microcapsules

Abstract

c) an inner shell that encapsulates the benefit agent; and d) a cross-linked polysaccharide outer shell; wherein the crosslinking is effected by at least one oligofunctional (meth)acrylate compound, The resulting core-shell microcapsules have a reduced content of materials derived from non-renewable sources.

Description

[Technical Field]

[0001] The present disclosure relates to encapsulated compositions comprising at least one core-shell microcapsule, as well as methods for preparing such encapsulated compositions and their use to enhance the performance of benefit agents in consumer products. [Background technology]

[0002] It is known to incorporate encapsulated benefit agents into consumer products such as household care products, personal care products, and fabric care products. Examples of benefit agents include fragrances, cosmetic agents, food ingredients, nutraceuticals, drugs, matrix enhancers, and the like. Microcapsules particularly suited for delivering such benefit agents are core-shell microcapsules, where the core typically contains the benefit agent and the shell is impermeable or partially impermeable to the benefit agent. Generally, these microcapsules are employed in aqueous media, and the encapsulated benefit agent is hydrophobic. A wide variety of shell materials can be used, provided that the shell material is impermeable or partially impermeable to the encapsulated benefit agent.

[0003] Benefit agents are encapsulated for a variety of reasons. Microcapsules can isolate and protect such materials from external suspension media, such as consumer product bases, that may be incompatible or unstable. They are also used to aid in the deposition of benefit agents onto substrates such as skin and hair, or, in the case of fragrance ingredients, fabrics and hard household surfaces. They also serve as a means of controlling the spatiotemporal release of benefit agents.

[0004] The prior art has proposed a wide variety of encapsulation vehicles and benefit agents suitable for preparing encapsulated compositions. Such encapsulation vehicles include synthetic resins made from polyamides, polyureas, polyurethanes, polyacrylates, melamine-derived resins, or mixtures thereof. Aminoplast capsules, especially melamine formaldehyde, have been found to be particularly successful. There is an increasing desire to provide microcapsules that contain a reduced proportion of materials derived from non-renewable resources, such as synthetic petrochemicals. However, it has been found to be difficult to provide such capsules that can be encapsulated with high encapsulation efficiency and that are sufficiently impermeable to benefit agents during storage. Summary of the Invention

[0005] Here, a) an inner shell that encapsulates the benefit agent; and b) a cross-linked polysaccharide outer shell; wherein the crosslinking is effected using at least one oligofunctional (meth)acrylate compound. "Benefit Agent" means any substance that, when added to a product, may enhance consumer awareness of the product or enhance the product's performance in an application. Exemplary benefit agents include fragrance ingredients, flavor ingredients, cosmetic ingredients, bioactive agents (such as disinfectants, insect repellents, and pheromones), substrate enhancers (such as silicones and brighteners), enzymes (such as lipases and proteases), dyes, pigments, nutraceuticals, and the like.

[0006] The inner shell of the microcapsules encapsulating the benefit agent may be made of any suitable material. This will, of course, depend on the nature of the benefit agent and the desired end use. It may be a natural material, such as gelatin, or one of the many synthetic materials known and used in the art as capsule wall forming agents. Representative examples include (meth)acrylates, aminoplast resins such as melamine formaldehyde and urea formaldehyde, polyureas, and the like. Specific embodiments of the inner shell are described in further detail herein.

[0007] The polysaccharide can be selected from any polysaccharide capable of cross-linking with a linker molecule, which is an oligofunctional (meth)acrylate compound, as further described herein. Such polysaccharides include those containing uronic acid units, i.e., those in which CHOH has been oxidized to form COOH groups. In certain embodiments, the polysaccharide includes hexuronic acid units. Polysaccharides containing uronic acid units, particularly hexuronic acid units, are widely available in nature.

[0008] The hexuronic acid unit is selected from the group consisting of a galacturonic acid unit, a glucuronic acid unit, in particular a 4-O-methyl-glucuronic acid unit, a glucuronic acid unit and a mannuronic acid unit. The polysaccharides containing carboxylic acid groups may be branched. Branched polysaccharides containing carboxylic acid groups have the advantage of forming a more compact network than linear polysaccharides and therefore may be more impermeable to the encapsulation shell, resulting in reduced leakage and higher encapsulation efficiency.

[0009] The carboxylic acid groups may be partially present in the form of the corresponding methyl ester. The proportion of the carboxylic acid groups present in the form of the corresponding methyl ester may be 3% to 95%, preferably 4% to 75%, more preferably 5% to 50%. Alternatively, the proportion of the carboxylic acid groups present in the form of the corresponding methyl ester may be less than 50%.

[0010] In the context of the present disclosure, polysaccharides containing 50% or more of their carboxylic acid groups present in the form of their corresponding methyl esters are referred to as "highly methoxylated." Polysaccharides containing less than 50% of their carboxylic acid groups present in the form of their corresponding methyl esters are referred to as "lowly methoxylated." The carboxylic acid groups may be at least partially present in the form of the corresponding carboxylate salts, in particular the corresponding sodium, potassium, magnesium, or calcium carboxylate salts.

[0011] In an alternative embodiment of the present disclosure, the carboxylic acid groups may be at least partially present in the form of a complex with a species selected from the group consisting of zirconium species, titanium species, and boron species, where the species is particularly an oxide. Without being bound by theory, it is speculated that the presence of carboxylates or complexes in polysaccharides limits their aqueous solubility, thereby facilitating the formation of capsule shells. Furthermore, polyvalent metal species may promote intermolecular cross-linking, which may also improve the encapsulation properties of the shell.

