 2 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. Acid form or salt form, such as sodium salt or ammonium salt, can be used, and the alkyl chain can include a cis or trans double bond. Alkyl ether carboxylic acids are available from Kao Huntsman and Clariant Other specific anionic surfactants can include C11.8 linear alkylbenzene sulfonates, alkyl ethoxylated sulfates having an average of 1.8 ethoxy groups, and alkyl ethoxylated sulfates having an average of 3 ethoxy groups.

[0091] Anionic surfactants can exist in acid form, and the acid form can be partially or completely neutralized to form a surfactant salt. Typical reagents for neutralization include: basic metal counterions such as hydroxides, for example, NaOH or KOH; ammonia; amines; and / or alkanolamines, such as monoethanolamine, diethanolamine and / or triethanolamine.

[0092] The composition may include a nonionic surfactant. Nonionic surfactants can be used to provide a cleaning benefit; they can also be used to provide processing and / or stability benefits, for example, to help dissolve spices. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-terminated poly (alkoxylated) alcohol surfactants, and mixtures thereof. The alkoxylate units can be ethyleneoxy units, propyleneoxy units, or mixtures thereof. The nonionic surfactants can be linear, branched (e.g., mid-chain branched), or combinations thereof. Specific nonionic surfactants can include alcohols having an average of about 12 to about 16 carbon atoms and an average of about 3 to about 9 ethoxy groups, such as C12-C14 EO7 nonionic surfactants.

[0093] The compositions disclosed herein may include a cationic surfactant. Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which may have up to 26 carbon atoms and may include alkoxylated quaternary ammonium (AQA) surfactants, dimethylhydroxyethyl quaternary ammonium and / or dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; ester cationic surfactants; amino surfactants, such as amidopropyl dimethylamine (APA); and mixtures thereof. For detergency, cationic surfactants are preferably used in combination with anionic surfactants.

[0094] The compositions disclosed herein may include a zwitterionic surfactant. Examples of zwitterionic surfactants include derivatives of secondary and tertiary amines; derivatives of heterocyclic secondary and tertiary amines; or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of suitable zwitterionic surfactants include betaines, including alkyl dimethyl betaine and cocodimethylamidopropyl betaine, C8 to C 18 (For example, C 12 to C 18 ) amine oxides and sulfo- and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propanesulfonates, in which the alkyl group can be C8 to C 18 Amine oxides may be preferred for performance reasons.

[0095] The compositions disclosed herein may include amphoteric surfactants. Examples of amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group can be straight or branched, and wherein one of the aliphatic substituents contains at least about 8 carbon atoms, or about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains a water-solubilizing anionic group, such as a carboxyl group, a sulfonate group, or a sulfate group. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurates, and mixtures thereof.

[0096] Capsule group

[0097] The liquid fabric care compositions of the present disclosure also comprise a population of capsules.As described in more detail below, the capsules may comprise a core surrounded by a substantially inorganic shell.

[0098] The capsules may be present in the composition in an amount of from about 0.05% to about 20%, or from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.2% to about 2% by weight of the composition. The composition may include a sufficient amount of capsules to provide the composition with from about 0.05% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 2% of the fragrance raw material by weight of the composition. When discussing the amount or weight percentage of capsules herein, this refers to the sum of the shell material and the core material.

[0099] The capsules may have an average shell thickness of 10 nm to 10,000 nm, preferably 170 nm to 1000 nm, more preferably 300 nm to 500 nm.

[0100] The capsules may have an average volume-weighted capsule diameter of 0.1 to 300 microns, preferably 10 to 200 microns, more preferably 10 to 50 microns. It has been advantageously found that large capsules (e.g., 10 μm or greater average diameter) can be provided according to embodiments herein without sacrificing overall capsule stability and / or while maintaining good burst strength.

[0101] It has been surprisingly discovered that, in addition to the inorganic shell, the volume core-shell ratio can play an important role in ensuring the physical integrity of the capsule. Shells that are too thin compared to the overall size of the capsule (core:shell ratio>98:2) often lack self-integrity. On the other hand, very thick shells relative to the capsule diameter (core:shell ratio<80:20) often have higher shell permeability in surfactant-rich matrices. Although one might intuitively believe that a thick shell would lead to lower shell permeability (because this parameter affects the average diffusion path of the active substance through the shell), it has been surprisingly discovered that capsules of the present invention with shells with thicknesses above a threshold have higher shell permeability. It is believed that this upper threshold depends in part on the capsule diameter. The volume core-shell ratio is determined according to the method provided in the test methods section below.

[0102] The capsules may have a volume core-shell ratio of 50:50 to 99:1, preferably 60:40 to 99:1, preferably 70:30 to 98:2, more preferably 80:20 to 96:4.

[0103] It may be desirable to have a specific combination of these capsule properties. For example, a capsule may have a volume core-shell ratio of about 99:1 to about 50:50, and have an average volume-weighted capsule diameter of about 0.1 μm to about 200 μm and an average shell thickness of about 10 nm to about 10,000 nm. A capsule may have a volume core-shell ratio of about 99:1 to about 50:50, and have an average volume-weighted capsule diameter of about 10 μm to about 200 μm and an average shell thickness of about 170 nm to about 10,000 nm. A capsule may have a volume core-shell ratio of about 98:2 to about 70:30, and have an average volume-weighted capsule diameter of about 10 μm to about 100 μm and an average shell thickness of about 300 nm to about 1000 nm.

[0104] The methods of the present disclosure can produce capsules with a low coefficient of variation in capsule diameter. Control over the capsule size distribution can advantageously allow a population to have improved and more uniform burst strength. A population of capsules can have a coefficient of variation in capsule diameter of 40% or less, preferably 30% or less, and more preferably 20% or less.

[0105] In order for capsules containing core materials to be functional and cost-effective in consumer product applications such as liquid detergents or liquid fabric softeners, they should: i) resist diffusion of the core during the shelf life of the liquid product (e.g., low leakage or permeability); ii) have the ability to deposit on a target surface during application (e.g., a washing machine cycle); and iii) be capable of releasing the core material by mechanical shell rupture at the appropriate time and place to provide the desired benefit to the end consumer.

[0106] The capsules described herein may have an average burst strength of 0.1 MPa to 10 MPa, preferably 0.25 MPa to 5 MPa, more preferably 0.25 MPa to 3 MPa. Completely inorganic capsules traditionally have poor burst strength, while for the capsules described herein, the burst strength of the capsules may be greater than 0.25 MPa, thereby providing improved stability and triggered release of the beneficial agent at a specified amount of burst stress.

[0107] Preferably, the capsules have an average volume-weighted diameter of 1 to 200 microns, preferably 1 to 10 microns, and even more preferably 2 to 8 microns. Preferably, the shell thickness is 1 nm to 10,000 nm, preferably 1 nm to 1,000 nm, and more preferably 10 nm to 200 nm. Preferably, the capsules have an average volume-weighted diameter of 1 to 10 microns and a shell thickness of 1 to 200 nm. It has been found that capsules having an average volume-weighted diameter of 1 to 10 microns and a shell thickness of 1 to 200 nm have a higher burst strength.

[0108] Without wishing to be bound by theory, it is believed that higher burst strength provides better durability during the washing process, as this process can cause mechanically weak capsules to break prematurely due to mechanical constraints in the washing machine.

[0109] It is believed that capsules having an average volume-weighted diameter of 1 to 10 microns and a shell thickness of 10 to 200 nm can provide resistance to mechanical constraints, particularly when prepared with a specific choice of silica precursor. It is preferred that the precursor have a molecular weight of 2 to 5 kDa, even more preferably 2.5 to 4 kDa. In addition, the concentration of the precursor can be carefully selected, for example, so that it is 20 to 60% by weight, preferably 40 to 60% by weight, of the oil phase used during the encapsulation process.

[0110] Without wishing to be bound by theory, it is believed that higher molecular weight precursors have slower migration times from the oil phase to the aqueous phase. This slower migration time is thought to be caused by a combination of three phenomena: diffusion, distribution, and reaction kinetics. This phenomenon can be important in the case of small-sized capsules, for example, because the total surface area between the oil and water in the system increases as the capsule diameter decreases. A higher surface area can lead to higher migration of the precursor from the oil phase to the aqueous phase, which can in turn reduce the polymerization yield at the interface. Therefore, higher molecular weight precursors can be used to mitigate the effects of increased surface area and achieve capsules according to the present disclosure.

[0111] In addition to the freshness / fragrance delivery benefits provided by the capsules according to the present disclosure, it is also believed that the fabric treatment compositions according to the present disclosure that include such capsules can provide a softness / feel benefit to the fabric. It is generally advantageous to have two benefits, such as freshness and feel benefits, provided by a single ingredient because this can lead to cost savings, reduced manufacturing complexity, and formulation efficiency. Such ingredients are particularly useful in products where consumers typically desire one or both benefits, such as liquid laundry detergents, fabric enhancers, or laundry additives in the form of beads or pastilles.

[0112] i. core

[0113] The capsule comprises a core. The core may be oil-based or water-based. Preferably, the core is oil-based. The core may be liquid at the temperature at which the product is formulated. The core may be liquid at or near room temperature.

[0114] The core includes fragrance. Based on the total weight of the core, the core may include from about 1% to 100% by weight of fragrance. Preferably, the core may include from 50% to 100% by weight of fragrance based on the total weight of the core, more preferably from 80% to 100% by weight of fragrance based on the total weight of the core. Generally, higher levels of fragrance are preferred to improve delivery efficiency.

[0115] The fragrance may comprise one or more, preferably two or more, fragrance raw materials. As used herein, the term "fragrance raw material" (or "PRM") refers to a compound having a molecular weight of at least about 100 g / mol, and which can be used alone or in combination with other fragrance raw materials to impart an odor, aroma, flavor or fragrance. Typical PRMs include, among others, alcohols, ketones, aldehydes, esters, ethers, nitrites and alkenes, such as terpenes. Lists of common PRMs can be found in various references, for example, "Perfume and Flavor Chemicals", Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology", Miller, PM and Lamparsky, D., Blackie Academic and Professional (1994).

[0116] PRMs can be characterized by their boiling point (BP) measured at atmospheric pressure (760 mm Hg), and their octanol / water partition coefficient (P), which can be described in terms of logP, as determined according to the test methods described in the Test Methods section. Based on these characteristics, PRMs can be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV fragrances, as described in detail below. A fragrance having multiple PRMs from different quadrants may be desirable, for example, to provide fragrance benefits at different contact points during normal use.

[0117] Perfume raw materials having a boiling point BP below about 250°C and a logP of less than about 3 are referred to as Quadrant I perfume raw materials. Quadrant I perfume raw materials are preferably limited to less than 30% of the perfume composition. Perfume raw materials having a boiling point BP above about 250°C and a logP greater than about 3 are referred to as Quadrant IV perfume raw materials, perfume raw materials having a boiling point BP above about 250°C and a logP less than about 3 are referred to as Quadrant II perfume raw materials, and perfume raw materials having a boiling point BP below about 250°C and a logP greater than about 3 are referred to as Quadrant III perfume raw materials. Suitable Quadrant I, II, III, and IV perfume raw materials are disclosed in U.S. Patent No. 6,869,923 Bl.

[0118] The fragrance microcapsules contain a fragrance. Preferably, the microencapsulated fragrance comprises a mixture of at least 3, or even at least 5, or at least 7 fragrance raw materials. The microencapsulated fragrance may comprise at least 10, or at least 15, fragrance raw materials. A mixture of fragrance raw materials can, for example, provide more complex and desirable aesthetics at multiple contact points and / or better fragrance performance or longevity. However, it may be desirable to limit the number of fragrance raw materials in a fragrance to reduce or limit formulation complexity and / or cost.

[0119] The fragrance may comprise at least one natural-source fragrance raw material. Such components may be desirable for sustainability / environmental reasons. Natural-source fragrance raw materials may include natural extracts or essences, which may include mixtures of PRMs. Such natural extracts or essential oils may include orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essences, sandalwood oil, pine oil, cedar, and the like.

[0120] In addition to the perfume raw materials, the core may also include a pro-fragrance, which may help improve the persistence of the freshness benefit. The pro-fragrance may comprise a non-volatile material that is released or converted into a perfume material, such as by simple hydrolysis, or may be a pro-fragrance triggered by a pH change (e.g., triggered by a drop in pH), or may be an enzyme-released pro-fragrance, or a light-triggered pro-fragrance. Depending on the pro-fragrance selected, the pro-fragrance may exhibit different release rates.

[0121] The core of the encapsulate of the present disclosure may contain a core modifier, such as a distribution modifier and / or a density modifier. In addition to the flavor, the core may contain from greater than 0% to 80%, preferably from greater than 0% to 50%, more preferably from greater than 0% to 30% of a core modifier based on the total core weight. The distribution modifier may include a material selected from the group consisting of vegetable oils, modified vegetable oils, C4-C 24 Monoesters, diesters, and triesters of fatty acids, isopropyl myristate, lauryl benzophenone, lauryl laurate, methyl behenate, methyl laurate, methyl palmitate, methyl stearate, and mixtures thereof. The partition modifier may preferably include or consist of isopropyl myristate. The modified vegetable oil may be esterified and / or brominated. The modified vegetable oil may preferably include castor oil and / or soybean oil. U.S. Patent Application Publication No. 20110268802, incorporated herein by reference, describes other partition modifiers that can be used in the fragrance encapsulates of the present invention.

