Method for preparing microcapsules

Abstract

The present invention relates to a novel method for preparing core-shell microcapsules. The microcapsules are also the subject of the present invention. Consumer products, in particular perfumed or flavored consumer products, comprising said microcapsules are also part of the present invention.

Description

[Technical Field]

[0001] The present invention relates to a novel method for preparing core-shell microcapsules. Microcapsules are also the subject of the present invention. Consumer products containing the aforementioned microcapsules, particularly flavored or aromatic consumer products, are also part of the present invention.

[0002] Background of the Invention One of the problems facing the fragrance and flavor industry is that the olfactory effects produced by active compounds are lost relatively quickly due to their volatility. Encapsulating these active substances protects the encapsulated components from "attacks" such as oxidation or moisture, while simultaneously allowing for a constant control of the release rate of the flavor or fragrance, thereby inducing sensory effects through continuous release.

[0003] Polyurea and polyurethane microcapsule slurry are widely used, for example, in the fragrance industry, because they provide a sustained, pleasant olfactory effect after being applied to various substrates. These microcapsules are widely disclosed in the prior art (see, for example, International Publication 2007 / 004166 or European Patent No. 2300146 by the present applicant).

[0004] In addition to performance in terms of stability and olfactory capabilities, consumer demand for environmentally friendly delivery systems is becoming increasingly important and is driving the development of novel delivery systems.

[0005] Therefore, there is still a need to provide novel microcapsules using more environmentally friendly materials, without compromising on performance, particularly in terms of stability in challenging media such as consumer product bases, and in terms of good performance in terms of delivery of active ingredients, such as olfactory performance in the case of fragrance components.

[0006] The present invention proposes a solution to the above problems based on a novel core-shell microcapsule containing a biopolymer film that provides a scaffold for attracting a silicon precursor. As a result, the silicon precursor can silicate the biopolymer film and / or form a silicated film around the biopolymer film.

Brief Description of the Drawings

[0007] [Figure 1] It is a figure showing a scanning electron micrograph of microcapsule A according to the present invention. [Figure 2a] It is a figure showing the silicon (Si) element EDS (energy dispersive spectrometry) mapping of microcapsule A in Fig. 1. [Figure 2b] It is a figure showing the SEM-EDS spectrum of the region of Fig. 1. [Figure 3] It is a figure showing an optical image of microcapsule A dried on a slide glass. [Figure 4] It is a figure showing a scanning electron micrograph of microcapsule B according to the present invention. [Figure 5] It is a figure showing a scanning electron micrograph of microcapsule C according to the present invention. [Figure 6] It is a figure showing a scanning electron micrograph of microcapsule D according to the present invention. [Figure 7] It is a figure showing a scanning electron micrograph of microcapsule H according to the present invention. [Figure 8] It is a figure showing a scanning electron micrograph of microcapsule J taken after washing with water and drying according to the present invention. [Figure 9] It is a figure showing a scanning electron micrograph of microcapsule J after spray drying (coarse collection). [Figure 10] It is a figure showing a scanning electron micrograph of spray-dried microcapsule J (coarse collection), indicating that the capsules are intact when the carrier dissolves after resuspension in water. [Figure 11]FIG. showing the optical image of microcapsule K dried on a slide glass according to the present invention. [Figure 12] FIG. showing the scanning electron micrograph of microcapsule K according to the present invention. [Figure 13] FIG. showing the optical image of microcapsule L dried on a slide glass according to the present invention. [Figure 14] FIG. showing the scanning electron micrograph of microcapsule L according to the present invention. [Figure 15] FIG. showing the ratio of the headspace intensity of each of microcapsules L, M, and O evaluated before and after applying friction to demonstrate the pop effect when provided to a paper blotter. [Figure 16a] FIG. showing the scanning electron micrograph of microcapsule A intact after incubation with a fabric softener at 37°C for 2 months in a sealed jar. [Figure 16b] FIG. showing the scanning electron micrograph of microcapsule A intact after incubation with a fabric softener at 37°C for 2 months in a sealed jar. [Figure 17a] FIG. showing the backscattered electron micrograph of microcapsule A after heating at 500°C, showing the presence of silicon in the shell after extreme heat treatment. [Figure 17b] FIG. showing the silicon (Si) element EDS (energy dispersive spectroscopy) mapping of the corresponding region in FIG. 17a, showing the presence of silicon in the shell after extreme heat treatment. [Figure 17c] FIG. showing the SEM-EDS spectrum of the corresponding region in FIG. 17a, showing the presence of silicon in the shell after extreme heat treatment.