[0012] The linker molecule is selected from oligofunctional acrylate or methacrylate compounds, and may also be selected from any compound having multiple ethylenically unsaturated terminal double bonds, typically 2 to 6, and especially 2 to 4 such bonds. While any such compound may be used, specific examples are as follows: 3: 3-(acryloyloxy)-2-hydroxypropyl methacrylate 15: Ethylene glycol dimethacrylate 16: 1,3-butylene glycol dimethacrylate 17: 1,3,5-triacryloylhexahydro-1,3,5-triazine 18: Tris(2-acryloyloxyethyl)isocyanurate 19: Pentaerythritol tetraacrylate [ka]

[0013] In certain embodiments, the inner shell is formed by the reaction of an aminosilane with a multifunctional diisocyanate. The aminosilane may be selected from compounds of formula (I): [ka]

[0014] In formula (I), R 1, R 2 and R 3 are each independently a C1-C4 linear or branched alkyl or alkenyl residue, especially methyl or ethyl, and R 4 The amine functional group is a C1-C, including, inter alia, primary, secondary or tertiary amines. 12 is preferably a C1-C4, linear or branched alkyl or alkenyl residue.

[0015] When the functional group is a primary amine, it may be a terminal primary amine. 4 is then preferably a C1-C8, even more preferably a C1-C4, linear terminal primary aminoalkyl residue. Specific aminosilanes in this category are selected from the group consisting of aminomethyltriethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, 5-aminopentyltriethoxysilane, 6-aminohexyltriethoxysilane, 7-aminoheptyltriethoxysilane, and 8-aminooctyltriethoxysilane.

[0016] Without being bound by theory, it is believed that the silane groups polycondense with each other to form a silica network at the liquid-liquid interface, further stabilizing this interface.

[0017] The aminosilane may be a bipodal aminosilane. By "bipodal aminosilane" is meant a molecule containing at least one amino group and two residues, each having at least one alkoxysilane moiety. In certain embodiments of the present disclosure, at least one bipodal aminosilane has formula (II). (OR 4 ) (3-f) (R 3 ) f Si-R 2 -XR 2 -Si(OR 4 ) (3-f) (R 3 ) f Formula (II)

[0018] In the above formula (II), X is —NR 1 -, -NR 1 -CH2-NR 1 -, -NR 1 -CH2-CH2-NR 1 -, -NR 1 -CO-NR 1 -,or [ka] Represents.

[0019] In the above formula (II), R 1 R each independently represents H, CH3 or C2H5. 2 R each independently represents a linear or branched alkylene group having 1 to 6 carbon atoms. 3 each independently represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms; each R4 independently represents H or a straight-chain or branched alkyl group having 1 to 4 carbon atoms; and f represents 0, 1, or 2.

[0020] Bidentate aminosilanes are particularly advantageous in forming stable oil-water interfaces compared to conventional silanes. Examples of bidentate aminosilanes include, but are not limited to, bis(3-(triethoxysilyl)propyl)amine, N,N'-bis(3-(trimethoxysilyl)propyl)urea, bis(3-(methyldiethoxysilyl)propyl)amine, N,N'-bis(3-(trimethoxysilyl)propyl)ethane-1,2-diamine, bis(3-(methyldimethoxysilyl)propyl)-N-methylamine, and N,N'-bis(3-(triethoxysilyl)propyl)piperazine.

[0021] The bidentate aminosilane can be a secondary aminosilane.Using a secondary bidentate aminosilane instead of a primary aminosilane reduces the reactivity of the polymer stabilizer to electrophilic species, especially aldehyde.Therefore, the beneficial agent that contains high levels of aldehyde can be encapsulated with less tendency to have adverse interactions between core-forming materials and shell-forming materials. In a particular embodiment, the secondary bidentate aminosilane is bis(3-(triethoxysilyl)propyl)amine. This particular secondary aminosilane has the advantage that during polycondensation of the ethoxysilane groups, ethanol is released instead of the more toxic and less desirable methanol.

[0022] Other aminosilanes can also be used in combination with the aforementioned bidentate aminosilanes, particularly those described hereinabove. The weight ratio of aminosilane to polymeric surfactant may be from 0.1 to 1.1, especially from 0.2 to 0.9, even more especially from 0.3 to 0.7, for example 0.5.

[0023] The polyfunctional isocyanate may be selected from alkyl, alicyclic, aromatic and alkylaromatic having two or more (eg, 3, 4, 5, etc.) isocyanate groups in the molecule, and anion-modified polyfunctional isocyanates.

[0024] Preferably, at least one polyfunctional isocyanate is an aromatic or alkylaromatic polyfunctional isocyanate, and the alkylaromatic polyfunctional isocyanate preferably has a methyl isocyanate group attached to the aromatic ring. Both aromatic and methyl isocyanate-substituted aromatic polyfunctional isocyanates have superior reactivity compared to alkyl and alicyclic polyfunctional isocyanates. Among these, 2-ethylpropane-1,2,3-triyltris((3-(isocyanatomethyl)phenyl)carbamate) is particularly preferred due to its tripodal nature, which favors the formation of intermolecular crosslinks, and its intermediate reactivity, which favors network uniformity. This alkylaromatic polyfunctional isocyanate is commercially available, sold by Mitsui under the trademark Takenate™ D-100N or by Covestro under the trademark Desmodur™ Quix 175.

[0025] In certain embodiments, the initial inner shell formation is stabilized in suspension in the aqueous phase using a polymeric stabilizer, such as those described in International Publication WO 2020 / 233887 and further described herein below.

[0026] The polymeric stabilizer is formed by combining a polymeric surfactant with at least one aminosilane. By "polymeric surfactant" is meant a polysaccharide or a mixture containing at least one polysaccharide that, when dissolved in one or both of the oil and water phases, reduces the interfacial tension between the oil and water phases.