[0122] ii. Shell

[0123] The capsule of the present disclosure comprises a shell surrounding the core.

[0124] The shell may include a first shell member. The shell may preferably include a second shell member surrounding the first shell member. The first shell member may include a condensation layer formed from a condensation product of a precursor. As described in detail below, the precursor may include one or more precursor compounds. The first shell member may include a nanoparticle layer. The second shell member may include an inorganic material.

[0125] The shell may be substantially inorganic (defined later). The substantially inorganic shell may comprise a first shell component comprising a condensation layer surrounding the core and may further comprise a nanoparticle layer surrounding the condensation layer. The substantially inorganic shell may further comprise a second shell component surrounding the first shell component. The first shell component comprises an inorganic material, preferably a metal / semi-metal oxide, more preferably SiO2, TiO2 and Al2O3, and even more preferably SiO2. The second shell component comprises an inorganic material, preferably a material selected from the group consisting of metal / semi-metal 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, and even more preferably selected from SiO2 and CaCO3. Preferably, the second shell component material has the same type of chemical properties as the first shell component to maximize chemical compatibility.

[0126] The first shell member may include a condensation layer surrounding the core. The condensation layer may be a condensation product of one or more precursors. The one or more precursors may include at least one compound selected from the group consisting of formula (I), formula (II), and mixtures thereof, wherein formula (I) is (M v O z Y n ) w , and wherein the formula (II) is (M v O z Y n R 1 p ) w It may be preferred that the precursor comprises only formula (I) and no compound according to formula (II), for example in order to reduce the organic content of the capsule shell (ie no R 1 Group). Formulas (I) and (II) are described in more detail below.

[0127] The one or more precursors may have formula (I):

[0128] (M v O z Y n ) w (Formula I),

[0129] wherein M is one or more of silicon, titanium and aluminum, v is the valence number of M and is 3 or 4, z is 0.5 to 1.6, preferably 0.5 to 1.5, each Y is independently selected from -OH, -OR 2 、-NH2、-NHR 2 、-N(R 2 )2 , where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl, or a 5-12 membered heteroaryl group containing 1 to 3 ring heteroatoms selected from O, N and S, R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 Aryl, or a 5-12 membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N and S, n is 0.7 to (v-1), and w is 2 to 2000.

[0130] One or more precursors may have formula (I) wherein M is silicon. Possibly, Y is -OR 2 It is possible that n is from 1 to 3. It may be preferred that Y is -OR 2 and n is 1 to 3. It is possible that n is at least 2 and one or more of Y is -OR 2, and one or more of Y is -OH.

[0131] R 2 Can be C1 to C 20 Alkyl. R 2 Can be C6 to C 22 Aryl. R 2 It may be one or more of C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl and C8 alkyl. 2 It can be a C1 alkyl group. 2 Can be C2 alkyl. 2 Can be C3 alkyl. 2 It may be a C4 alkyl group.

[0132] Possibly, z is from 0.5 to 1.3, or from 0.5 to 1.1, from 0.5 to 0.9, or from 0.7 to 1.5, or from 0.9 to 1.3, or from 0.7 to 1.3.

[0133] Preferably, M is silicon, v is 4, and each Y is -OR 2 , n is 2 and / or 3, and each R 2 It is a C2 alkyl group.

[0134] The precursor may comprise polyalkoxysilane (PAOS).The precursor may comprise polyalkoxysilane (PAOS) ​​synthesized by a hydrolysis process.

[0135] The precursor may alternatively or additionally comprise one or more compounds of formula (II):

[0136] (M v O z Y n R 1 p ) w (Formula II),

[0137] wherein M is one or more of silicon, titanium and aluminum, v is the valence number of M and is 3 or 4, z is 0.5 to 1.6, preferably 0.5 to 1.5, each Y is independently selected from -OH, -OR 2 、-NH2、-NHR 2 、-N(R 2 )2 , where R 2 Selected from C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl, or a 5-12 membered heteroaryl group containing 1 to 3 ring heteroatoms selected from O, N and S, R 3 H, C1 to C 20 Alkyl, C1 to C20 Alkylene, C6 to C 22 aryl, or 5-12 membered heteroaryl containing 1 to 3 ring heteroatoms selected from O, N and S; n is 0 to (v-1); each R 1 Independently selected from the group consisting of: C1 to C 30 Alkyl; C1 to C 30 Alkylene; C1 to C2 substituted by a member (e.g., one or more) selected from the group consisting of halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -C(O)OH, -C(O)O-alkyl, -C(O)O-aryl, -C(O)O-heteroaryl, and mixtures thereof 30 Alkyl; C1 to C2 substituted by a member selected from the group consisting of halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -C(O)OH, -C(O)O-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl 30 Alkylene; and p is a number greater than zero and up to pmax, wherein pmax=60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is R 1 The molecular weight of the group, and wherein w is 2 to 2000.

[0138] R 1 It can be a C1 to C2 substituted group that is independently selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H (i.e., C(O)OH), -C(O)O-alkyl, -C(O)O-aryl, and -C(O)O-heteroaryl. 30 Alkyl. R 1 It can be a C1 to C2 substituted group which is independently selected from halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, CO2H, -C(O)O-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl. 30 Alkylene.

[0139] As mentioned above, in order to reduce or even eliminate the organic content in the first shell part, it may be preferred to reduce or even eliminate the presence of compounds according to formula (II) having R1 groups. The precursor, condensation layer, first shell part and / or shell may be free of compounds according to formula (II).

[0140] 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 molecular weight distribution. It is believed that selecting a specific Mw and / or DB can be used to obtain capsules that maintain their mechanical integrity after drying on the surface and have low shell permeability in a surfactant-based matrix. The 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 a Mw of 600Da to 100,000Da, preferably 700Da to 60,000Da, more preferably 1,000Da to 30,000Da. This feature provides useful properties of the precursors to obtain capsules of the present invention. The precursors of formula (I) and / or (II) may have a PDI of 1 to 50.

[0141] The condensation layer comprising a metal / semimetal oxide may be formed from the condensation product of a precursor comprising at least one compound of formula (I) and / or at least one compound of formula (II), optionally in combination with one or more monomeric precursors of a metal / semimetal oxide, wherein the metal / semimetal oxide comprises TiO2, Al2O3 and SiO2, preferably SiO2. The monomeric precursor of the metal / semimetal oxide may comprise a compound of formula M(Y) V-n R n wherein M, Y and R are as defined in formula (II) and n may be an integer from 0 to 3. The monomeric precursor of the metal / semi-metal oxide may preferably be in the form where M is silicon, wherein the compound has the general formula Si(Y) 4-n R n , wherein Y and R are as defined for formula (II) and n can be an integer from 0 to 3. Examples of such monomers are TEOS (tetraethoxyorthosilicate), TMOS (tetramethoxyorthosilicate), TBOS (tetrabutoxyorthosilicate), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES) and tetraacetoxysilane (TAcS). These are not intended to limit the scope of monomers that can be used, and it will be apparent to those skilled in the art what suitable monomers may be used in combination herein.

[0142] The first shell component may include an optional nanoparticle layer. The nanoparticle layer comprises nanoparticles. The nanoparticles of the nanoparticle layer may be one or more of SiO2, TiO2, Al2O3, ZrO2, ZnO2, CaCO3, clay, silver, gold, and copper. Preferably, the nanoparticle layer comprises SiO2 nanoparticles.

[0143] The nanoparticles may have an average diameter of 1 nm to 500 nm, preferably 50 nm to 400 nm.

[0144] The pore size of the capsule can be regulated by changing the shape of the nanoparticle and / or by using a combination of different nanoparticle sizes. For example, non-spherical irregular nanoparticles can be used because they can have improved accumulation when forming the nanoparticle layer, and it is believed that this can produce a denser shell structure. When limited permeability is required, this can be favourable. The nanoparticles used can have a more regular shape, such as a sphere. Any imagined nanoparticle shape can be used herein.

[0145] The nanoparticles may be substantially free of hydrophobic modification. The nanoparticles may be substantially free of organic compound modification. The nanoparticles may include organic compound modification. The nanoparticles may be hydrophilic.

[0146] The nanoparticles may contain surface modifications such as, but not limited to, linear or branched C1 to C 20 Alkyl groups, surface amino groups, surface methacryloyl groups, surface halogens or surface thiols. These surface modifications allow the nanoparticle surface to have covalently bound organic molecules thereon. When inorganic nanoparticles are disclosed in this document, this means including any or no such surface modifications without explicit reference.

[0147] The capsules of the present disclosure can be defined as comprising a substantially inorganic shell comprising a first shell member and a second shell member. Substantially inorganic means that the first shell member may comprise an organic content of up to 10% by weight or up to 5% by weight, preferably up to 1% by weight, as defined later in the organic content calculation. Preferably, the first shell member, the second shell member, or both, as the case may be, comprise an organic content of no more than about 5% by weight, preferably no more than about 2% by weight, and more preferably about 0% by weight, based on the weight of the first or second shell member.

[0148] While the first shell component can be used to create a mechanically robust scaffold or framework, it can also provide low shell permeability in liquid products containing surfactants, such as laundry detergents, shower gels, cleaning agents, and the like (see Surfactants in Consumer Products, J. Falbe, Springer-Verlag). The second shell component can significantly reduce shell permeability, which improves capsule impermeability in surfactant-based matrices. The second shell component can also significantly improve capsule mechanical properties, such as capsule rupture force and rupture strength. Without being bound by theory, it is believed that the second shell component contributes to the densification of the entire shell by depositing the precursor in pores retained in the first shell component. The second shell component also adds an additional inorganic layer to the surface of the capsule. These improved shell permeability and mechanical properties provided by the second shell component only occur when used in combination with the first shell component as defined herein.

[0149] A more detailed description of shell structures, their materials, and how they interact with each other to provide optimal performance can be found in U.S. Patent Applications 16 / 851,173, 16 / 851,176, and 16 / 851,194, the disclosures of which are incorporated herein by reference in their entireties.

[0150] iii. Method for preparing capsules

[0151] Capsule of the present disclosure can be by first hydrophobic material and any one of the precursor of condensation layer as defined above are mixed, thereby form oil phase and form, wherein this oil phase can comprise oil base and / or oil-soluble precursor.Then described precursor / hydrophobic material mixture is used as dispersed phase or as the continuous phase combined with water, wherein in the former case, forms O / W (oil-in-water) emulsion, and in the latter case once via method well known to those skilled in the art two-phase is mixed and homogenized just form W / O (water-in-oil) emulsion.Preferably, form O / W emulsion.Nano-particle can be present in water and / or oil phase, and has nothing to do with desired emulsion type.Oil phase can comprise the precursor of oil base core modifier and / or oil base benefit agent and condensation layer.The suitable core material that is used for oil phase is described in this paper earlier.

[0152] Once either emulsion is formed, the following steps can be performed:

[0153] (a) Nanoparticles migrate to the oil / water interface, forming a nanoparticle layer.

[0154] (b) The precursor of the condensation layer comprising the metal / semi-metal oxide precursor will begin to undergo a hydrolysis / condensation reaction with water at the oil / water interface, thereby forming a condensation layer surrounded by the nanoparticle layer. The precursor of the condensation layer may further react with the nanoparticles of the nanoparticle layer.

[0155] The condensation layer-forming precursor may be present in an amount of 1 to 50 wt %, preferably 10 to 40 wt %, based on the total weight of the oil phase.

[0156] The oil phase composition may comprise any compound as defined above in the core section.Prior to emulsification, the oil phase may comprise from 10% to about 99% by weight of the benefit agent.

[0157] In the method for preparing capsules according to the present disclosure, the oil phase can be the dispersed phase, and the continuous aqueous (or water) phase can include water, an acid or a base, and the nanoparticles. At least when the oil phase and the aqueous phase are mixed together, the aqueous (or water) phase can have a pH of 1 to 11, preferably 1 to 7. The acid can be a strong acid. The strong acid can include one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4, and HClO3, preferably HCl. The acid can be a weak acid. The weak acid can be acetic acid or HF. The concentration of the acid in the continuous aqueous phase can be 10 -7 M to 5 M. The base can be an inorganic base or an organic base, preferably an inorganic base. The inorganic base can be a hydroxide, such as sodium hydroxide and ammonia. For example, the mineral can be about 10 -5 M to 0.01 M NaOH, or about 10 -5 M to about 1 M ammonia. The above enumerated list of acids and bases and their concentration ranges is not meant to limit the scope of the invention, and other suitable acids and bases that allow for control of the pH of the continuous phase are contemplated herein.

[0158] In the method for preparing capsules according to the present disclosure, the pH can be varied throughout the process by adding acid and / or base. For example, the method can be initiated with an aqueous phase at an acidic or neutral pH, and then a base can be added during the process to increase the pH. Alternatively, the method can be initiated with an aqueous phase at an alkaline or neutral pH, and then an acid can be added during the process to lower the pH. Furthermore, the method can be initiated with an aqueous phase at an acidic or neutral pH, and then an acid can be added during the process to further lower the pH. Furthermore, the method can be initiated with an aqueous phase at an alkaline or neutral pH, and then a base can be added during the process to further increase the pH. Any suitable pH variation can be used. Furthermore, any suitable combination of acid and base can be used in the method at any time to achieve the desired pH. Any of the above-described nanoparticles can be used in the aqueous phase. The nanoparticles can be present in an amount of about 0.01% to about 10% by weight, based on the total weight of the aqueous phase.