[0008] Detailed Description of the Invention In fact, it is currently known that by complexing a protein with a polycation (for example, between a whey protein isolate and a chitosan oligosaccharide) and using the aforementioned complex as an emulsifier to prepare an oil-in-water emulsion, microcapsules encapsulating hydrophobic materials, preferably active ingredients, can be obtained. A biopolymer shell made of the aforementioned complex can be formed at the oil / water interface. The silicon precursor can be attracted to or into the biopolymer membrane, thereby silicifying the biopolymer membrane.

[0009] Therefore, the method of the present invention provides a solution to the above-mentioned problems, as it can prepare microcapsules having desired physical integrity and stability for various applications.

[0010] Unless otherwise stated, percentages (%) refer to the weight percentage of the composition.

[0011] A "hydrophobic material" refers to a material that forms a two-phase dispersion when mixed with water. According to the present invention, a hydrophobic material can be an "inert" material such as a solvent or an active ingredient. According to one embodiment, the hydrophobic material is a hydrophobic active ingredient.

[0012] "Active ingredient" refers to a single compound or a combination of components.

[0013] "Fragrance oil" or "flavor oil" means a single compound or a mixture of several compounds that impart fragrance or flavor.

[0014] "Consumer product" or "final product" means a manufactured product that is ready for distribution, sale, and use by consumers.

[0015] For clarity, the term "dispersion" in this invention means a system in which particles, aggregates, precipitates, complexes, and / or emulsion droplets are dispersed in a continuous phase of different compositions, which specifically includes suspensions or emulsions. "Dispersion" according to this invention may encompass two-phase dispersion or multiple dispersion (more than two phases).

[0016] In the present invention, a “core-shell microcapsule” or similar means a capsule having a particle size distribution in the micron range (for example, an average diameter (d(v,0.5)) preferably contained in about 1 to 3000 microns), comprising a shell and an internal continuous oil phase surrounded by the shell. According to the present invention, the terms “average diameter” and “average size” are used interchangeably.

[0017] The microcapsules of the present invention preferably have an average size of more than 10 microns, more preferably more than 15 microns, and even more preferably more than 20 microns.

[0018] According to one embodiment, the microcapsules have an average size that is contained within 10 to 500 microns, preferably 10 to 100 microns, and more preferably 10 to 50 microns.

[0019] "Microcapsule slurry" refers to microcapsules dispersed in a liquid. According to the embodiment, the slurry is an aqueous slurry, meaning the microcapsules are dispersed in the aqueous phase.

[0020] "Biopolymer membrane" or "biopolymer shell" means a layer containing a complex between a protein and a polycation, preferably an organic polycation.

[0021] "Polycation" refers to a polyvalent cation or molecule that has two or more positive charges.

[0022] A "polyfunctional monomer" refers to a molecule that chemically reacts or combines as a unit to form a polymer or supramolecular polymer. The polyfunctional monomer as defined in this invention has at least two functional groups capable of forming a microcapsule shell.

[0023] "Protein" refers to a single protein or a combination of proteins.

[0024] "Whey protein isolate" refers to a product containing more than 90% protein by weight, processed to remove fat and lactose.

[0025] A "protein / polycation complex" refers to a material formed by the interaction of a protein and a polycation. In this invention, complexes, precipitates, particles, or aggregates are used without distinction.

[0026] "Chitosan oligosaccharide" preferably refers to a chitosan oligomer having an average molecular weight (MW) of less than 5,000 Da.

[0027] A "composite shell" means that the shell is composed of two or more materials. According to a particular embodiment, the microcapsule shell has an inner layer formed of a biopolymer material and an outer layer formed of a silicon-based material. According to a particular embodiment, the microcapsule shell has an inner layer rich in a biopolymer material and an outer layer rich in a silicon-based material. According to one embodiment, the inner and outer layers are linked layers, and the shell means a shell consisting of layers linked by chemical or physical interactions, thereby forming a composite structure. Examples of physical or chemical interactions include covalent bonds, ionic bonds, coordination covalent bonds, hydrogen bonds, van der Waals interactions, hydrophobic interactions, chelation effects, or steric effects. Further use of thermal processing, heat treatment, and annealing may be used to facilitate physical interactions and form a composite structure.