[0027] In certain embodiments of the present disclosure, the polymeric stabilizer is formed by combining pectin with bis(3-(triethoxysilyl)propyl)amine. Preferably, the polymeric stabilizer is formed by combining pectin with bis(3-(triethoxysilyl)propyl)amine and 2-ethylpropane-1,2,3-triyltris((3-(isocyanatomethyl)phenyl)carbamate). The combination of these natural polymeric surfactants with bidentate secondary aminosilanes provides particularly advantageous interfacial stability and release characteristics. The stabilized interface is sufficiently impermeable to effectively encapsulate at least one benefit agent contained in the core. The polymeric stabilizer effectively forms a shell that encapsulates at least one perfume ingredient contained in the core. The volume average size (d50) of the core-shell microcapsules according to the present disclosure is generally 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 30 μm.

[0028] In another aspect, the present disclosure relates to encapsulated compositions, particularly those described hereinabove. The encapsulated composition comprises at least one core-shell microcapsule. The at least one core-shell microcapsule comprises a core containing at least one benefit agent and a shell surrounding the core. The shell comprises a polymeric stabilizer formed by a combination of a polymeric surfactant and at least one aminosilane. The shell additionally comprises a polysaccharide, preferably a polysaccharide containing beta(1→4)-linked monosaccharide units, even more preferably a cellulose derivative, especially one selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl methylcellulose, cellulose acetate, and carboxymethyl cellulose, preferably hydroxyethyl cellulose.

[0029] For the avoidance of doubt, the polymeric stabilizer referred to in the preceding paragraph need not be a polysaccharide containing carboxylic acid groups. If the polymeric stabilizer referred to in the preceding paragraph is a polysaccharide containing carboxylic acid groups, the further polysaccharide contained in the shell is a different polysaccharide.

[0030] It has been found that polymeric stabilizers are a relevant factor in balancing the stability of microcapsules with respect to both perfume leakage during storage and perfume release during use. In particular, the importance of providing additional stability at the oil-water interface has been recognized. Thus, polymeric stabilizers provide a highly stable platform, allowing the addition of additional shell materials and / or shell precursors to form new encapsulated perfume compositions. More specifically, the addition of polysaccharides, preferably polysaccharides containing beta(1→4)-linked monosaccharide units, and even more preferably cellulose derivatives, leads to more sustainable microcapsules with excellent release properties.

[0031] The polysaccharide may be deposited on the outer surface of the capsule shell formed by the polymeric stabilizer, resulting in a multi-layer shell containing at least one layer of polymeric stabilizer and one layer of polysaccharide. Increasing the amount of encapsulating material may improve the impermeability of the encapsulating shell. For the avoidance of doubt, the present disclosure is by no means limited to shells having clearly defined, discrete layers, although this is one possible embodiment. More specifically, the layers may be graded and discontinuous. On the other hand, the shell may also be essentially uniform.

[0032] The polysaccharides may react with the unreacted isocyanate groups and increase the density of the crosslinked shell, but they may also interact with the polymer stabilizer through physical forces and interactions such as hydrogen bonding, ionic interactions, hydrophobic interactions, or electron transfer interactions. The shell further comprising a polysaccharide can be further stabilized with a stabilizer. Preferably, the stabilizer comprises at least two carboxylic acid groups. Even more preferably, the stabilizer is selected from the group consisting of citric acid, benzene-1,3,5-tricarboxylic acid, 2,5-furandicarboxylic acid, itaconic acid, poly(itaconic acid), and combinations thereof.

[0033] Another aspect of the present disclosure relates to a method for preparing an encapsulated composition, particularly an encapsulated composition as described herein, comprising the steps of: a) providing a polymeric surfactant; b) providing an aqueous phase; c) dissolving or dispersing the polymeric surfactant in the aqueous phase; d) providing at least one aminosilane; e) providing an oil phase comprising at least one benefit agent; f) Optionally: dissolving at least one aminosilane in the oil phase; g) emulsifying an oil phase and an aqueous phase in the presence of both a polymeric surfactant and an aminosilane to form an emulsion of oil droplets in the aqueous phase; h) causing at least one aminosilane and a polymeric surfactant to form a shell at the oil-water interface of the emulsified oil droplets, thereby forming a slurry of microcapsules; i) adding a polysaccharide, preferably a polysaccharide comprising beta(1→4) linked monosaccharide units, even more preferably a cellulose derivative, in particular a polysaccharide selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, carboxymethyl cellulose, preferably hydroxyethyl cellulose, to the microcapsule slurry formed in step h); j) Crosslinking polysaccharides with oligoacrylates / methacrylates Oil-in-water emulsions have the advantage of providing multiple droplets that can be used as templates for shell formation, where a shell is built around each of these droplets. In addition, the droplet size distribution within the emulsion may be controlled by controlling emulsification conditions such as stirring speed and stirrer geometry. The result is multiple microcapsules with a controlled average size and size distribution, where the oil phase is encapsulated to form the microcapsule core.

[0034] In a variation of step i), instead of adding all of the polysaccharide in this step, some polysaccharide can be added in step g) and thus incorporated into the shell formed by the aminosilane / polymer surfactant shell. The oligoacrylate / methacrylate then reacts with both the polysaccharide in the shell and the polysaccharide added in step i). Regarding step (h), the formation of the polymeric stabilizer is preferably initiated by adjusting the pH to a range of 4.0 to 7.5, depending on the polymeric surfactant. For high methoxylated pectin, the optimum pH range is 6.5±0.5, for alginate the optimum pH range is 7.0±0.5, and for low methoxylated pectin and gum arabic the optimum pH range is 4.5±0.5.