[0159] The method can include mixing the oil phase and the water phase at a ratio of about 1 :10 to about 1 :1 oil phase to water phase.

[0160] The second shell member can be formed by mixing the capsule having the first shell member with a solution of a second shell member precursor. The solution of the second shell member precursor can contain a water-soluble or oil-soluble second shell member precursor. The second shell member precursor can be one or more of the compound of formula (I) as defined above, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS), triethoxymethylsilane (TEMS), diethoxy-dimethylsilane (DEDMS), trimethylethoxysilane (TMES) and tetraacetoxysilane (TAcS). The second shell member precursor can also contain Si(Y) 4-n R n One or more of the type silane monomers, wherein Y is a hydrolyzable group, R is a non-hydrolyzable group, and n can be an integer from 0 to 3. Examples of such monomers are given earlier in this paragraph, and these are not intended to limit the scope of monomers that can be used. The second shell component precursor may contain silicates, titanates, aluminates, zirconates and / or zincates. The second shell component precursor may contain carbonates and calcium salts. The second shell component precursor may contain salts of iron, silver, copper, nickel and / or gold. The second shell component precursor may contain zinc, zirconium, silicon, titanium and / or aluminum alkoxides. The second shell component precursor may contain one or more of a silicate solution such as sodium silicate, a tetrasilicon solution, an iron sulfate salt and an iron nitrate salt, a titanium alkoxide solution, an aluminum trialkoxide solution, a zinc dialkoxide solution, a zirconium alkoxide solution, a calcium salt solution, and a carbonate solution. The second shell component containing CaCO3 can be obtained from the combined use of a calcium salt and a carbonate. The second shell component comprising CaCO 3 can be obtained from calcium salts without adding carbonates by in situ generation of carbonate ions from CO 2 .

[0161] The second shell component precursor may comprise any suitable combination of any of the above-listed compounds.

[0162] The second shell member precursor solution can be added dropwise to the capsule comprising the first shell member. The second shell member precursor solution and the capsule can be mixed together for 1 minute to 24 hours. The second shell member precursor solution and the capsule can be mixed together at room temperature or at an elevated temperature, such as 20°C to 100°C.

[0163] The second shell member precursor solution may include the second shell member precursor in an amount of 1 wt % to 50 wt % based on the total weight of the solution of the second shell member precursor.

[0164] The capsule having the 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 can contain an acid and / or a base. The acid can be a strong acid. The strong acid can include one or more of HCl, HNO3, H2SO4, HBr, HI, HClO4, and HClO3, preferably HCl. In other embodiments, the acid can be a weak acid. In embodiments, the weak acid can be acetic acid or HF. The concentration of the acid in the second shell component precursor solution can be 10 -7 M to 5 M. The base can be an inorganic base or an organic base, preferably an inorganic base. The inorganic base can be a hydroxide, such as sodium hydroxide and ammonia. For example, the mineral can be about 10 -5 M to 0.01 M NaOH, or about 10 -5 M to about 1 M ammonia. The list of acids and bases enumerated above is not meant to limit the scope of the present invention, and other suitable acids and bases that allow for control of the pH of the second shell component precursor solution are contemplated herein.

[0165] The method for forming the second shell component may include pH variations during the process. For example, the process for forming the second shell component may be initiated at an acidic or neutral pH, and then a base may be added during the process to increase the pH. Alternatively, the process for forming the second shell component may be initiated at an alkaline or neutral pH, and then an acid may be added during the process to lower the pH. Furthermore, the process for forming the second shell component may be initiated at an acidic or neutral pH, and then an acid may be added during the process to further lower the pH. Furthermore, the process for forming the second shell component may be initiated at an alkaline or neutral pH, and then a base may be added during the process to further increase the pH. Any suitable pH variation may be used. Furthermore, any suitable combination of acid and base may be used in the solution of the second shell component precursor at any time to achieve the desired pH. The method for forming the second shell component may include maintaining a stable pH during the process, with a maximum deviation of + / - 0.5 pH units. For example, the process for forming the second shell component may be maintained at an alkaline, acidic, or neutral pH. Alternatively, the process for forming the second shell component may be maintained within a specific pH range by controlling the pH using an acid or base. Any suitable pH range may be used. Furthermore, any suitable combination of acid and base may be used in the solution of the second shell component precursor at any time to maintain a stable pH within the desired range.

[0166] A more detailed description of the method for making the capsules and the relevant properties of all shell component precursors (i.e., the condensation layer precursor, the nanoparticles, and the second shell component precursor) can be found in U.S. patent applications 16 / 851173, 16 / 851176, and 16 / 851194, the entire disclosure of which defines the method for making the capsules of the present invention.

[0167] Whether preparing an oil-based or aqueous core, the emulsion can be cured under conditions that cure the precursor, thereby forming a shell surrounding the core.

[0168] The reaction temperature for curing can be increased to increase the rate at which cured capsules are obtained. The curing process can cause condensation of the precursors. The curing process can be completed at or above room temperature. The curing process can be carried out at a temperature of 30°C to 150°C, preferably 50°C to 120°C, and more preferably 80°C to 100°C. The curing process can be completed over any suitable period of time to allow the capsule shell to be strengthened by the condensation of the precursor materials. The curing process can be carried out for 1 minute to 45 days, preferably 1 hour to 7 days, and more preferably 1 hour to 24 hours. The capsule is considered cured when it no longer collapses. The determination of capsule collapse is described in detail below. During the curing step, it is believed that hydrolysis of the Y moiety (from formula (I) and / or (II) occurs, followed by subsequent condensation of the -OH group with another -OH group or another moiety of the Y type (wherein the two Y moieties are not necessarily the same). The hydrolyzed precursor moiety will initially condense with the surface moieties of the nanoparticles (provided that they contain such moieties). As shell formation proceeds, the precursor moiety will react with the preformed shell.

[0169] The emulsion can be cured to cause condensation of the shell precursor. The emulsion can be cured to cause condensation of the shell precursor by reaction with the nanoparticles. An example of the hydrolysis and condensation steps of the silica-based shell described herein is shown below:

[0170] Hydrolysis: ≡Si-OR+H2O→≡Si-OH+ROH

[0171] Condensation: ≡Si-OH+≡Si-OR→≡Si-O-Si≡+ROH

[0172] ≡Si-OH+≡Si-OH→≡Si-O-Si≡+H2O.

[0173] For example, when using a precursor of formula (I) or (II), the hydrolysis and condensation steps are described below:

[0174] Hydrolysis: ≡M-Y+H2O→≡M-OH+YH

[0175] Condensation: ≡M-OH+≡MY→≡MOM≡+YH

[0176] ≡M-OH+≡M-OH→≡MOM≡+H2O.

[0177] The capsules can be provided as a slurry composition (or simply referred to herein as a "slurry"). The result of the methods described herein can be a slurry containing capsules. The slurry can be formulated into a product, such as a consumer product.

[0178] Auxiliary ingredients

[0179] In addition to the above-mentioned conditioners and fragrance capsules, the liquid fabric care compositions of the present disclosure may include one or more auxiliary ingredients. Appropriate levels of auxiliary ingredients may be selected to promote improved performance, processing, and / or aesthetics. One or more auxiliary ingredients may be selected from processing aids, fragrance delivery systems, structurants, rheology modifiers, other auxiliary agents, or mixtures thereof. Several of these auxiliary agents are discussed in more detail below.

[0180] Processing aids

[0181] The composition may include one or more processing aids. The processing aids may include one or more of an aggregation-inhibiting substance (such as a divalent salt) and a particle suspending polymer. The aggregation-inhibiting substance may include salts that can have a charge shielding effect around the capsule, such as magnesium chloride, calcium chloride, magnesium bromide, and magnesium sulfate. The composition may also include one or more of the following: xanthan gum, carrageenan, guar gum, shellac, alginate, chitosan; cellulosic materials such as carboxymethyl cellulose, hydroxypropyl methylcellulose, cationic cellulosic materials; polyacrylic acid; polyvinyl alcohol; hydrogenated castor oil; and ethylene glycol distearate. The composition may include one or more carriers. The one or more carriers may be a polar solvent, a non-polar solvent, or a mixture thereof. Polar solvents may include water, ethylene glycol, propylene glycol, polyethylene glycol, and glycerol; non-polar solvents may include mineral oil, silicone oil, and hydrocarbon paraffin oil.

[0182] Additional fragrance delivery systems

[0183] In addition to the capsules of the present disclosure, the composition may further comprise one or more additional fragrance delivery systems. The additional fragrance delivery systems may comprise free fragrance, pro-fragrance, other fragrance capsules (e.g., core-shell capsules comprising greater than 5 wt. % organic material in the shell), and mixtures thereof.

[0184] To combat malodors associated with damp fabrics, a fragrance delivery system comprising free (e.g., unencapsulated) fragrance may be particularly effective. The composition may comprise 0.01% to 10% by weight, or 0.1% to 5% by weight, or even 0.2% to 2% by weight of free fragrance. The composition may comprise at least 0.75% or at least 1% free fragrance by weight of the composition. Preferably, the free fragrance comprises a mixture of at least 3, or even at least 5, or at least 7, or at least 10, or at least 15 fragrance raw materials.

[0185] The compositions of the present disclosure may include a pro-fragrance, which may help improve the persistence of the freshness benefit. The pro-fragrance may comprise a non-volatile material that is released or converted into a fragrance material, such as by simple hydrolysis, or may be a pro-fragrance triggered by a pH change (e.g., triggered by a drop in pH), or may be an enzyme-released pro-fragrance, or a light-triggered pro-fragrance. Depending on the pro-fragrance selected, the pro-fragrance may exhibit different release rates.

[0186] The composition may include other fragrance capsules. These capsules may be core-shell capsules and may contain greater than 5% by weight of organic material in the shell, based on the weight of the shell material. Such capsules may be considered "organic" capsules in the present disclosure to distinguish them from the inorganic capsules described and claimed herein. The shell material of the organic capsules may include materials, preferably polymeric materials, derived from melamine, polyacrylamide, silicone, polystyrene, polyurea, polyurethane, polyacrylate-based materials, gelatin, styrene malic anhydride, polyamide, and mixtures thereof. The organic capsules may be coated with a deposition aid, a cationic polymer, a nonionic polymer, an anionic polymer, or a mixture thereof. Suitable deposition polymers may be selected from the group consisting of polyvinyl formaldehyde, partially hydroxylated polyvinyl formaldehyde, polyvinylamine, polyethyleneimine, ethoxylated polyethyleneimine, polyvinyl alcohol, polyacrylates, cationic polysaccharides (such as chitosan), and combinations thereof. The organic capsules may have a volume weighted average particle size of about 0.5 microns to about 100 microns, preferably about 1 micron to about 60 microns, or alternatively about 25 microns to about 60 microns, more preferably about 25 microns to about 60 microns.

[0187] Rheology modifiers / Structuring agent

[0188] The compositions of the present disclosure may include rheology modifiers and / or structurants. Rheology modifiers can be used to "thicken" or "thinn" a liquid composition to a desired viscosity. Structuring agents can be used to promote phase stability and / or suspend or inhibit aggregation of particles in a liquid composition, such as encapsulates as described herein.

[0189] Suitable rheology modifiers and / or structurants may include non-polymeric crystalline hydroxyl-functional structurants (including those based on hydrogenated castor oil), polymeric structurants, cellulosic fibers (e.g., microfibrillated cellulose, which may be derived from bacteria, fungi, or plant sources, including from wood), diamido gelling agents, or combinations thereof.

[0190] Polymer structuring agents may be of natural or synthetic origin. Polymer structuring agents of natural origin may include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives and mixtures thereof. Polysaccharide derivatives may include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof. Synthetic polymer structuring agents may include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated polyurethanes, hydrophobically modified nonionic polyols and mixtures thereof. Polycarboxylate polymers may include polyacrylates, polymethacrylates or mixtures thereof. Polyacrylates may include C1-C12 derivatives of unsaturated mono- or dicarbonic acids and (meth) acrylic acid. 30 Copolymers of alkyl esters. Such copolymers are available from Noveon under the trade name Carbopol Aqua 30. Another suitable structurant is sold under the trade name Rheovis CDE, available from BASF.

[0191] The structurant may be in the form of a structurant system comprising more than one structurant material. For example, the structurant system may be in the form of a polysaccharide system. Preferred polysaccharides include xanthan gum, glucomannan, galactomannan, and combinations thereof. Glucomannan may be derived from natural gums such as konjac gum. Galactomannan may be derived from natural gums such as locust bean gum. The polysaccharide may also include carrageenan. Xanthan gum may be modified, such as by deacetylation. The polysaccharide may comprise at least two polysaccharides, such as a first polysaccharide and a second polysaccharide. The first polysaccharide may be xanthan gum. The second polysaccharide may be selected from the group consisting of glucomannan, galactomannan, and combinations thereof. The second polysaccharide may be selected from the group consisting of konjac gum, locust bean gum, and combinations thereof. Preferably, the first polysaccharide is xanthan gum and the second polysaccharide is konjac gum. Such polysaccharide systems are particularly useful in sprayable products. When the composition is in the form of a sprayable product, the total concentration of polysaccharides present in the liquid composition may be less than about 0.5% by weight, or preferably less than about 0.2% by weight, or preferably less than about 0.1% by weight, more preferably less than 0.08% by weight, and most preferably less than 0.06% by weight. Without wishing to be bound by theory, it is believed that minimizing the level of total polysaccharides present in the sprayable composition reduces residue and / or optimizes spray characteristics.