[0028] "Silicon-based materials" refer to materials that contain the element silicon.

[0029] Method for preparing core-shell microcapsule slurry In a first embodiment, the present invention relates to a method for preparing a core-shell microcapsule slurry, (i) A step of mixing the protein and polycation in a dispersed phase, (ii) A step of adding an oil phase containing a hydrophobic material, preferably a fragrance or flavor, to the dispersed phase to form a dispersion, (iii) A step of curing to form a microcapsule slurry Includes, Add at least one silicon precursor in step (i) and / or step (ii) and / or step (iii). Regarding the method.

[0030] According to one embodiment, the dispersion obtained in step ii) is a two-phase dispersion.

[0031] Therefore, according to a particular embodiment, the method is (i) A step of mixing the protein and polycation in a dispersed phase, (ii) A step of adding an oil phase containing a hydrophobic material, preferably a fragrance or flavor, to the dispersed phase to form a two-phase dispersion, (iii) A step of curing to form a microcapsule slurry Includes, Add at least one silicon precursor in step (i) and / or step (ii) and / or step (iii).

[0032] Without being bound by any theory, the inventors believe that proteins (e.g., whey protein isolate (WPI)) and polycations (e.g., chitosan oligosaccharides) can be compounded by favorable interactions, including electrostatic interactions between the negatively charged portion of the protein and the positively charged portion of the polycation.

[0033] Protein / polycation complexes can act as emulsifiers and form biopolymer films at the oil-in-water interface. The formed biopolymer film then provides a silicification scaffold and attracts silicon precursors to form a composite shell containing both silicon-based material and biopolymer-based material (made of a complex of protein and polycation).

[0034] In the first step of this method, the protein and polycation are mixed in a dispersed phase. It should be understood that the protein and polycation have attractive interactions and form a complex. Natural materials have multiple different functional groups and moieties that can interact with other materials by electrostatic, hydrogen bonding, and van der Waals interactions across a range of pH, ionic strength, temperature, solution, and processing conditions.

[0035] Those skilled in the art will be able to select appropriate conditions for forming the composite.

[0036] The aforementioned protein and polycation are mixed under conditions sufficient to form a suspension of the complex between the protein and the polycation. Typically, the mixing step is carried out at a pH of 4–8, preferably 4–7, and most preferably 5–6.

[0037] According to the present invention, proteins and polycations can interact to form a complex. Typically, proteins are negatively charged, and polycations are positively charged.

[0038] According to a particular embodiment, the protein is selected from the group consisting of whey protein (preferably whey protein isolate), milk protein, casein salts such as sodium caseinate or calcium caseinate, casein, hydrolyzed protein, gelatin, gluten, pea protein, soy protein, silk protein, β-lactoglobulin, ovalbumin, bovine serum albumin, and mixtures thereof.

[0039] According to one embodiment, the protein is selected from the group consisting of potato protein, chickpea protein, algal protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupin bean protein, and mixtures thereof.

[0040] According to an embodiment, the protein is selected from the group consisting of potato protein, chickpea protein, algal protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupin bean protein, whey protein (preferably whey protein isolate), milk protein, casein salts such as sodium caseinate or calcium caseinate, casein, hydrolyzed protein, gelatin, gluten, pea protein, soy protein, silk protein, β-lactoglobulin, ovalbumin, bovine serum albumin, and mixtures thereof.

[0041] According to a particular embodiment, the polycation is chitosan, chitosan oligomer, chitosan oligosaccharide, Ca 2+ 、Mg 2+ 、Zn 2+ 、Ba 2+ 、Sr 2+ and other cations, and mixtures selected from the group consisting thereof.

[0042] When the cation is added as a polycation (e.g., Ca 2+ 、Mg 2+ 、Zn 2+ 、Ba 2+ 、Sr 2+ ), it is to be understood that it is added in the form of salts such as CaCl2, CaBr2, CaI₂, calcium acetate, calcium lactate, Ca(NO₃)₂, Mg(NO₃)₂, MgCl₂, MgBr₂, MgI₂, magnesium acetate, ZnCl₂, ZnBr₂, ZnI₂, Zn(NO₃)₂, ZnSO₄, zinc acetate, BaCl₂, Sr(NO₃)₂, SrCl₂, SrBr₂, SrI₂, and strontium acetate.