[0035] The temperature is preferably maintained at room temperature for at least 1 hour and then increased to at least 60° C., preferably at least 70° C., more preferably at least 80° C., but not exceeding 90° C., for example 85° C. Under such conditions, the formation of the shell is well controlled, which means that optimal stabilization of the interface is obtained. An appropriate agitation speed and configuration of the mixer can be selected to obtain the required average droplet size and droplet size distribution. A feature of the present disclosure is that the polymeric stabilizer has sufficient surface activity and can promote the formation of dispersed oil droplets of the desired size.

[0036] The process described herein may utilize a 1-liter vessel equipped with a turbine or a cross-beam agitator with a pitch beam, such as a MIG agitator, with a ratio of agitator diameter to reactor diameter of 0.6-0.8. Microcapsules may be formed in reactors with a volume average particle size (d50) of 30 microns or less, more specifically 20 microns or less, at agitation speeds of about 100 to about 1200 rpm, more specifically about 600-1000 rpm. Preferably, a MIG agitator is used operating at a speed of 850 + / - 50 rpm. However, those skilled in the art will readily appreciate that such agitation conditions may vary depending on the reactor size and batch size, the exact geometry of the agitator, and the diameter ratio (i.e., the ratio of the agitator diameter to the reactor diameter). For example, for a MIG agitator with an agitator-to-reactor diameter ratio of 0.5-0.9 and a slurry volume ranging from 0.5 to 8 tons, a preferred agitation speed in the context of this disclosure is 150 rpm to 50 rpm.

[0037] In certain embodiments of the present disclosure, the weight ratio of aminosilane to polymeric surfactant in the emulsion is set within the range of 0.1 to 1.1, more specifically 0.2 to 0.9, and even more specifically 0.3 to 0.7, such as 0.35 or 0.65. In certain embodiments of the present disclosure, the weight ratio of shell material to oil in the emulsion is set within the range of 0.01 to 0.5, more specifically 0.025 to 0.4, and even more specifically 0.05 to 0.3.

[0038] The encapsulated composition obtained by the process described herein may be used as is or a polysaccharide, preferably a polysaccharide comprising beta(1→4) linked monosaccharide units, even more preferably a cellulose derivative, especially a cellulose derivative selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl methylcellulose, cellulose acetate and carboxymethyl cellulose, preferably hydroxyethyl cellulose, may be added to the microcapsule shell formed in step h), as described in optional step i) above. After the formation of the microcapsules, the encapsulated composition is typically cooled to room temperature. The encapsulated composition may be further processed before, during, or after cooling. Further processing may include treating the composition with an antimicrobial preservative, which are well known in the art. Further processing may also include adding a suspending aid, such as a hydrocolloid suspending aid, to aid in stable physical dispersion of the microcapsules and prevent creaming or coalescence. Any additional adjuvants conventional in the art may also be added during further processing.

[0039] According to the process of the present disclosure, the core-shell microcapsules may be further coated with a functional coating, if desired. The functional coating may coat all or only a portion of the microcapsule shell. Whether the functional coating is charged or uncharged, its primary purpose is to alter the surface properties of the microcapsules to achieve a desired effect, such as facilitating deposition of the microcapsules on treated surfaces such as fabric, human skin, or hair. The functional coating may be post-coated onto already formed microcapsules or physically incorporated into the microcapsule shell during shell formation. They may be attached to the shell by physical forces, physical interactions such as hydrogen bonding, ionic interactions, hydrophobic interactions, or electron transfer interactions, or may be covalently bonded to the shell.

[0040] The at least one benefit agent may be at least one perfume ingredient. At least one perfume ingredient may be selected from the group consisting of ADOXAL™ (2,6,10-trimethylundec-9-enal); AGRUMEX™ (2-(tert-butyl)cyclohexyl acetate); ALDEHYDE C 10 DECYLIC (decanal); ALDEHYDE C 11 MOA (2-methyldecanal); ALDEHYDE C 11 UNDECYLENIC (undec-10-enal); ALDEHYDE C 110 UNDECYLIC (undecanal); ALDEHYDE C 12 LAURIC (dodecanal); ALDEHYDE C 12 MNA PURE (2-methylundecanal); ALDEHYDE ISO C 11 ((E)-undec-9-enal); ALDEHYDE MANDARINE 10% / TEC ((E)-dodec-2-enal); ALLYL AMYL GLYCOLATE(ALLYL 2-(ISOPENTYLOXY)ACETATE);

[0041] ALLYL CYCLOHEXYL PROPIONATE (allyl 3-cyclohexylpropanoate); ALLYL OENANTHATE (allyl heptanoate); AMBER CORE™ (1-((2-(tert-butyl)cyclohexyl)oxy)butan-2-ol); AMBERMAX™ (1,3,4,5,6,7-hexahydro-beta,1,1,5,5-pentamethyl-2H-2,4a-methanonaphthalene-8-ethanol); AMYL SALICYLATE (pentyl 2-hydroxybenzoate); APHERMATE (1-(3,3-dimethylcyclohexyl)ethyl formate); BELAMBRE™ ((1R,2S,4R)-2'-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxane]); BIGARYL (8-(sec-butyl)-5,6,7,8-tetrahydroquinoline);

[0042] BOISAMBRENE FORTE™ ((ethoxymethoxy)cyclododecane); BOISIRIS™ ((1S,2R,5R)-2-ethoxy-2,6,6-trimethyl-9-methylenebicyclo[3.3.1]nonane); BORNYL ACETATE ((2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl acetate); BUTYL BUTYRO LACTATE (1-butoxy-1-oxopropan-2-yl butyrate); BUTYL CYCLOHEXYL ACETATE PARA (4-(tert-butyl)cyclohexyl acetate); CARYOPHYLLENE ((Z)-4,11,11-trimethyl-8-methylenebicyclo[7.2.0]undec-4-ene); CASHMERAN™ (1,1,2,3,3-pentamethyl-2,3,6,7-tetrahydro-1H-inden-4(5H)-one); CASSYRANE™ (5-tert-butyl-2-methyl-5-propyl-2H-furan);