[0192] Other additives

[0193] The fabric care compositions of the present disclosure may contain other adjuncts suitable for inclusion in the product and / or for end use. For example, the fabric care compositions may contain cationic polymers, cleaning polymers, enzymes, solvents, emulsifiers, suds suppressors, dyes, hueing agents, brighteners, chelating agents, or combinations thereof.

[0194] Preparation method

[0195] The present disclosure relates to a method for preparing any of the liquid fabric care compositions described herein. The method for preparing a liquid fabric care composition (which may be a liquid fabric enhancer) may comprise the step of combining a capsule as described herein with a fabric treatment aid. The fabric treatment aid may be part of a liquid base composition. The method may comprise the step of providing a liquid base composition comprising an ingredient selected from the group consisting of a fabric treatment aid, water, and mixtures thereof. The capsule may be combined with a liquid base composition.

[0196] The liquid fabric care compositions of the present disclosure can be formulated into any suitable form and prepared by any method selected by the formulator. Fabric treatment auxiliaries, capsules and other auxiliaries (if any) can be combined in a batch process, in a recycle loop process and / or by an online mixing method. Suitable equipment for the methods disclosed herein may include a continuous stirred tank reactor, a homogenizer, a turbine agitator, a recirculation pump, a paddle mixer, a plowshare shear mixer, a ribbon blender, a vertical shaft granulator and a drum mixer (both of which can be in a batch process configuration and a continuous process configuration (when available)), a spray dryer and an extruder.

[0197] How to use

[0198] The present disclosure also relates to methods of using liquid fabric care compositions. For example, the present disclosure relates to methods of treating fabrics with compositions according to the present disclosure. Such methods can provide cleaning, conditioning, and / or refreshing benefits.

[0199] The method may include the step of contacting fabrics with a liquid fabric care composition of the present disclosure. The composition may be neat or diluted in a liquid, such as a wash liquor or rinse liquor. The composition may be diluted in water before, during, or after contacting the surface or article. The fabric may optionally be washed and / or rinsed before and / or after the contacting step. The composition may be applied directly to the fabric or provided to a dispensing container or drum of an automatic washing machine.

[0200] The method of treating fabrics may comprise the steps of: (a) optionally washing, rinsing and / or drying the fabrics; (b) contacting the fabrics with a composition as described herein, optionally in the presence of water; (c) optionally washing and / or rinsing the fabrics; and (d) optionally drying, whether passively and / or via active methods such as a laundry washing and drying machine. The method may occur during the wash cycle or rinse cycle, preferably the rinse cycle, of an automatic washing machine.

[0201] For purposes of the present invention, treatment may include, but is not limited to, scouring and / or mechanical agitation.The fabric may comprise most any fabric capable of being washed or treated under normal consumer use conditions.

[0202] The liquid containing the disclosed composition may have a pH of about 3 to about 11.5. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution when diluted. When the wash solvent is water, the water temperature is typically in the range of about 5°C to about 90°C, and the water to fabric ratio may typically be about 1:1 to about 30:1.

[0203] Uses of capsules

[0204] It has been found that the capsules according to the present disclosure can be used to provide various benefits to target fabrics, for example when formulated in a fabric care composition and used to treat the fabrics. The present disclosure may relate to the use of the capsules to provide a freshness benefit, a softening benefit, or a combination thereof to the fabrics when the fabrics are treated with a fabric care composition comprising the capsules.

[0205] For example, the present disclosure relates to the use of capsules according to the present invention to provide a freshening benefit to a fabric when the fabric is treated with a fabric care composition comprising such capsules. As used herein, "freshening benefit" refers to a desired fragrance-related benefit provided to a target fabric compared to a comparative fabric treated with the same fabric care composition in the absence of such capsules and / or when the comparative fabric is treated with the same fabric care composition comprising the comparative capsules. The freshening benefit can be assessed by any of the techniques described herein, such as via an olfactory panel and / or headspace analysis.

[0206] The present disclosure also relates to the use of the capsules according to the present disclosure to provide a softening benefit to a fabric when the fabric is treated with a fabric care composition comprising such capsules. As used herein, "softening benefit" refers to a benefit associated with an increase in softness, lubricity, friction reduction, or other hand feel benefits provided to a target fabric when compared to a comparative fabric treated with the same fabric care composition in the absence of such capsules and / or when compared to a comparative fabric treated with the same fabric care composition comprising the comparative capsules. The softening benefit can be assessed by any suitable technique.

[0207] The present disclosure also relates to the use of capsules according to the present disclosure to provide both a freshness benefit and a softening benefit to fabrics when treated with a fabric care composition comprising such capsules. It is often advantageous to have two benefits, such as freshness and a sensory benefit, provided by a single ingredient, as this can result in cost savings, reduced manufacturing complexity, and formulation efficiencies. Such ingredients are particularly useful in products where consumers typically desire one or both benefits, such as liquid laundry detergents, fabric enhancers, or laundry additives in the form of beads or pastilles.

[0208] The uses described herein relate to fabrics "treated" with a fabric care composition. The treatment may preferably be carried out in an automatic washing machine, preferably according to a conventional wash / rinse cycle. The fabric care composition may be in liquid or solid form, preferably a liquid, more preferably a liquid laundry detergent, a liquid fabric enhancer or a liquid fabric refresher spray, most preferably a liquid fabric enhancer. The fabric care composition may be a liquid fabric care composition according to the present disclosure, which may include the ingredients and amounts as described herein, including the disclosure relating to capsules.

[0209] combination

[0210] Specific contemplated combinations of the present disclosure are described herein in the following lettered paragraphs. These combinations are illustrative in nature and not restrictive.

[0211] A. A liquid fabric care composition comprising: a fabric treatment aid, wherein the fabric treatment aid is selected from the group consisting of a conditioning active, a surfactant, or a mixture thereof, wherein the conditioning active, if present, is selected from the group consisting of an alkyl quaternary ammonium compound, an alkyl ester quaternary ammonium compound, and a mixture thereof, and wherein the surfactant, if present, is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof; and a population of capsules comprising a core and a shell surrounding the core, wherein the core comprises a perfume raw material, wherein the shell comprises: a substantially inorganic first shell member comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer; an inorganic second shell member surrounding the first shell member, wherein the second shell member surrounds the nanoparticle layer; wherein the precursor comprises at least one compound selected from the group consisting of formula (I), formula (II), and mixtures thereof, wherein formula (I) is (M v O z Y n ) w , wherein formula (II) is (M v O z Y n R 1 p ) w , wherein for formula (I), formula (II) or a mixture thereof: each M is independently selected from the group consisting of silicon, titanium and aluminum, v is the valence number of M and is 3 or 4, z is 0.5 to 1.6, each Y is independently selected from -OH, -OR 2 ,halogen, -NH2, -NHR2 、-N(R 2 )2 and where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl or 5-12 membered heteroaryl, wherein the heteroaryl contains 1 to 3 ring heteroatoms selected from O, N and S, wherein R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl or 5-12 membered heteroaryl, wherein the heteroaryl contains 1 to 3 ring heteroatoms selected from O, N and S, w is 2 to 2000; wherein for formula (I), n is 0.7 to (v-1); and wherein for formula (II), n is 0 to (v-1); each R 1 Independently selected from the group consisting of: C1 to C 30 Alkyl; C1 to C 30 Alkylene; C1 to C2 substituted by a member selected from the group consisting of halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -CO2H, -C(O)-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl 30 Alkyl; C1 to C2 substituted by a member selected from the group consisting of halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -C(O)OH, -C(O)O-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl 30 Alkylene; and p is a number greater than zero and up to pmax, wherein pmax=60 / [9*Mw(R 1 )+8], where Mw(R 1 ) is R 1 The molecular weight of the group.

[0212] B. A liquid fabric care composition comprising: from about 5% to about 99.5% water, by weight of the composition; and a population of capsules comprising a core and a shell surrounding the core, wherein the core comprises a perfume raw material, and wherein the shell is as described in paragraph A.

[0213] C. A liquid fabric care composition according to any of paragraphs A or B, wherein the precursor comprises at least one compound according to formula (I), preferably wherein the precursor is free of compounds according to formula (II).

[0214] D. A liquid fabric care composition according to any of paragraphs A to C, wherein the precursor comprises at least one compound according to formula (II).

[0215] E. A liquid fabric care composition according to any of paragraphs A to D, wherein the capsule population is characterized by one or more of the following: (a) an average volume-weighted capsule diameter of about 10 μm to about 200 μm, preferably about 10 μm to about 190 μm; (b) an average shell thickness of about 170 nm to about 1000 nm; (c) a volume core / shell ratio of about 50:50 to 99:1, preferably 60:40 to 99:1, more preferably 70:30 to 98:2, even more preferably 80:20 to 96:4; (d) a first shell component comprising an organic content of no more than about 5 wt%, preferably no more than about 2 wt%, more preferably about 0 wt%, based on the weight of the first shell component; or (e) mixtures thereof.

[0216] F. A liquid fabric care composition according to any of paragraphs A to E, wherein the compound of formula (I), formula (II), or both, is characterized by one or more of the following: (a) a polystyrene equivalent weight average molecular weight (Mw) of from about 700 Da to about 30,000 Da; (b) a degree of branching of from 0.2 to about 0.6; (c) a molecular weight polydispersity index of from about 1 to about 20; or (d) a mixture thereof.

[0217] G. A liquid fabric care composition according to any of paragraphs A to F, wherein for Formula (I), Formula (II), or both, M is silicon.

[0218] H. A liquid fabric care composition according to any of paragraphs A to G, wherein for formula (I), formula (II), or both, Y is OR, wherein R is selected from a methyl group, an ethyl group, a propyl group, or a butyl group, preferably an ethyl group.

[0219] I. The liquid fabric care composition of any of paragraphs A to H, wherein the second shell component comprises a material selected from the group consisting of calcium carbonate, silica, and combinations thereof.

[0220] J. The liquid fabric care composition according to any of paragraphs A to I, wherein the inorganic nanoparticles of the first shell component include at least one of metal nanoparticles, mineral nanoparticles, metal oxide nanoparticles, or semi-metal oxide nanoparticles, preferably, wherein the inorganic nanoparticles comprise one or more materials selected from the group consisting of SiO2, TiO2, Al2O3, Fe2O3, Fe3O4, CaCO3, clay, silver, gold, or copper, more preferably, wherein the inorganic nanoparticles comprise one or more materials selected from the group consisting of SiO2, CaCO3, Al2O3, and clay.

[0221] K. A liquid fabric care composition according to any of paragraphs A to J, wherein the inorganic second shell component comprises at least one of SiO2, TiO2, Al2O3, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, iron, silver, nickel, gold, copper or clay, preferably at least one of SiO2 or CaCO3, more preferably SiO2.

[0222] L. A liquid fabric care composition according to any of paragraphs A to K, wherein the liquid fabric care composition comprises from about 5% to about 99.5% water, by weight of the composition, preferably from about 50% to about 99.5%, more preferably from about 60% to about 95%, even more preferably from about 75% to about 90% water, by weight of the composition.

[0223] M. A liquid fabric care composition according to any one of paragraphs A to L, wherein the liquid fabric care composition is characterized by -1 and a viscosity at 21° C. of 1 centipoise to 1500 centipoise (1 mPa*s to 1500 mPa*s), 100 centipoise to 1000 centipoise (100 mPa*s to 1000 mPa*s), or 200 centipoise to 500 centipoise (200 mPa*s to 500 mPa*s).

[0224] N. A liquid fabric care composition according to any of paragraphs A to M, wherein the fabric treatment adjunct comprises the conditioning active, preferably wherein the conditioning active is present at a level of from about 1% to about 35% by weight of the composition.

[0225] O. A liquid fabric care composition according to any of paragraphs A to N, wherein the fabric treatment aid comprises the conditioning active, and wherein the conditioning active comprises an alkyl ester quat, preferably selected from the group consisting of monoester alkyl quats, diester alkyl quats, triester alkyl quats, and mixtures thereof.

[0226] P. A liquid fabric care composition according to any of paragraphs A to O, wherein the fabric treatment aid comprises a surfactant, preferably wherein the surfactant is present at a level of from about 1% to about 50%, more preferably from about 5% to about 45%, even more preferably from about 10% to about 40%, by weight of the composition.

[0227] Q. A liquid fabric care composition according to any of paragraphs A to P, wherein the fabric treatment aid comprises a surfactant, wherein the surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof.

[0228] R. A liquid fabric care composition according to any of paragraphs A to Q, wherein the liquid fabric care composition further comprises a material selected from silicones, non-ester quaternary ammonium compounds, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof, preferably silicones.

[0229] S. The liquid fabric care composition of any of paragraphs A to R, wherein the population of encapsulates is present at a level of from about 0.1% to about 10% by weight of the liquid fabric care composition.

[0230] T. The liquid fabric care composition of any of paragraphs A to S, wherein the liquid fabric care composition further comprises a structurant.

[0231] U. The liquid fabric care composition of any of paragraphs A to T, wherein the liquid fabric care composition is a liquid fabric enhancer.

[0232] V. The liquid fabric care composition of any of paragraphs A to U, wherein the liquid fabric care composition is packaged in a sprayable bottle.

[0233] W. A method for treating a surface, preferably a fabric, wherein the method comprises the step of contacting the surface with a liquid fabric care composition according to any of paragraphs A to V, optionally in the presence of water.