[0043] According to certain embodiments, the polycation is a chitosan oligosaccharide.

[0044] Chitosan oligosaccharides preferably have a low molecular weight, preferably less than 5000, and preferably less than 3000.

[0045] According to a particular embodiment, the protein is a whey protein isolate, and the polycation is a chitosan oligosaccharide.

[0046] According to a particular embodiment, preferably Ca 2+ Mg 2+ Zn 2+ Ba 2+ Sr 2+ A cation selected from the group consisting of the following is added to the protein (in the form of a salt).

[0047] According to a particular embodiment, the dispersed phase comprises a protein, a cation (added in the form of a salt), and a chitosan oligosaccharide.

[0048] According to a particular embodiment, the weight ratio of protein to polycation in the slurry is 5:1 to 1:3, preferably 3:1 to 1:2, and more preferably 2:1.

[0049] There are no particular restrictions on the properties of the solvent that can be used in step i), as long as it can dissolve / disperse the protein / polycation complex.

[0050] According to a particular embodiment, the dispersed phase contains water, and preferably consists of water.

[0051] According to another specific embodiment, the water content is 10% by weight or less, preferably 5% by weight or less, and more preferably 3% by weight or less, based on the total weight of the dispersed phase.

[0052] According to certain embodiments, the dispersed phase does not contain water.

[0053] According to one embodiment, the dispersed phase comprises a solvent selected from the group consisting of glycerol, 1,4-butanediol, ethylene glycol, and mixtures thereof.

[0054] In the second step, an oil phase containing a hydrophobic material, preferably a fragrance or flavor, is added to the dispersion phase to form a dispersion, preferably a two-phase dispersion, where the average droplet size is preferably 1 to 1000 microns, more preferably 1 to 500 microns, and even more preferably 5 to 50 microns.

[0055] The protein / polycation complex formed in step i) acts as an emulsifier to form a two-phase dispersion. Any known technique, such as homogenization, sonication, shear mixing, and stirring, can be used to form the dispersion.

[0056] Hydrophobic materials The hydrophobic material according to the present invention may be an "inert" material such as a solvent or active ingredient. A single hydrophobic material or a mixture of hydrophobic materials can be used.

[0057] When a hydrophobic material is the active ingredient, it is preferably selected from the group consisting of flavors, flavor components, fragrances, fragrance components, nutritional supplements, cosmetics, pesticides, odor neutralizing components, biocides, and mixtures thereof.

[0058] The term "odor neutralizing agent" is understood to mean an agent capable of reducing the perception of malodors, that is, the perception of unpleasant or offensive smells to the human nose.

[0059] According to certain embodiments, the hydrophobic material includes a phase change material (PCM).

[0060] According to a particular embodiment, the hydrophobic material comprises a mixture of a fragrance and another component selected from the group consisting of nutritional supplements, cosmetics, pesticides, and biocides.

[0061] According to a particular embodiment, the hydrophobic material comprises a mixture of a biocide and another component selected from the group consisting of fragrances, nutritional supplements, cosmetics, and pesticides.

[0062] According to a particular embodiment, the hydrophobic material comprises a mixture of an insecticide and another component selected from the group consisting of fragrances, nutritional supplements, cosmetics, and biocides.

[0063] According to certain embodiments, the hydrophobic material contains a fragrance.

[0064] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0065] According to a particular embodiment, the hydrophobic material comprises a biocide.

[0066] According to a particular embodiment, the hydrophobic material comprises an insecticide.

[0067] "Fragrance" (or "fragrance oil") as used herein means a component or composition that is liquid at approximately 20°C. According to any one of the embodiments described above, the aforementioned fragrance oil may be a mixture of components in the form of a fragrance component alone or a fragrance composition. "Fragrance component" as used herein means a compound used primarily for the purpose of imparting or modifying a scent. In other words, for such a component to be considered a fragrance component, it must not merely have a scent, but must be recognized by those skilled in the art as being able to impart or modify the scent of a composition in a positive or pleasant manner. For the purposes of the present invention, fragrance oils also include combinations of fragrance components with substances that together improve, enhance or modify the delivery of the fragrance component, such as fragrance precursors, modifiers, emulsions or dispersions, as well as combinations that impart additional benefits beyond modifying or imparting a scent, such as persistence, blooming, odor neutralization, antimicrobial effects, microbial stability, and pest control.