[0043] CITRAL ((E)-3,7-dimethylocta-2,6-dienal); CITRAL LEMAROME™ N ((E)-3,7-dimethylocta-2,6-dienal); CITRATHAL™ R ((Z)-1,1-diethoxy-3,7-dimethylocta-2,6-diene); CITRONELLAL (3,7-dimethyloct-6-enal); CITRONELLOL (3,7-dimethyloct-6-en-1-ol); CITRONELLYL ACETATE (3,7-dimethyloct-6-en-1-yl acetate); CITRONELLYL FORMATE (3,7-dimethyloct-6-en-1-yl formate); CITRONELLYL NITRILE (3,7-dimethyloct-6-enenitrile); CITRONELLYL PROPIONATE (3,7-dimethyloct-6-en-1-ylpropionate); CLONAL (dodecanenitrile); CORANOL (4-cyclohexyl-2-methylbutan-2-ol);

[0044] COSMONE™ ((Z)-3-methylcyclotetradec-5-enone); CYCLAMEN ALDEHYDE (3-(4-isopropylphenyl)-2-methylpropanal); CYCLOGALBANATE (allyl 2-(cyclohexyloxy)acetate); CYCLOHEXYL SALICYLATE (cyclohexyl 2-hydroxybenzoate); CYCLOMYRAL (8,8-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalene-2-carbaldehyde); DAMASCENONE ((E)-1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one); DAMASCONE ALPHA ((E)-1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one); DAMASCONE DELTA ((E)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-1-one);

[0045] DECENAL-4-TRANS((E)-Deca-4-enal); DELPHONE (2-Pentylcyclopentanone); DIHYDRO ANETHOLE (Propanedioic acid 1-(1-(3,3-dimethylcyclohexyl)ethyl) 3-ethyl ester); DIHYDRO JASMONE (3-Methyl-2-pentylcyclopent-2-enone); DIMETHYL BENZYL CARBINOL (2-Methyl-1-phenylpropan-2-ol); DIMETHYL BENZYL CARBINYL ACETATE (2-Methyl-1-phenylpropan-2-yl acetate); DIMETHYL BENZYL CARBINYL BUTYRATE (2-Methyl-1-phenylpropan-2-yl butyrate); DIMETHYL OCTENONE (4,7-dimethyloct-6-en-3-one); DIMETOL (2,6-dimethylheptan-2-ol);

[0046] DIPENTENE (1-methyl-4-(prop-1-en-2-yl)cyclohex-1-ene); DUPICAL™ ((E)-4-((3aS,7aS)-hexahydro-1H-4,7-methanoinden-5(6H)-ylidene)butanal); EBANOL™ ((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); ETHYL CAPROATE (ethyl hexanoate); ETHYL CAPRYLATE (ethyl octanoate); ETHYL LINALOOL ((E)-3,7-dimethylnona-1,6-dien-3-ol); ETHYL LINALYL ACETATE ((Z)-3,7-dimethylnona-1,6-dien-3-yl acetate); ETHYL Ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate; Ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate;

[0047] EUCALYPTOL ((1s,4s)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane); FENCHYL ACETATE ((2S)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-yl acetate); FENCHYL ALCOHOL ((1S,2R,4R)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol); FIXOLIDE™ (1-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethanone); FLORALOZONE™ (3-(4-ethylphenyl)-2,2-dimethylpropanal); FLORHYDRAL (3-( 3-isopropylphenyl)butanal); FLOROCYCLENE™ ((3aR,6S,7aS)-3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-ylpropionate); FLOROPAL™ (2,4,6-trimethyl-4-phenyl-1,3-dioxane); FRESKOMENTHE™ (2-(sec-butyl)cyclohexanone);

[0048] FRUITATE ((3aS,4S,7R,7aS)-ethyl octahydro-1H-4,7-methanoindene-3a-carboxylate); FRUTONILE (2-methyldecanenitrile); GALBANONE™ PURE (1-(3,3-dimethylcyclohex-1-en-1-yl)pent-4-en-1-one); GARDOCYCLENE™ ((3aR,6S,7aS)-3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl isobutyrate); GERANIOL ((E)-3,7-dimethylocta-2,6-dien-1-ol); GERANYL ACETATE SYNTHETIC ((E)-3,7-dimethylocta-2,6-dien-1-yl acetate); GERANYL ISOBUTYRATE ((E)-3,7-dimethylocta-2,6-dien-1-yl isobutyrate); GIVESCONE™ (ethyl 2-ethyl-6,6-dimethylcyclohex-2-enecarboxylate);

[0049] HABANOLIDE™ ((E)-Oxacyclohexadec-12-en-2-one); HEDIONE™ (Methyl 3-oxo-2-pentylcyclopentaneacetate); HERBANATE™ ((2S)-Ethyl 3-isopropylbicyclo[2.2.1]hept-5-ene-2-carboxylate); HEXENYL-3-CIS BUTYRATE ((Z)-Hex-3-en-1-yl butyrate); HEXYL CINNAMIC ALDEHYDE ((E)-2-benzylideneoctanal); HEXYL ISOBUTYRATE (Hexyl isobutyrate); HEXYL SALICYLATE (Hexyl 2-hydroxybenzoate); INDOFLOR™ (4,4a,5,9b-Tetrahydroindeno[1,2-d][1,3]dioxine); IONONE BETA((E)-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one); IRISONE ALPHA((E)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); IRONE ALPHA((E)-4-(2,5,6,6-tetramethylcyclohex-2-en-1-yl)but-3-en-2-one); ISO E SUPER™ (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone);