[0234] X. A method of preparing a liquid fabric care composition, comprising: providing a liquid base composition comprising a member selected from the group consisting of a fabric treatment adjunct, water, and mixtures thereof, wherein the fabric treatment adjunct is selected from the group consisting of a conditioning active, a surfactant, or mixtures thereof, wherein the conditioning active, if present, is selected from the group consisting of alkyl quaternary ammonium compounds, alkyl ester quaternary ammonium compounds, and mixtures thereof, and wherein the surfactant, if present, is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof; and providing a population of capsules to the base composition, wherein the capsules and / or liquid care composition are as described in any one of paragraphs A to V.

[0235] Y. Use of the capsules to provide a freshness benefit, a softening benefit, or a combination thereof to fabrics when the fabrics are treated with a fabric care composition comprising the capsules, wherein the capsules are as described in any one of paragraphs A to V.

[0236] Test Method

[0237] It should be understood that the test methods disclosed in the Test Methods section of this application should be used to determine the corresponding parameter values ​​of applicant's claimed subject matter as claimed and described herein.

[0238] Method for determining logP

[0239] The logarithm of the octanol / water partition coefficient (logP) was calculated for each PRM in the tested fragrance mixture. The logP of the individual PRMs was calculated using the Consensus logP Computational Model version 14.02 (Linux) available from Advanced Chemistry Development Inc. (ACD / Labs) (Toronto, Canada) to provide dimensionless logP values. The Consensus logP Computational Model from ACD / Labs is part of the ACD / Labs model suite.

[0240] Viscosity method

[0241] use The viscosity of the pure product was measured at about 20°C-21°C using a DV-E rotational viscometer, spindle 2, at 60 rpm.

[0242] Average shell thickness measurement

[0243] The capsule shell, including the first shell component and the second shell component, when present, was measured in nanometers using a focused ion beam scanning electron microscope (FIB-SEM; FEI Helios Nanolab 650) or equivalent on a delivery capsule containing twenty beneficial agents. The sample was prepared by diluting a small amount of liquid capsule dispersion (20 μl) with distilled water (1:10). The suspension was then deposited on an ethanol-cleaned aluminum rod and transferred to a carbon coater (Leica EM ACE600 or equivalent). The sample was vacuumed in the coater (vacuum level: 10 -5 The sample was dried at 500 mbar (1000 mbar). Next, 25 nm to 50 nm of carbon was quickly deposited onto the sample to deposit a conductive carbon layer onto the surface. The aluminum rod was then transferred to a FIB-SEM to prepare a cross section of the capsule. Using the cross-section cleaning mode, the cross section was prepared by ion milling at a 30 kV accelerating voltage with an emission current of 2.5 nA. Images were collected in immersion mode (dwell time of approximately 10 μs) at 5.0 kV and 100 pA with a magnification of approximately 10,000.

[0244] Images of the broken shells were collected as cross-sectional views of 20 randomly selected beneficial delivery capsules, unbiased by their size, to form a representative sample representing the size distribution of the capsules. The shell thickness of each of the 20 capsules was measured at three different random locations using calibrated microscope software by drawing a measurement line perpendicular to the tangent line to the outer surface of the capsule shell. 60 individual thickness measurements were recorded and used to calculate the average thickness.

[0245] Mean and coefficient of variation of volume-weighted capsule diameter

[0246] Capsule size distribution was determined by single particle optical sensing (SPOS) (also known as optical particle counting (OPC)) using an AccuSizer 780AD instrument or equivalent and accompanying software CW788 version 1.82 (Particle Sizing Systems, Santa Barbara, California, USA) or equivalent. The instrument was configured with the following conditions and options: flow rate = 1 mL / sec; lower size threshold = 0.50 μm; sensor model = LE400-05SE or equivalent; autodilution = on; collection time = 60 seconds; number of channels = 512; container fluid volume = 50 ml; maximum overlap = 9200. The measurement was started by rinsing the sensor with water until the background count was less than 100. A sample of the suspension of delivery capsules was introduced, and the density of the capsules was adjusted with DI water by autodilution as needed to obtain a capsule count of up to 9200 capsules / mL. The suspension was analyzed over a 60-second period. The size range used was 1 μm to 493.3 μm.

[0247] Volume distribution:

[0248]

[0249]

[0250]

[0251] in:

[0252] CoV v – Coefficient of variation of volume-weighted size distribution

[0253] σ v – Standard deviation of the volume-weighted size distribution

[0254] μ v – Average value of volume-weighted size distribution

[0255] d i – diameter in fraction i

[0256] x i,v – Frequency in fraction i (corresponding to diameter i) of the volume-weighted size distribution

[0257]

[0258] Volumetric core-shell ratio evaluation

[0259] The volume core-shell ratio value is determined as follows and is dependent on the average shell thickness as measured by the Shell Thickness Test Method. The volume core-shell ratio of a capsule whose average shell thickness is measured is calculated by the following formula:

[0260]

[0261] where thickness is the average shell thickness of the capsule population measured by FIBSEM, and D 胶囊 is the mean volume-weighted diameter of the capsule population measured by optical particle counting.

[0262] This ratio can be converted into a core-shell ratio fraction by calculating the core weight percentage using the following formula:

[0263]

[0264] And the shell percentage can be calculated based on the following formula:

[0265] % shell = 100 - % core.

[0266] Branching method

[0267] The degree of branching of the precursor was determined as follows: (29Si) nuclear magnetic resonance spectroscopy (NMR) was used to measure the degree of branching.

[0268] Sample preparation

[0269] Each sample was diluted to a 25% solution using deuterated benzene (Benzene-D6 "100%" (D, 99.96%, purchased from Cambridge Isotope Laboratories Inc., Tewksbury, MA, or equivalent). 0.015 M chromium (III) acetylacetonate (99.99% purity, purchased from Sigma-Aldrich, St. Louis, MO, or equivalent) was added as a paramagnetic relaxation reagent. If glass NMR tubes (Wilmed-LabGlass, Vineland, NJ, or equivalent) were used 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 samples. The same glass tubes must be used for analysis of both the blank and the samples.

[0270] Sample analysis

[0271] The degree of branching is determined using a Bruker 400 MHz nuclear magnetic resonance spectroscopy (NMR) instrument or equivalent. Standard silicon (29Si) methods (e.g., from Bruker) are used with default parameters set to a minimum of 1000 scans and a relaxation time of 30 seconds.

[0272] Sample processing

[0273] Use system software such as MestReNova version 12.0.4-22023 (purchased from Mestrelab Research) or equivalent that is applicable to NMR spectrum to store and process sample.Application phase adjustment and background correction.There is the big broad signal that extends to-136ppm from-70ppm, and this is the result using glass NMR tube and the glass that is present in the probe shell.This signal suppresses by subtracting the spectrum of blank sample from the spectrum of synthetic sample, and prerequisite is to analyze blank and sample using identical pipe and identical method parameter.In order to further illustrate any slight difference in aspects such as data collection, pipe, the region outside the peak of institute's concerned region is integrated and normalized to consistent value.For example, for all blanks and samples, integral-117ppm to-115ppm and integral value are set to 4.

[0274] The resulting spectrum yields up to five major peak areas. The first peak (Q0) corresponds to unreacted TAOS. The second set of peaks (Q1) corresponds to the end groups. The next set of peaks (Q2) corresponds to linear groups. The next set of broad peaks (Q3) are semi-dendritic units. The last set of broad peaks (Q4) are dendritic units. When analyzing PAOS and PBOS, each group falls within a defined ppm range. Representative ranges are described in the table below:

[0275]

[0276]

[0277] Polymethoxysilane has different chemical shifts for Q0 and Q1, overlapping signals for Q2, and unchanged Q3 and Q4, as shown in the following table:

[0278] Group ID Number of bridging oxygen per silicon ppm range Q0 0 -78 to -80 Q1 1 -85 to -88 Q2 2 -91 to -96 Q3 3 -100 to -106 Q4 4 -108 to -115

[0279] The ppm ranges shown in the table above may not apply to all monomers. Other monomers may cause chemical shift changes, however, the correct assignment of Q0-Q4 should not be affected.

[0280] Using MestReNova, each set of peaks was integrated and the degree of branching was calculated using the following formula:

[0281]

[0282] Molecular weight and polydispersity index determination method

[0283] The molecular weight (polystyrene equivalent weight average molecular weight (Mw)) and polydispersity index (Mw / Mn) of the condensation layer precursors described herein were determined using size exclusion chromatography with refractive index detection. Mn is the number average molecular weight.

[0284] Sample preparation

[0285] 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 volume with toluene. After the sample has dissolved in the solvent, it is passed through a 0.45 μm nylon filter and loaded into the instrument's autosampler.

[0286] Sample analysis

[0287] The HPLC system with automatic sampler (such as Waters 2695HPLC separation module, Waters Corporation, Milford MA, or equivalent) connected to a refractive index detector (such as Wyatt 2414 refractive index detector, Santa Barbara, CA, or equivalent) is used for polymer analysis. Separation is carried out on three chromatographic columns, each chromatographic column is 7.8mm ID × 300mm long, filled with 5μm polystyrene-divinylbenzene medium, connected in series, and it has a molecular weight cutoff value of 1kDA, 10kDA and 60kDA respectively. Suitable chromatographic columns are TSKGel G1000HHR, G2000HHR and G3000HHR chromatographic columns (purchased from TOSOH Bioscience, King of Prussia, PA) or equivalent. Use 6mm ID × 40mm long 5μm polystyrene-divinylbenzene guard column (such as TSKgel Guardcolumn HHR-L, TOSOH Bioscience, or equivalent) to protect the analytical column. Toluene (HPLC grade or equivalent) was pumped isocratically at 1.0 mL / min while the column and detector were maintained at 25° C. 100 μL of the prepared sample was injected for analysis. Sample data was stored and processed using software with GPC calculation capabilities (e.g., ASTRA version 6.1.7.17 software, available from Wyatt Technologies, Santa Barbara, CA, or equivalent).

[0288] The system is calibrated using ten or more narrowly dispersed polystyrene standards (e.g., the standard ReadyCal Set, (e.g., Sigma Aldrich, PN 76552, or equivalent)) with known molecular weight (in the range of approximately 0.250 kDa-70 kDa) and using a third-order fit of the Mp versus retention time curve.

[0289] Using the system software, calculate and record the weight average molecular weight (Mw) and polydispersity index (Mw / Mn).

[0290] Method for calculating the organic matter content in the first shell component

[0291] As used herein, the definition of an organic moiety in the inorganic shell of the capsule according to the present disclosure is: any moiety X that cannot be cleaved from a metal precursor bearing a metal M (where M belongs to the group of metals and semimetals and X belongs to the group of non-metals) via hydrolysis of an MX bond connecting the moiety to an inorganic precursor of a metal or semimetal M under specific reaction conditions will be considered organic. A minimum degree of hydrolysis of 1% when exposed to neutral pH distilled water for a duration of 24 hours without stirring was set as the reaction condition.

[0292] This method allows one to calculate the theoretical organic content assuming complete conversion of all hydrolyzable groups. Thus, it allows one to estimate the theoretical organic percentage for any silane mixture, with the result representing only the precursor mixture itself, not the actual organic content of the first shell component. Therefore, when a certain percentage of organic content is disclosed for a first shell component anywhere in this document, it should be understood that any mixture containing unhydrolyzed or prepolymerized precursors may have a theoretical organic content, according to the following calculation, lower than the disclosed amount.

[0293] Examples of silanes (but not limited to; see formula at the end of this section) :

[0294] Consider a mixture of silanes, where the mole fraction of each is Y i , and wherein i is the ID number of each silane. The mixture can be represented as follows:

[0295] Si(XR) 4-n R n

[0296] Wherein XR is a hydrolyzable group under the conditions mentioned in the above definition, R i ni It is not hydrolyzable under the above conditions, and n i =0, 1, 2 or 3.

[0297] This silane mixture will produce a shell with the following general formula:

[0298]

[0299] The weight percentage of the organic portion as previously defined can then be calculated as follows:

[0300] 1) Find the mole fraction of each precursor (including nanoparticles)

[0301] 2) Determine the general formula of each precursor (including nanoparticles)

[0302] 3) General formula for calculating the mixture of precursor and nanoparticles based on mole fractions

[0303] 4) Converted into reactive silane (all hydrolyzable groups are converted into oxygen groups)

[0304] 5) Calculate the weight ratio of the organic part relative to the total mass (assuming 1 mol of Si in the framework)

[0305] Example :

[0306]

[0307] To calculate the general formula of a mixture, multiply each atomic index in the individual chemical formulas by their respective mole fractions. Then, for mixtures, when similar indices occur (usually for ethoxy groups), take the sum of the fractional indices.

[0308] Note: Due to the calculation method (the sum of all mole fractions of Si is 1), the sum of all Si fractions in the mixture formula will always add to 1.

[0309] SiO 1*0.57+2*0.25 (OEt) 2*0.57+4*0.07+2*0.10 Me 2*0.10

[0310] SiO 1.07 (OEt) 1.62 Me 0.20

[0311] To convert the unreacted formula to the reacted formula, simply divide the indices of all hydrolyzable groups by 2 and then add them together (along with any pre-existing oxygen groups, if applicable) to obtain the fully reacted silane.