[0068] The properties and types of fragrance components present in the oil phase are not guaranteed to be described in more detail here, nor are they exhaustive in any case, and those skilled in the art can select them according to their intended use or application and the desired sensory stimulation effect based on their general knowledge. Generally speaking, these fragrance components belong to various chemical classes such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds, and essential oils (e.g., thyme oil), and the aforementioned fragrance components may be of natural or synthetic origin. Many of these components are listed in reference texts such as S. Arctander's book *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its latest edition, or other works of similar nature, as well as in the extensive patent literature in the field of fragrances.

[0069] In particular, the following are some commonly used fragrance components in fragrance formulations, for example: - Aldehyde components: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal, nonanal and / or nonenal; - Aromatic - Herbal ingredients: Eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0 2,7 [Undecane-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxatian, 2,2,7-8,9-10-tetramethylspiro[5.5]undecane-8-one, menthone and / or alpha-pinene; - Balsam components: Coumarin, ethyl vanillin and / or vanillin; - Citrus components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpene, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-mentadiene; - Floral ingredients: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanol, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, 2-(methylamino)benzoate methyl, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, ( 1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl) -2-Buten-1-one, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexen-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, berzyl acetate, geraniol, p-mentha-1-en-8- All, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, methyl cis-dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, verzyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, (S)-2-(1,1-dimethylpropoxy)propanoate propyl, 2-methoxynaphthalene, 2,2,A mixture of 2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamic aldehyde, 8-decene-5-olido, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, berzyl isobutyrate and / or methyl ionone isomers; - Fruity components: γ-Undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxatian, 4-decanolide, ethyl 2-methylpentanoate, hexyl acetate, ethyl 2-methylbutanoate, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, 2-methyl-1,3-dioxolane-2-ethyl acetate, 1,4-cyclohexanedicarboxylate diethyl, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl[3-ethyl-2-oxyranyl]acetate and / or 1,4-cyclohexanedicarboxylate diethyl; - Green components: 2-methyl-3-hexanone(E)-oxime, 2,4-dimethyl-3-cyclohexen-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styraryl acetate, allyl(2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; - Musk-based components: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecene-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecene-2-one, 1-oxa-13-cyclohexadecene-2-one, (9Z)-9-cycloheptadecene-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3-methyl-5-cyclo Lopentadecene-1-one, 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, oxacyclohexadecan-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate; - Woody components: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxiran-2,9'-tricyclo[6.2.1.0 2,7 Undeca[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undeca-8-ene-1-ylacetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, Clearwood®, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopentene-1' -yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methylcedyl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalene-2-yl)ethane-1-one and / or isobornyl acetate; - Other components (e.g., amber, powdery spicy, or watery): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and its stereoisomers, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylbyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal.

[0070] Furthermore, it is understood that the aforementioned components may also be compounds known to release various types of fragrance compounds, also known as pro-fragrances, in a controlled manner. Non-limiting examples of suitable pro-fragrances include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, and 2-(dodecylthio) Cutane-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hexa-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-ylhexadecanoate, bis(3,7-dimethylocta-2,6-dienyl)succinate, (2-((2-Me (Tylundeca-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, (3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, 1-(((Z)-hexa-3-en-1-yl)oxy)-2-methylundeca-1-ene, (2-((2-methylundeca-1-en-1-yl)oxy )ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undeca-1-ene, 1-methoxy-4-(1-phenethoxypropa-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxypropa-1-en-2-yl)benzene, 2-(1-phenethoxypropa-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,Examples include 7-dimethylocta-6-en-1-yl)oxy)propa-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylbyl)oxy)-3-methoxybenzaldehyde, or mixtures thereof.

[0071] The fragrance components can be dissolved in solvents currently used in the fragrance industry. The solvent is preferably not an alcohol. Examples of such solvents include diethyl phthalate, isopropyl myristate, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is highly hydrophobic and sterically hindered, such as Abalyn® or benzyl benzoate. Preferably, the fragrance contains less than 30% solvent. More preferably, the fragrance contains less than 20% solvent, and even more preferably less than 10%, all of which are defined by weight relative to the total weight of the fragrance. Most preferably, the fragrance contains essentially no solvent.