[0050] ISOCYCLOCITRAL (2,4,6-trimethylcyclohex-3-enecarbaldehyde); ISONONYL ACETATE (3,5,5-trimethylhexyl acetate); ISOPROPYL METHYL-2-BUTYRATE (isopropyl 2-methylbutanoate); ISORALDEINE™ 70 ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); JASMACYCLENE™ ((3aR,6S,7aS)-3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl acetate); JASMONE CIS ((Z)-3-methyl-2-(pent-2-en-1-yl)cyclopent-2-enone); KARANAL™ (5-(sec-butyl)-2-(2,4-dimethylcyclohex-3-en-1-yl)-5-methyl-1,3-dioxane); KOAVONE ((Z)-3,4,5,6,6-pentamethylhept-3-en-2-one); LEAF ACETAL ((Z)-1-(1-ethoxyethoxy)hex-3-ene); LEMONILE™ ((2E,6Z)-3,7-dimethylnona-2,6-dienenitrile);

[0051] LIFFAROME™ GIV ((Z)-hex-3-en-1-yl methyl carbonate); LILIAL™ (3-(4-(tert-butyl)phenyl)-2-methylpropanal); LINALOOL (3,7-dimethylocta-1,6-dien-3-ol); LINALYL ACETATE (3,7-dimethylocta-1,6-dien-3-yl acetate); MAHONIAL™ ((4E)-9-hydroxy-5,9-dimethyl-4-decenal); MALTYL ISOBUTYRATE (2-methyl-4-oxo-4H-pyran-3-yl isobutyrate); MANZANATE (ethyl 2-methylpentanoate); MELONAL™ (2,6-dimethylhept-5-enal); MENTHOL (2-isopropyl-5-methylcyclohexanol); MENTHONE (2-isopropyl-5-methylcyclohexanone); METHYL CEDRYL KETONE (1-((1S,8aS)-1,4,4,6-tetramethyl-2,3,3a,4,5,8-hexahydro-1H-5,8a-methanoazulen-7-yl)ethanone); METHYL NONYL KETONE EXTRA (undecane-2-one);

[0052] METHYL OCTYNE CARBONATE (METHYL NON-2-YNOATE); METHYL PAMPLEMOUSSE (6,6-DIMETHOXY-2,5,5-TRIMETHYLHEX-2-ENE); MYRALDENE (4-(4-METHYLPENT-3-EN-1-YL)CYCLOHEX-3-ENE CARBOXYLDEHYDE); NECTARYL (2-(2-(4-METHYLCYCLOHEX-3-EN-1-YL)PROPYL)CYCLOPENTANONE); NEOBERGAMATE™ FORTE (2-METHYL-6-METHYLENEOCT-7-EN-2-YL ACETATE); NEOFOLIONE™ ((E)-METHYL NON-2-ENOATE); NEROLIDYLE™ ((Z)-3,7,11-TRIMETHYLDODEC-1,6,10-TRIEN-3-YL ACETATE); NERYL ACETATE HC((Z)-3,7-dimethylocta-2,6-dien-1-yl acetate); NONADYL(6,8-dimethylnonan-2-ol); NONENAL-6-CIS((Z)-non-6-enal); NYMPHEAL™ (3-(4-isobutyl-2-methylphenyl)propanal); ORIVONE™ (4-(tert-pentyl)cyclohexanone);

[0053] PARADISAMIDE™ (2-ethyl-N-methyl-N-(m-tolyl)butanamide); PELARGENE (2-methyl-4-methylene-6-phenyltetrahydro-2H-pyran); PEONILE™ (2-cyclohexylidene-2-phenylacetonitrile); PETALIA™ (2-cyclohexylidene-2-(o-tolyl)acetonitrile); PIVAROSE™ (2,2-dimethyl-2- Phenylethyl propanoate; PRECYCLEMONE™ B (1-methyl-4-(4-methylpent-3-en-1-yl)cyclohex-3-enecarbaldehyde); PYRALONE™ (6-(sec-butyl)quinoline); RADJANOL™ SUPER ((E)-2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-en-1-ol); RASPBERRY KETONE (N112) (4-(4-hydroxyphenyl)butan-2-one); RHUBAFURANE™ (2,2,5-trimethyl-5-pentylcyclopentanone);

[0054] ROSACETOL (2,2,2-trichloro-1-phenylethyl acetate); ROSALVA (dec-9-en-1-ol); ROSYFOLIA ((1-methyl-2-(5-methylhex-4-en-2-yl)cyclopropyl)-methanol); ROSYRANE™ SUPER (4-methylene-2-phenyltetrahydro-2H-pyran); SERENOLIDE (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl cyclopropanecarboxylate); SILVIAL™ (3-(4-isobutylphenyl)-2-methylpropanal); SPIROGALBANONE™ (1-(spiro[4.5]dec-6-en-7-yl)pent-4-en-1-one); STEMONE™ ((E)-5-methylheptan-3-one oxime); SUPER MUGUET™ ((E)-6-ethyl-3-methyloct-6-en-1-ol); SYLKOLIDE™ ((E)-2-((3,5-dimethylhex-3-en-2-yl)oxy)-2-methylpropyl cyclopropanecarboxylate);

[0055] TERPINENE GAMMA (1-METHYL-4-PROPAN-2-YL CYCLOHEXA-1,4-DIENE); TERPINOLENE (1-METHYL-4-(PROPAN-2-YLIDENE) CYCLOHEX-1-ENE); TERPINYL ACETATE (2-(4-METHYLCYCLOHEX-3-EN-1-YL)PROPAN-2-YL ACETATE); TETRAHYDRO LINALOOL (3,7-DIMETHYLOCTANE-3-OL); TETRAHYDRO MYRCENOL (2,6-dimethyloctan-2-ol); THIBETOLIDE (oxacyclohexadecan-2-one); TRIDECENE-2-NITRILE ((E)-tridec-2-enenitrile); UNDECAVERTOL ((E)-4-methyldec-3-en-5-ol); VELOUTONE™ (2,2,5-trimethyl-5-pentylcyclopentanone); VIRIDINE™ ((2,2-dimethoxyethyl)benzene); ZINARINE™ (2-(2,4-dimethylcyclohexyl)pyridine); and mixtures thereof.