[0312] SiO 1.88 Me 0.20

[0313] In this case, the expected result is SiO1.9Me0.2, since the sum of all indices must satisfy the following formula:

[0314] A+B / 2=2,

[0315] Where A is the oxygen atom index and B is the sum of all non-hydrolyzable indices. Small rounding errors may occur during the calculation and should be corrected. The indices on the oxygen atoms are then readjusted to satisfy the formula.

[0316] Therefore, the final chemical formula is SiO 1.9 Me 0.2 , and the weight ratio of organic matter is calculated as follows:

[0317] Weight ratio = (0.20*15) / (28+1.9*16+0.20*15) = 4.9%

[0318] General :

[0319] The above formula can be generalized by taking into account the valence of the metal or semimetal M, giving the following modified formula:

[0320] M(XR) V-ni R i ni

[0321] And a similar approach is used, but the valence V of the corresponding metal is taken into account.

[0322] Method for measuring the iodine value of quaternary ammonium ester compounds

[0323] The iodine value of the quaternary ammonium ester fabric compound is that of the parent fatty acid from which the fabric conditioning active is formed and is defined as the grams of iodine which react with 100 grams of the parent fatty acid from which the fabric conditioning active is formed.

[0324] First, the quaternary ammonium ester compound is hydrolyzed according to the following protocol: 25 g of the fabric treatment composition is mixed with 50 mL of water and 0.3 mL of sodium hydroxide (50% active). The mixture is boiled on a hot plate for at least one hour while preventing the mixture from drying out completely. After one hour, the mixture is allowed to cool and the pH is adjusted to neutral (pH between 6 and 8) with 25% sulfuric acid using pH test paper strips or a calibrated pH electrode.

[0325] Next, extract fatty acid from the mixture via the liquid-liquid extraction with hexane or petroleum ether acidification: in the extraction cylinder, the sample mixture is diluted to 160mL with water / ethanol (1:1), 5 grams of sodium chloride, 0.3mL sulfuric acid (25% activity) and 50mL hexane are added. Stopper the cylinder and shake at least 1 minute. Then, make the cylinder stand, until form 2 layers. The top layer that will comprise the fatty acid hexane solution is transferred to another container. Use hot plate to evaporate hexane then, leave the fatty acid of extraction.

[0326] Next, the iodine value of the parent fatty acid forming the fabric conditioning active is determined according to ISO 3961:2013. The method for calculating the iodine value of the parent fatty acid comprises dissolving a predetermined amount (0.1-3 g) in 15 mL of chloroform. The dissolved parent fatty acid is then reacted with 25 mL of iodine monochloride in acetic acid (0.1 M). 20 mL of a 10% potassium iodide solution and 150 mL of deionized water are added thereto. After the halogen has been added, the excess iodine monochloride is determined by titrating with a sodium thiosulfate solution (0.1 M) in the presence of a blue starch indicator powder. At the same time, a blank is measured using the same amount of reagent and under the same conditions. The difference between the volume of sodium thiosulfate used in the blank and the volume of sodium thiosulfate used in the reaction with the parent fatty acid allows the iodine value to be calculated.

[0327] Leakage method

[0328] Testing for capsule leakage in liquid compositions (eg, liquid fabric enhancer / "LFE" compositions and / or heavy-duty liquid / "HDL" detergents) is performed as follows.

[0329] The homogenized slurry (with known fragrance activity, defined as the weight fraction of fragrance in the total slurry) is added and thoroughly dispersed into a known amount of LFE base or HDL base so that the fragrance weight fraction in the final formulation is 0.25 wt% (or 0.2 wt% to 0.3 wt%).

[0330] The formulated product was stored in jars or glass containers covered with airtight lids at 35°C and 40% relative humidity for 7 days, with the volume of the headspace above the liquid not exceeding 5 times the volume of the liquid itself.

[0331] Sample preparation

[0332] After 7 days of storage, samples of capsules, total oil, and free oil were prepared as follows:

[0333] (a) Capsule Sample Preparation: 0.1 g to 0.11 g of the slurry-containing formulation was introduced into the bottom of a GC vial (see GC vial details and methods below), which was then sealed with a crimp cap to create an airtight environment. This step was performed twice to obtain two readings, and the average of the two values ​​was used if they were not significantly different from each other, in which case the analysis was repeated. The GC vial was then analyzed by GC / MS, as detailed below.

[0334] (b) Preparation of the Total Oil Sample: A 1-gram aliquot of the formulation was introduced into a 7-ml cylindrical vial with a diameter of 1 to 1.5 cm, equipped with a magnetic stir bar no longer than the radius of the 7-ml vial to ensure proper mixing within the vial. The 1-gram aliquot in the 7-ml vial was then mixed on a stir plate at 500 rpm for 24 hours to ensure that the capsules were broken by the abrasive action of the stir bar against the bottom of the 7-ml vial. Optical microscopy was used to verify that no intact capsules remained. If such capsules were found, this step was repeated for an additional 24 hours, or until all or nearly all capsules were broken. The formulation containing the broken capsules was then introduced into a GC vial in a manner similar to step (a). This produced a total oil sample. It should be noted that the capsule sample and the total oil sample were not analyzed on the same day, as the total oil sample needed to be prepared after the seepage sample had been removed from storage. It should be noted that the capsule sample and the total oil sample were not analyzed on the same day, as the total oil sample needed to be prepared after the capsule sample had been removed from storage. This did not (or substantially) affect the results.

[0335] (c) Preparation of Free Oil Sample: Prepare an LFE or HDL formulation containing 0.2 to 0.3 wt% (preferably 0.25 wt%) free oil by adding and thoroughly dispersing a known amount of a fragrance oil composition into a known amount of LFE or HDL. The fragrance oil composition formulated herein is representative of the fragrance oil composition present in the slurry. The free oil formulation is then introduced into a GC sample vial in a manner similar to step (a). This creates a reference sample that must be used when analyzing capsule samples and total oil samples.

[0336] On each day of analysis, a capsule sample or a total oil sample must be run along with a reference sample.

[0337] GC / MS method

[0338] For each test sample and reference sample, a 0.1 gram to 0.11 gram aliquot of the sample was transferred to a 20 ml headspace vial (Gerstel SPME vial 20 ml, part number 093640-035-00) and immediately sealed (with a Gerstel Crimp cap for SPME, part number 093640-050-00). Two headspace vials were prepared for each sample. The sealed headspace vials were then allowed to equilibrate. The samples reached equilibrium after 3 hours at room temperature, but could be left standing for longer periods without compromising or changing the results, up to 24 hours after the headspace vials were sealed. After equilibration, the samples were analyzed by GC / MS.

[0339] GC / MS analysis was performed by sampling the headspace of each vial via SPME (50 / 30 μm DVB / Carboxen / PDMS, Sigma-Aldrich part number 57329-U) with a vial penetration of 25 mm and an extraction time of 1 minute at room temperature. The SPME fiber was then thermally desorbed online into the GC injector (270° C., splitless mode, 0.75 mm SPME inlet liner (Restek, part number 23434) or equivalent, 300 seconds desorption time, and 43 mm injector penetration). The fragrance composition was analyzed by fast GC / MS in full scan mode. Specific mass ion extractions were obtained for each component.

[0340] Leakage calculation

[0341] Leakage was calculated for capsule samples and total oil samples separately as follows, where "area" represents the area under the chromatographic peak corresponding to the PRM of interest:

[0342] For each PRM, the PRM leakage is given by:

[0343]

[0344] Once all PRMs are calculated for both the total oil sample and the capsule sample, the corrected PRM leakage can be calculated using the following formula:

[0345]

[0346] Once the corrected PRM leakage has been calculated for all PRMs, the average leakage can be found by taking the arithmetic mean of each corrected PRM leakage.

[0347] Example

[0348] The examples provided below are intended to be illustrative in nature and not intended to be limiting.

[0349] Example 1. Synthesis of non-hydrolyzable precursors

[0350] sample A.

[0351] Under nitrogen atmosphere, 1000g tetraethoxysilane (TEOS, purchased from Sigma Aldrich) is added to a clean, dry round-bottomed flask equipped with a stirring rod and a distillation apparatus. Add 490ml acetic anhydride (purchased from Sigma Aldrich) and 5.8g tetrakis (trimethylsiloxy) titanium (purchased from Gelest) and the contents of the flask are stirred at 135°C for 28 hours. During this period, the ethyl acetate generated by the reaction of the ethoxysilane group and the acetic anhydride is distilled out. The reaction flask is cooled to room temperature and placed on a rotary evaporator (Buchi Rotovapor R110) used in combination with a water bath and a vacuum pump (Welch 1402 DuoSeal) to remove any residual solvent and volatile compounds. The polyethoxysilane (PEOS) produced is a yellow viscous liquid with the following specifications found in Table 1. The ratio of TEOS to acetic anhydride can be changed to control the parameters presented in Table 1.

[0352] Table 1 .

[0353] PEOS parameters result Degree of branching (DB) 0.26 Molecular weight (Mw) 1.2 kDa Polydispersity Index (PDI) 3.9

[0354] sample B.

[0355] Under nitrogen atmosphere, 1000 grams of TEOS (available from Sigma Aldrich) are added into the clean dry round-bottom flask that is equipped with stirring rod and distilling apparatus.Then, add 564 grams of diacetic anhydride (available from Sigma Aldrich) and 5.9 grams of tetrakis (trimethylsiloxide) titanium (available from Gelest, Sigma Aldrich), and under agitation the content of flask is heated to 135 ℃.Under vigorous stirring, temperature of reaction is remained on 135 ℃ of places and continues 30 hours, during this period, distill out the organic ester that generates by the reaction of alkoxysilane group and diacetic anhydride and the other organic ester that generates by the condensation of silyl acetate group and other alkoxysilane groups, this condensation occurs when generating polyethoxysilane (PEOS).The reaction flask is cooled to room temperature and placed on the rotary evaporator (BuchiRotovapor R110) that is combined with water-bath and vacuum pump (Welch 1402DuoSeal), to remove any residual solvent. The degree of branching (DB), molecular weight (Mw) and polydispersity index (PDI) of the synthesized PEOS polymer are 0.42, 2.99 and 2.70, respectively.

[0356] Example 2. Synthesis of capsule populations

[0357] Group A .

[0358] The oil phase is prepared by mixing the precursor with the benefit agent and / or core modifier (one part precursor to four parts benefit agent and / or core modifier) ​​and homogenizing (or even dissolving if all compounds are miscible). 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 using an ultrasonic bath for at least 30 minutes.

[0359] Once the phases were prepared separately, they were combined (one part oil phase to four parts water) and the oil phase was dispersed into the water phase using an IKA ultraturrax S25N-10G mixing tool at 13,400 RPM / 1 minute. Once the emulsification step was complete, the resulting emulsions were cured at various time and temperature combinations (see Table 2A; "RT" = room temperature, approximately 22°C). To deposit the second shell component, the capsules were post-treated with a second shell component solution: the slurry was pre-diluted in 0.1 M HCl and treated with a controlled addition of a 10 wt% aqueous sodium silicate solution using a suspended magnetic stirring reactor at 350 RPM at room temperature (details regarding pre-dilution and infusion rate, as well as the amount of sodium silicate solution, are provided in Table 2A; a 25% dilution equals a 4-fold dilution). The pH was maintained constant at pH 7 using 1 M HCl (aq) and 1 M NaOH (aq) solutions. The capsules were stirred at 300 RPM for 24 hours, then centrifuged at 2500 rpm for 10 minutes and redispersed in deionized water.

[0360] To test whether the capsules collapse, the slurry must be diluted (at least 10 times) in deionized water. A few drops of the subsequent dilution are added to a microscope slide and allowed to dry overnight at room temperature. The next day, the dried capsules are observed under an optical microscope (without using a cover glass) by light transmission to assess whether the capsules have maintained their spherical shape.

[0361] Table 2A .

[0362]

[0363]

[0364] Figure 1 A schematic diagram of a method for preparing a capsule 8 having a first shell component 6 is shown, the capsule being prepared with a hydrophobic core 4. For example, in a first frame 100, an oil phase 1 is provided to an aqueous phase 2. The oil phase 2 contains a hydrophobic benefit agent, such as one or more fragrance raw materials, and a liquid precursor material. Nanoparticles 3 have surrounded the oil phase 1, for example forming a Pickering emulsion. In a second frame 101, a hydrolyzed precursor 5 begins to form at the interface around the core 4, wherein the core 4 contains the oil phase containing the benefit agent. In a third frame 102, a first shell component 6 is formed around the core 4, wherein the first shell component is formed by the nanoparticles 3 and the hydrolyzed precursor 5.

[0365] Figure 2 The schematic diagram in box 103 shows a capsule 9 having a shell 10 with a first shell part 6 and a second shell part 7 surrounding a core 4. The capsule 9 is shown in an aqueous phase 2. The core 4 comprises one or more flavor raw materials. Figure 3A scanning electron microscope image of a cross section of such a capsule 9 is shown. The core 4 is surrounded by a shell 10, wherein the shell 10 comprises a first shell part 6 surrounded by a second shell part 7.

[0366] Table 2B shows some parameters of the capsules of Sample A of Table 2A.

[0367] Table 2B .

[0368] parameter Sample A results Average diameter (μm) 37.5 CoV PSD (%) 24.7 Average shell thickness (nm) 371.2 Thickness to diameter ratio (%) 1.0％ Effective core-shell ratio 92:8 Shell organic matter% 0％

[0369] group B.

[0370] Five batches were prepared following the following procedure and after the curing step, the 5 batches were combined to produce a combined slurry:

[0371] An oil phase was prepared by mixing 3 g of the PEOS precursor synthesized above with 2 g of a benefit agent and / or core modifier (here, a fragrance oil) and homogenizing (or even dissolving, if all compounds were miscible). A 100 g aqueous phase was prepared by mixing 0.5 g of NaCl, 3.5 g of Aerosil 300 fumed silica from Evonik, and 96 g of deionized water. The fumed silica was dispersed in the aqueous phase using an IKA ultra-turrax (S25N) at 20,000 RPM for 15 min.

[0372] Once each phase was prepared separately, 5 g of the oil phase was dispersed into 16 g of the aqueous phase using an IKA Ultra-Turrax mixer (S25N-10g) at 25,000 RPM for 5 minutes to achieve the desired average oil droplet diameter. The pH was then adjusted to 1 using dropwise addition of 0.1 M HCl. Once the emulsification step was complete, the resulting emulsion was allowed to stand at room temperature for 4 hours without stirring and then at 90°C for 16 hours until sufficient solidification had occurred to prevent the capsules from collapsing. After the solidification step, the five batches were combined to obtain a combined capsule slurry.

[0373] To deposit the second shell component, the combined capsule slurry was post-treated with a second shell component solution. 50 g of the combined slurry was diluted with 50 g of 0.1 M HCl (aq). The pH was adjusted to 7 using dropwise addition of 1 M NaOH (aq). The diluted slurry was then treated with controlled addition (40 μl / min) of a second shell component precursor solution (20 ml of 15 wt% sodium silicate (aq)) at room temperature and 300 RPM using a suspended magnetic stirring reactor. The pH was maintained constant at pH 7 by continuous injection of 1.6 M HCl (aq) and 1 M NaOH (aq). The capsules were then centrifuged every 10 minutes at 2500 RPM. The supernatant was discarded, and the capsules were redispersed in deionized water.

[0374] To test whether the capsules collapsed, the slurry was diluted 10 times in deionized water. A few drops of the subsequent dilution were added to a microscope slide and allowed to dry overnight at room temperature. The next day, the dried capsules were observed under an optical microscope through light transmission to assess whether the capsules maintained their spherical shape (without using a cover glass). The capsules remained after drying and did not collapse. The average volume-weighted diameter of the capsules measured was 5.3 μm and the CoV was 46.2%. The percentage of organic matter content in the shell was 0%.

[0375] Example 3. Exemplary Liquid Fabric Care Composition Formulations

[0376] Exemplary formulations of liquid fabric care compositions, particularly liquid fabric enhancer ("LFE") compositions, are provided below in Table 3. A "base" liquid fabric enhancer containing no capsules can be prepared according to the following composition, but without the perfume capsules (ie, 0 wt%).

[0377] Table 3 .

[0378]

[0379]

[0380] 1 Esterquat 1: a mixture of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester, (2-hydroxypropyl)-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid ester and bis-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid ester, wherein the fatty acid ester is prepared from a C12-C18 fatty acid mixture (REWOQUAT DIP V20MConc from Evonik)

[0381] 2 Esterquat 2: N,N-bis(hydroxyethyl)-N,N-dimethylammonium chloride fatty acid ester, prepared from a C12-C18 fatty acid mixture (REWOQUAT CI-DEEDMAC, from Evonik)

[0382] 3 Esterquat 3: Esterification product of fatty acids (C16-18 and C18 unsaturated) with triethanolamine, quaternized with dimethyl sulfate (REWOQUAT WE 18 from Evonik)

[0383] *Capsules according to any of the samples AF in Table 2A above or as described in the subsequent Examples

[0384] Example 4. Comparison of leakage of different types of capsules in LFE formulations

[0385] This example compares the leakage profiles of different types of capsules.A base liquid fabric enhancer ("LFE") was prepared having the formulation provided in Example 3, Table 3, Composition 1.

[0386] Example 4-1 : A population of fragrance capsules encapsulating a mixture of fragrance raw materials "Fragrance 1" according to Example 2, Sample A was prepared. According to the present disclosure, the population of capsules includes a first shell component and a second shell component based on silica.

[0387] Comparative Example 4-1 : Encapsulates prepared according to the method disclosed in US Publication No. 2011 / 0268802, comprising a population of polyacrylate shelled fragrance capsules encapsulating the same fragrance raw material mixture ("Fragrance 1").

[0388] The two types of capsules were each added to a sample of a base liquid fabric softener composition to provide an equal amount of fragrance (0.25% by weight, based on the weight of the composition). The resulting product was stored at 35°C for one week. At the end of the storage period, samples of each product composition were analyzed for fragrance leakage from the capsules using headspace analysis. The data are reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially provided to the capsule. The results are provided in Table 4. Figure 4 Graph showing leakage results.

[0389] Table 4 .

[0390]

[0391] As shown in Table 4 above, capsules according to the present disclosure leaked relatively less on average for the PRMs tested compared to capsules having polyacrylate walls.

[0392] Furthermore, the standard deviation of the leakage rates of the capsules according to the present disclosure is relatively small compared to the standard deviation of the leakage rates of the polyacrylate capsules, indicating that the leakage rates of different PRMs are more consistent.

[0393] Example 5. Comparison of leakage of different types of capsules in HDL formulations

[0394] A basic heavy-duty liquid ("HDL") detergent composition was prepared having the formulation provided in Table 5A.

[0395] Table 5A .

[0396]

[0397]

[0398] Example 5-1

[0399] A population of fragrance capsules was prepared encapsulating a mixture of fragrance raw materials "Fragrance 1" according to Example 2, Sample A. According to the present disclosure, one population of capsules comprised a first shell member and a second shell member based on silica.

[0400] Comparative Example 5-1

[0401] Encapsulates prepared according to the method disclosed in US Publication No. 2011 / 0268802 comprised a population of polyacrylate shelled fragrance capsules encapsulating the same fragrance raw material mixture ("Fragrance 1").

[0402] Comparative Example 5-2

[0403] Capsules according to those disclosed in EP2500087B1 were prepared. 144 grams of fragrance 1 were weighed into a container. In a separate container, 96 grams of a 1 wt% CTAC solution were prepared by mixing 3.84 grams of a 25 wt% CTAC solution with DI water and adjusting the mass to 96 grams. The fragrance and surfactant mixture were mixed using an IKA ultraturrax mixer (S25N mixing tool) at 8000 rpm for 5 minutes.

[0404] Next, 144 g of water with a pH of 3.8 (adjusted with concentrated HCl) was added to the emulsion system prepared above.

[0405] Next, 27 g of a mixture containing 26.73 g of TEOS and 0.27 g of dimethyldiethoxysilane was added dropwise to the emulsion system under constant mixing. When all precursors were added, the mixture was heated to 50° C. and stirred at 200 rpm in a jacketed reactor with an overhead mixer for 2 hours.

[0406] Comparative Example 5-3

[0407] Capsules prepared according to those disclosed in WO2010013250A2 were prepared. The oil phase was prepared by mixing 20 grams of TEOS, 78 grams of isopropyl myristate (IPM), and 52 grams of fragrance 1. Next, the aqueous phase was prepared by weighing 10 grams of a 25% by weight CTAC (water) solution and adjusting the weight to 150 grams with DI water to achieve a CTAC concentration of 1.67% by weight. The two phases were mixed together at 6000 rpm for 1 minute using an Ultraturrax mixer (S25N tool from IKA). Next, 50 grams of Ludox TM50 were added, and the system was further mixed at 8000 rpm for another minute. Next, the pH was adjusted to 5 with 1M HCl.

[0408] To the above mixture were added 50 g of a 10 wt% aqueous solution of PVOH (selvol 540) and 5 g of a 25 wt% aqueous solution of sodium silicate. The pH was then readjusted to 4 and the system was stirred at 200 rpm at room temperature for 20 hours using an overhead mixer.

[0409] Each of the four capsule types was added to a sample of a heavy-duty liquid composition to provide an equivalent amount of fragrance (0.25%). The resulting product was stored at 35°C for one week. At the end of the storage period, a sample of each product composition was analyzed for fragrance leakage from the capsule using headspace analysis. The data is reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially supplied to the capsule. The results are provided in Table 5B.

[0410] Table 5B .

[0411]

[0412]

[0413] *The leakage values ​​for Comparative Examples 5-2 and 5-3 are sometimes higher than 100%. This is due to inherent measurement error, which can indicate leakage values ​​higher than 100% when the capsules are completely or nearly completely leaking. It has been found that the error in this method increases as the absolute leakage values ​​themselves become higher. These capsules are considered herein to have nearly complete or complete leakage during the test conditions.

[0414] As shown in Table 5B above, the capsules according to the present disclosure leaked relatively more on average for the PRMs tested compared to the capsules with polyacrylate walls (Comparative Example 5-1). However, the standard deviation of the leakage rates for the capsules according to the present disclosure was relatively small compared to the standard deviation of the leakage rates for the polyacrylate capsules, indicating a more consistent leakage rate across the different PRMs. Without wishing to be bound by theory, it is believed that consistent leakage rates across the different PRMs provide consistency in the flavor profile of the core flavor oil upon flavor release. Therefore, the silica-based capsules tested offer certain advantages in HDL products compared to the polyacrylate capsules tested.

[0415] Additionally, Comparative Examples 5-2 and 5-3, prepared according to the disclosure of previously disclosed silica capsules, exhibited high leakage of approximately 100%*, while Example 5-1, representing a capsule of the present disclosure, exhibited lower leakage but also consistent leakage for all PRMs tested. This demonstrates the importance of selecting the correct combination of the first shell component and the second shell component, as disclosed herein.

[0416] Example 6. Beneficial effects of the second shell component

[0417] This embodiment investigates the beneficial effects associated with the second shell member.

[0418] Example 6-1 : A population of capsules comprising a first shell member and a second shell member based on silica according to the present disclosure (Example 2, Sample A) was prepared, encapsulating "Fragrance 1".

[0419] Comparative Example 6-1 Comparative capsules having the same silica-based first shell member as in Example 6-1 but without the second shell member were also prepared, encapsulating the same fragrance mixture as in Example 6-1 ("Fragrance 1").

[0420] According to the formulation provided in Example 3, Table 3, Composition 1, two types of capsules were each administered to samples of a base liquid fabric enhancer ("LFE") at levels that provided equivalent amounts of fragrance. The resulting products were stored at 35°C for one week. At the end of the storage period, samples of each product composition were analyzed for fragrance leakage from the capsules using headspace analysis. Data are reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially administered to the capsule. The results are provided in Table 6.

[0421] Table 6 .

[0422]

[0423] As shown in Table 6, the leakage in the capsules with the second shell member was relatively less and relatively more consistent compared to the capsules without the second shell member.

[0424] Example 7. Benefits of Combining with Different Alkyl Ester Quats

[0425] According to Example 2, Sample A, capsules encapsulating fragrance 1 having a first shell component and a second shell component based on silica were prepared according to the present disclosure and provided in equal amounts to three different liquid base compositions, resulting in three products that can be used as liquid fabric care compositions (e.g., liquid fabric enhancers). Each composition (Compositions 1, 2, and 3) contained a different conditioning active, as provided in Table 3 of Example 3.

[0426] The resulting product was stored at 35°C for one week. At the end of the storage period, samples of each product composition were analyzed for fragrance leakage from the capsules using headspace analysis. Data are reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially supplied to the capsule. The results are provided in Table 7.

[0427] Table 7 .

[0428]

[0429] As shown in Table 7, leakage in capsules having first and second shell components based on silica was relatively similar and consistent across product formulations including various quaternary ammonium compound types.

[0430] Example 8. Beneficial effects of different fragrance mixtures

[0431] According to the present disclosure, two different fragrances were encapsulated in capsules having a first shell member and a second shell member based on silica, respectively (Samples C and D from Example 2, Table 2A).

[0432] According to the formulation provided in Example 3, Table 3, Composition 1, two types of capsules were each administered to samples of liquid fabric enhancer ("LFE") at levels providing equivalent fragrance. The resulting products were stored at 35°C for one week. At the end of the storage period, samples of each product composition were analyzed for fragrance leakage from the capsules using headspace analysis. Data are reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially administered to the capsule. The results are provided in Table 8.

[0433] Table 8 .PA230708C

[0434]

[0435] As shown in Table 8, capsules according to the present disclosure exhibited relatively low and consistent leakage in different fragrance formulations when stored in liquid fabric enhancer products. See also, for example, Example 7 above, which shows a low leakage profile for capsules containing Fragrance 1, as demonstrated in several composition matrices.

[0436] Example 9. Comparison with known capsule (1)

[0437] In this example, silica-based capsules according to the present disclosure were compared with silica-based capsules disclosed in EP 3 078 415 A (see Comparative Examples 9-1 and 9-2 below) using Fragrance 4. Each capsule was subjected to a leakage test.

[0438] Example 9-1 :

[0439] According to Example 2, Table 2A, Sample E, a population of fragrance capsules comprising a first shell member and a second shell member based on silica encapsulating a mixture of fragrance raw materials ("Fragrance 4") was prepared.