[0056] A comprehensive list of perfume ingredients that may be encapsulated in accordance with the present disclosure can be found in perfumery literature, such as "Perfume & Flavor Chemicals", S. Arctander, Allured Publishing, 2000.

[0057] The at least one benefit agent may be a cosmetic ingredient. Preferably, the cosmetic ingredient has a calculated octanol / water partition coefficient (ClogP) of 1.5 or greater, more preferably 3 or greater. Alternatively, preferably, the cosmetic ingredient has a ClogP of 2-7. Particularly useful cosmetic ingredients are selected from the group consisting of emollients, smoothing actives, moisturizing actives, soothing and relaxing actives, decorative actives, anti-aging actives, draining actives, remodeling actives, skin leveling actives, preservatives, antioxidant actives, antibacterial or bacteriostatic actives, cleansing actives, lubricating actives, structuring actives, hair conditioning actives, whitening actives, texturizing actives, softening actives, anti-dandruff actives, and exfoliating actives.

[0058] Particularly useful cosmetic ingredients include, but are not limited to, hydrophobic polymers such as alkyldimethylsiloxanes, polymethylsilsesquioxanes, polyethylene, polyisobutylene, styrene-ethylene-styrene and styrene-butylene-styrene block copolymers, hydrogenated isoparaffins, mineral oils such as silicone oils, vegetable oils such as argan oil, jojoba oil, aloe vera oil, fatty acids and fatty alcohols and their esters, glycolipids, phospholipids, ceramides, sphingolipids such as sterols and steroids, terpenes, sesquiterpenes. , triterpenes and their derivatives, essential oils such as arnica oil, artemisia oil, bark tree oil, birch leaf oil, calendula oil, cinnamon oil, echinacea oil, eucalyptus oil, ginseng oil, jujube oil, helianthus oil, jasmine oil, lavender oil, lotus seed oil, perilla oil, rosemary oil, sandalwood oil, tea tree oil, thyme oil, valerian oil, absinthe oil, ylang ylang oil, and yucca oil.

[0059] The resulting encapsulated composition is provided in the form of a slurry of microcapsules suspended in an aqueous suspension medium and may be incorporated directly into a consumer product base. However, if desired, the slurry may be dried to form the encapsulated composition into a dry powder. Drying of the microcapsule slurry is conventional and may be carried out according to techniques known in the art, such as spray drying, evaporation, freeze drying, or the use of a desiccant. Typically, as is conventional in the art, the dried microcapsules are dispersed or suspended in a suitable powder, such as powdered silica, which may act as a bulking agent or flow aid. Such a suitable powder may be added to the encapsulated composition before, during, or after the drying process.

[0060] A further aspect of the present disclosure relates to an encapsulated composition obtainable by any of the methods described herein. Another aspect of the present disclosure relates to the use of an encapsulated composition as described herein to enhance the performance of a benefit agent in a consumer product. The present disclosure also relates to consumer products comprising the encapsulated compositions as described herein, which may be selected from the group consisting of fabric care detergents and conditioners, hair care conditioners, shampoos, heavy-duty liquid detergents, hard surface cleaners, detergent powders, soaps, shower gels and skin care products, especially fabric softeners and hair conditioners.

[0061] The encapsulated compositions described herein are particularly useful when employed as perfume delivery vehicles in consumer goods where the microcapsules adhere well to the substrate to which they are adapted to provide optimal perfume benefit, including fabric treatment products such as hair shampoos and conditioners and laundry detergents and conditioners. A further aspect of the present disclosure relates to a polymeric stabilizer formed by combining a surfactant with at least one aminosilane polymer, particularly an aminosilane as described hereinabove. The polymeric surfactant comprises a polysaccharide containing carboxylic acid groups, particularly a polymeric surfactant as described hereinabove.

[0062] Another aspect of the present disclosure relates to the use of polymeric stabilizers as described herein in the encapsulation of benefit agents, which stabilize the oil / water interface, thereby providing a template for preparing encapsulated fragrance and / or cosmetic compositions.

[0063] The present disclosure also relates to methods of enhancing the performance of benefit agents in consumer products by adding an encapsulated composition according to the present disclosure. Additionally, the present disclosure relates to a method of encapsulating a benefit agent, wherein a polymeric stabilizer as described herein stabilizes and encapsulates oil droplets of an oil-in-water emulsion, wherein the oil phase contains at least one benefit agent. The present disclosure is further illustrated by the following examples which set forth specific embodiments and should not be construed as limiting in any way. [Example]