[0440] Comparative Example 9-1 :

[0441] The aqueous phase was prepared by diluting a 25 wt% CTAC (aqueous) solution (supplied by Sigma Aldrich) in DI water to a CTAC concentration of 0.52 wt%. The oil phase was prepared by mixing 40 g of "Fragrance 4" and 10 g of TEOS. The oil phase was mixed with 100 g of the aqueous phase using an ultraturrax mixer (S25N mixing tool from IKA) at 8500 rpm for 1 minute. The pH of the resulting emulsion was adjusted to 3.9 using 1 M NaOH (supplied by Sigma Aldrich). The emulsion was then stirred continuously at 160 rpm with an overhead stirrer and heated at 30° C. for 17 hours in a jacketed reactor that was covered to prevent evaporation of water or any other components. After 17 hours of reaction time, capsules formed. The capsules collapsed when air-dried.

[0442] Comparative Example 9-2 :

[0443] Capsules were prepared using the same method as Comparative Example 9-1, except that after forming the capsule slurry, the pH was adjusted to 3.2, and 5.7 g of TEOS was added dropwise over 320 minutes while maintaining the temperature at 30°C and the mixing rate at 160 rpm using an overhead stirrer. After all the TEOS was added, the slurry was mixed for an additional 18 hours using an overhead stirrer at 30°C and 160 rpm to produce capsules. The capsules did not collapse upon air drying.

[0444] Capsule slurries obtained from Example 9-1 and Comparative Examples 9-1 and 9-2 were each applied to samples of liquid fabric enhancer ("LFE") at levels providing equivalent fragrance, according to the formulation provided in Example 3, Table 3, Composition 1. The resulting products were stored at 35°C for one week. At the end of the storage period, samples of each product composition were analyzed for fragrance leakage from the capsules using headspace analysis. Data are reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially applied to the capsules. The results are provided in Table 9.

[0445] Table 9 .

[0446]

[0447]

[0448] As shown in Table 9, the test composition comprising the capsules of Example 9-1 was characterized by lower and more uniform leakage in the PRM compared to the comparative capsules.

[0449] Example 10. Comparison with known capsule (2)

[0450] In this example, silica-based capsules according to the present disclosure were compared with known capsules disclosed in EP2500087B1 (see Comparative Example 10-1 below) and WO2010013250A2 (see Comparative Example 10-2 below) using Fragrance 1. Example 10-2 and Comparative Example 10-2 each also contained a core modifier, specifically isopropyl myristate, or "IPM." Each capsule was subjected to a leakage test.

[0451] Example 10-1

[0452] The capsules of this example were prepared according to the protocol of Example 2, Sample F. The oil phase consisted of one part precursor and four parts a mixture of benefit agent and core modifier (Fragrance 1 and Isopropyl Myristate (IPM), respectively, in a 40 / 60 w / w ratio).

[0453] Example 10-2

[0454] The capsules of this example were prepared according to the protocol of Example 2, Sample A. The oil phase consisted of 1 part of the precursor and 4 parts of the fragrance 1.

[0455] Comparative Example 10-1

[0456] Capsules according to those disclosed in EP2500087B1 were prepared. 144 grams of fragrance 1 were weighed into a container. In a separate container, 96 grams of a 1 wt% CTAC solution were prepared by mixing 3.84 grams of a 25 wt% CTAC solution with DI water and adjusting the mass to 96 grams. The fragrance and surfactant mixture were mixed using an IKA ultraturrax mixer (S25N mixing tool) at 8000 rpm for 5 minutes.

[0457] Next, 144 g of water with a pH of 3.8 (adjusted with concentrated HCl) was added to the emulsion system prepared above.

[0458] Next, 27 g of a mixture containing 26.73 g of TEOS and 0.27 g of dimethyldiethoxysilane was added dropwise to the emulsion system under constant mixing. When all precursors were added, the mixture was heated to 50° C. and stirred at 200 rpm in a jacketed reactor with an overhead mixer for 2 hours.

[0459] Comparative Example 10-2

[0460] Capsules prepared according to those disclosed in WO2010013250A2 were prepared. The oil phase was prepared by mixing 20 grams of TEOS, 78 grams of isopropyl myristate (IPM), and 52 grams of fragrance 1. Next, the aqueous phase was prepared by weighing 10 grams of a 25% by weight CTAC (water) solution and adjusting the weight to 150 grams with DI water to achieve a CTAC concentration of 1.67% by weight. The two phases were mixed together at 6000 rpm for 1 minute using an Ultraturrax mixer (S25N tool from IKA). Next, 50 grams of Ludox TM50 were added, and the system was further mixed at 8000 rpm for another minute. Next, the pH was adjusted to 5 with 1M HCl.

[0461] To the above mixture were added 50 g of a 10 wt% aqueous solution of PVOH (selvol 540) and 5 g of a 25 wt% aqueous solution of sodium silicate. The pH was then readjusted to 4 and the system was stirred at 200 rpm at room temperature for 20 hours using an overhead mixer.

[0462] According to the formulation provided in Example 3, Table 3, Composition 1 above, capsule slurries obtained from Examples 10-1 and 10-2 and Comparative Examples 10-1 and 10-2 were each applied to samples of liquid fabric enhancer ("LFE") at levels providing equivalent amounts of fragrance. The resulting products were stored at 35°C for one week. At the end of the storage period, samples of each product composition were analyzed for fragrance leakage from the capsules using headspace analysis. Data are reported as a percentage, determined by comparing the amount of each fragrance raw material found in the headspace to the amount initially applied to the capsules. The results are provided in Table 10. Figure 5 Graph showing leakage results.

[0463] Table 10 .

[0464]

[0465]

[0466] As indicated by the results shown in Table 10, it is important to use a first shell component (comprising the correct precursor of formula (I)) in combination with a second shell component as described in the present disclosure in order to obtain both low leakage and uniform leakage for the PRMs tested.

[0467] Example 11. Exemplary Fabric Freshener Spray Formulations

[0468] Exemplary formulations for fabric refresher spray compositions are provided in Table 11. The liquid compositions provided in Table 11 can be packaged in any sprayer disclosed herein. The compositions can be sprayed onto target fabrics.

[0469] Table 11 .

[0470]

[0471] 1 Konjac gum aqueous solution ( XP 3464, FMC Corporation, Philadelphia, PA); 1% active substance

[0472] 2 Xanthan gum aqueous solution; 1% active ingredient

[0473] 3 Silica-based flavor capsules having a first member and a second shell member as disclosed in the present disclosure; see, for example, the capsules of Example 2.

[0474] 4 KemEcal 142PG, 100%, Kemira Chemicals, Inc., Atlanta, BA

[0475] 5 Diethylene glycol, 99.6% (100%), Indorama Ventures LLC, Pasadena, TX

[0476] 6 Polyalkylene oxide methylsiloxane copolymer, 60-100% (100%), Momentive TM ,

[0477] 7 Hydroxypropyl beta-cyclodextrin (CD) slurry - Cavasol W7 HP TL, 40%, Wacker Biosolutions, Munchen, Germany

[0478] 8 Ethanol- SDA40B / 190PF / DNB TBA / 137600,94.3%, Equistar Chemicals, LP, Houston, TX

[0479] 9 Koralone TM B-119 preservative, 1,2-benzisothiazolin-3-one, 19%, The Dow Chemical Company, Philadelphia, PA

[0480] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0481] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the presently disclosed or claimed inventions, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0482] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended that all such changes and modifications within the scope of the invention be encompassed in the appended claims.

Claims

1. A liquid fabric care composition comprising: Fabric treatment auxiliaries, wherein the fabric treatment aid is selected from the group consisting of conditioning actives, surfactants or mixtures thereof, in, If present, the conditioning active is selected from the group consisting of alkyl quaternary ammonium compounds, alkyl ester quaternary ammonium compounds, and mixtures thereof, and wherein the surfactant, if present, is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and mixtures thereof, wherein the anionic surfactant is selected from the group consisting of alkoxylated alkyl sulfates, alkylbenzene sulfonates, methyl ester sulfonates, paraffin sulfonates, alpha-olefin sulfonates, internal olefin sulfonates, alkyl ether carboxylates, and any mixtures thereof; and Capsule group, Each capsule in the capsule population comprises a core and a shell surrounding the core, wherein the core comprises a fragrance raw material, wherein the shell comprises: an inorganic first shell component comprising a condensation layer and a nanoparticle layer, wherein the condensation layer comprises a condensation product of a precursor, wherein the nanoparticle layer comprises inorganic nanoparticles, and wherein the condensation layer is disposed between the core and the nanoparticle layer; an inorganic second shell member surrounding the first shell member, wherein the inorganic second shell member surrounds the nanoparticle layer; wherein the precursor comprises at least one compound selected from the group consisting of formula (I), formula (II) and mixtures thereof; Wherein formula (I) is (M v O z Y n ) w , Wherein formula (II) is (M v O z Y n R 1 p ) w , Wherein for formula (I), formula (II) or a mixture thereof: each M is independently selected from the group consisting of silicon, titanium and aluminum, v is the valence number of M and is 3 or 4, z is 0.5 to 1.6, Each Y is independently selected from -OH, -OR 2 ,halogen, 、-NH2、-NHR 2 、-N(R 2 )2 and , where R 2 C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl or 5-12 membered heteroaryl, wherein the heteroaryl contains 1 to 3 ring heteroatoms selected from O, N and S, where R 3 H, C1 to C 20 Alkyl, C1 to C 20 Alkylene, C6 to C 22 aryl or 5-12 membered heteroaryl, wherein the heteroaryl contains 1 to 3 ring heteroatoms selected from O, N and S, w is 2 to 2000; Wherein for formula (I), n is 0.7 to (v-1); and Wherein for formula (II), n is 0 to (v-1); Each R 1 Independently selected from the group consisting of: C1 to C 30 Alkyl; C1 to C 30 Alkylene; C1 to C2 substituted by a member selected from the group consisting of halogen, -OCF3, -NO2, -CN, -NC, -OH, -OCN, -NCO, alkoxy, epoxy, amino, mercapto, acryloyl, -CO2H, -C(O)-alkyl, -C(O)O-aryl and -C(O)O-heteroaryl 30 Alkyl; C1 to C2 substituted by a member selected from the group consisting of 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 an alkylene group; and p is a number greater than zero and at most pmax, Where pmax = 60 / [9*Mw(R 1 ) + 8], Where Mw(R 1 ) is R 1 The molecular weight of the group.

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

3. A liquid fabric care composition according to claim 2, wherein the precursor is free of compounds according to formula (II).

4. A liquid fabric care composition according to any one of claims 1 or 2, wherein the precursor comprises at least one compound according to formula (II).

5. The liquid fabric care composition of claim 1 , wherein the capsule population is characterized by one or more of the following: (a) Average volume-weighted capsule diameter from 10 µm to 200 µm; (b) average shell thickness ranging from 170 nm to 1000 nm; (c) a volumetric core / shell ratio of 50:50 to 99:1; (d) the first shell member comprises an organic content of not more than 5% by weight based on the weight of the first shell member, or (e) mixtures thereof.

6. The liquid fabric care composition of claim 1 , wherein the compound of formula (I), formula (II), or both, is characterized by one or more of the following: (a) a polystyrene equivalent weight average molecular weight (Mw) of 700 Da to 30,000 Da; (b) a degree of branching of 0.2 to 0.6; (c) a molecular weight polydispersity index of 1 to 20; or (d) mixtures thereof.

7. The liquid fabric care composition of claim 1, wherein for Formula (I), Formula (II), or both, M is silicon.

8. The liquid fabric care composition of claim 1, wherein for Formula (I), Formula (II), or both, Y is OR, wherein R is selected from a methyl group, an ethyl group, a propyl group, or a butyl group.

9. The liquid fabric care composition of claim 1, wherein the inorganic second shell component comprises a material selected from the group consisting of calcium carbonate, silica, and combinations thereof.

10. The liquid fabric care composition of claim 1, wherein the inorganic nanoparticles of the first shell component comprise at least one of metal nanoparticles, mineral nanoparticles, metal oxide nanoparticles, or semi-metal oxide nanoparticles.

11. The liquid fabric care composition according to claim 10, wherein the inorganic nanoparticles comprise one or more materials selected from the group consisting of SiO2, TiO2, Al2O3, Fe2O3, Fe3O4, CaCO3, clay, silver, gold or copper.

12. The liquid fabric care composition according to claim 10, wherein the inorganic nanoparticles comprise one or more materials selected from the group consisting of SiO2, CaCO3, Al2O3 and clay.

13. The liquid fabric care composition of claim 1, wherein the inorganic second shell component comprises at least one of SiO2, TiO2, Al2O3, CaCO3, Ca2SiO4, Fe2O3, Fe3O4, iron, silver, nickel, gold, copper, or clay.

14. The liquid fabric care composition according to claim 13, wherein the inorganic second shell member comprises at least one of SiO2 or CaCO3.

15. The liquid fabric care composition of claim 1, wherein the liquid fabric care composition comprises from 5% to 99.5%, by weight of the composition, of water.

16. The liquid fabric care composition of claim 1, wherein said fabric treatment aid comprises said conditioning active, Wherein the conditioning active is present at a level of from 1% to 35% by weight of the composition.

17. The liquid fabric care composition according to claim 1, wherein said fabric treatment aid comprises said surfactant, Wherein the surfactant is present at a level of from 1% to 50% by weight of the composition.

18. The liquid fabric care composition of claim 1, wherein the liquid fabric care composition further comprises a structurant.

19. A method for treating a surface, wherein the method comprises the following steps: The surface is contacted with a liquid fabric care composition according to any preceding claim, optionally in the presence of water.

20. The method of claim 19, wherein the surface is a fabric.

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