[0064] Example 1 General Preparation In a 100 g reactor equipped with a mechanical overhead stirrer, 11.5 g of fragrance (Part I) was mixed with 0.7 g of bis(3-(triethoxysilyl)propyl)amine (CAS 13497-18-2) and 0.5 g of Takenate™ D-110N (1,3-propanediol, 2-ethyl-2-(hydroxyethyl)-, polymer with bis(isocyanatomethyl)-cyclohexatriene (CAS 51852-81-4)) at ambient temperature with mild agitation. 27 g of fragrance was added to the mixture with further agitation, and then 66 g of water was carefully added with agitation stopped. Agitation was resumed to create an emulsion, to which 1.35 g of pectin (Roeper APA 104 high methoxy) was added as a powder. The temperature was then increased to 45°C in 30 minutes and maintained for 2 hours, followed by a further increase to 55°C and maintained for 1 hour. The heat was again increased to 85°C, and at 70°C, 0.3 g of trimesic acid was added as a powder. At 85°C, 2.3 g of starch (HiCap™ 100), 0.4 g of a linker acrylate (selected from those listed below), and 60 μl of a radical initiator (selected from those listed below) were added as a 4 wt% aqueous solution. After 30 minutes, another 60 μl of radical initiator was added, and the temperature was increased to 90°C and maintained for 1 hour and 30 minutes. Heating was stopped and the reaction mixture was allowed to cool slowly to room temperature.

[0065] The initiators used were as follows: [ka]

[0066] The linker molecule is as follows: [ka]

[0067] The specific combinations used in the typical preparations are as follows: [Table 1] The result of these preparations is a slurry of fragrance-containing microcapsules in the size range of 5-50 μm.

[0068] Typical characterizations that followed included size distribution measurements by optical diffraction, solid content residue upon drying at 120°C, perfume extraction upon maceration of capsules dispersed in a liquid fabric softener base at 37°C, and determination of polymer residue in the liquid phase by size exclusion chromatography.

[0069] Evaluating fragrance stability in fabric softeners The capsules prepared above were tested for stability in unscented liquid fabric softener base ("LFS"). Each capsule sample was incorporated by adding 0.5-1.0% by weight of the capsule slurry to a sample of LFS and stirring at room temperature for 10 minutes. The samples were visually evaluated for mechanical integrity and fragrance content using a microscope at 4x and 10x magnification immediately after incorporation into the base (t0) and after maceration at 37°C for 5 days (t5). Changes in capsule shape, and specifically the fragrance content within the capsule, between t0 and t5 were compared to determine their stability. The amount of fragrance still encapsulated in the capsules was visually determined by image analysis. The visual determination of the amount of fragrance still encapsulated was within ±5% of the value determined by gas chromatography (GC-MS) (after appropriate extraction of the fragrance from the sample).

[0070] The results are shown in the following table. [Table 2] *Liquid fabric softener, 37°C for 5 days; Scale Legend: Pass = fragrance retention ≥ 60%; Disqualified = More than 60% of the flavoring is extracted from the base. nd = not determined. The proportion of polymer incorporated into the capsule shell (as a percentage of the total polymer used) is determined by the proportion of free (unreacted) polymer in the continuous medium.

Claims

1. a) an inner shell that encapsulates a benefit agent; and b) a cross-linked polysaccharide outer shell wherein the crosslinking is effected using at least one oligofunctional (meth)acrylate compound.

2. 10. The core-shell capsule of claim 1, wherein the polysaccharide comprises uronic acid units.

3. 3. The core-shell capsule of claim 2, wherein the uronic acid units are hexuronic acid units, particularly galacturonic acid units and glucuronic acid units, more particularly hexuronic acid units selected from the group consisting of 4-O-methyl-glucuronic acid units, guluronic acid units and mannuronic acid units.

4. 2. The core-shell capsule of claim 1, wherein the oligofunctional (meth)acrylate compound is selected from the group consisting of 3-(acryloyloxy)-2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 3,5-triacryloylhexahydro-1,3,5-triazine, tris(2-acryloyloxyethyl)isocyanurate, and pentaerythritol tetraacrylate.

5. 10. The core-shell capsule of claim 1, wherein the inner shell is formed by the reaction between a silane and a polyfunctional diisocyanate.

6. 10. The core-shell capsule of claim 1, wherein the initial shell is stabilized in aqueous suspension by a polymeric stabilizer that is a product of a polymeric surfactant and an aminosilane, the polymeric surfactant comprising a polysaccharide or a mixture containing at least one polysaccharide that has the property of lowering the interfacial tension between the oil and water phases when dissolved in one or both phases.

7. 7. The core-shell capsule of claim 6, wherein the polymeric stabilizer is formed by a combination of pectin and bis(3-(triethoxysilyl)propyl)amine or a combination of pectin and a mixture of bis(3-(triethoxysilyl)propyl)amine and 2-ethylpropane-1,2,3-triyltris((3-(isocyanatomethyl)phenyl)carbamate).

8. A method for preparing an encapsulated composition, in particular an encapsulated composition as described above, comprising the steps of: (a) providing a polymeric surfactant; (b) providing an aqueous phase; (c) dissolving or dispersing the polymeric surfactant in the aqueous phase; (d) providing at least one aminosilane; (e) providing an oil phase comprising at least one benefit agent; (f) optionally dissolving at least one aminosilane in the oil phase; (g) emulsifying an oil phase and an aqueous phase in the presence of both a polymeric surfactant and an aminosilane to form an emulsion of oil droplets in the aqueous phase; (h) allowing the at least one aminosilane and the polymeric surfactant to form a shell at the oil-water interface of the emulsified oil droplets, thereby forming a slurry of microcapsules; (i) adding a polysaccharide, preferably a polysaccharide comprising beta (1→4) linked monosaccharide units, even more preferably a cellulose derivative, in particular a cellulose derivative selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, and carboxymethyl cellulose, preferably hydroxyethyl cellulose, to the microcapsule slurry formed in step h); (j) Crosslinking polysaccharides with oligoacrylates / methacrylates.

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