[0072] Preferred fragrance components are those with high steric hindrance (bulky materials), particularly those from one of the following groups: - Group 1: Fragrance components containing a cyclohexane, cyclohexene, cyclohexanone, or cyclohexenone ring substituted with at least one linear or branched C1-C4 alkyl or alkenyl substituent; - Group 2: Fragrance components comprising a cyclopentane, cyclopentene, cyclopentanone, or cyclopentenone ring substituted with at least one linear or branched C4-C8 alkyl or alkenyl substituent; - Group 3: Fragrance components containing a phenyl ring, or fragrance components containing a cyclohexane, cyclohexene, cyclohexanone, or cyclohexenone ring substituted with at least one linear or branched C5-C8 alkyl or alkenyl substituent, or at least one phenyl substituent and optionally one or more linear or branched C1-C3 alkyl or alkenyl substituents; - Group 4: Fragrance components containing at least two condensed or linked C5 and / or C6 rings; - Group 5: Fragrance components containing camphor-like ring structures; - Group 6: At least one C7~C 20 Fragrance components containing a ring structure; - Group 7: A fragrance component having a logP value greater than 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent.

[0073] Examples of components in each of these groups are as follows: - Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (manufacturer: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomentone, 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate methyl (manufacturer: Firmenich SA, Geneva, Switzerland), neron, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-p-mentadiene-7-ol (manufacturer: Firmenich Firmenich SA (located in Geneva, Switzerland), 1-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-mentanyl acetate, (1R,2S,4R)-4,6,6-trimethylbicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2Hpyran (manufacturer: Firmenich SA, located in Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanediethyl dicarboxylate (manufacturer: Firmenich SA, located in Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethylbenzo[B]furan-2-one (manufacturer: Firmenich SA, located in Geneva, Switzerland), ((6R)-perhydro-3,6-dimethylbenzo[B]furan-2-one (manufacturer: Firmenich SA (located in Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbald; - Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (Manufacturer: Givaudan SA, Bernier, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (Manufacturer: Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol (Manufacturer: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentaneacetate (Manufacturer: Firmenich Firmenich SA (located in Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (manufacturer: Firmenich SA, located in Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Firmenich SA, located in Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (manufacturer: Givaudan SA, located in Bernier, Switzerland); - Group 3: Damascone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), (1'R)-2-[2-(4'-methyl-3'-cyclohexen-1'-yl)propyl]cyclopentanone, α-ionone, β-ionone, damascenone, mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (manufacturer: Firmenich Firmenich SA (Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl-1'cyclohexyl)ethoxycarbonyl]methylpropanoate (Manufacturer: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (Manufacturer: International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (Manufacturer: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (Manufacturer: Firmenich SA (located in Geneva, Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpenyl isobutyrate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate (manufactured by Firmenich SA, located in Geneva, Switzerland), 8-methoxy-1-p-menthen, (1S,1'R)-2-[1-(3',3'-Dimethyl-1'-Cyclohexyl)Ethoxy]-2-Methylpropanoate (Manufacturer: Firmenich SA, Geneva, Switzerland), p-tert-Butylcyclohexanone, Mententhiol, 1-Methyl-4-(4-Methyl-3-Pentenyl)-3-Cyclohexene-1-Caraldehyde, Allyl Cyclohexylpropionate, Cyclohexyl Salicylate, 2-Methoxy-4-Methylphenylmethyl Carbonate, Ethyl 2-Methoxy-4-Methylphenyl Carbonate, 4-Ethyl-2-Methoxyphenylmethyl Carbonate; - Group 4: Methylcedylketone (Manufacturer: International Flavors and Fragrances, USA), 2-methylpropanoic acid (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6 Deca-3-en-8-yl and 2-methylpropanoic acid (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6Mixture with deca-4-en-8-yl, vetyverol, vetyverone, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone (manufactured by International Flavors and Fragrances, USA), (5RS,9RS,10SR)-2,6,9,10-tetramethyl-1-osaspiro[4.5]deca-3,6-diene and (5RS,9SR,10RS) isomers, 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]deca-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indenone (manufactured by International Flavors and Fragrances (USA), mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (Manufacturer: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undeca-4-ene-9-spiro-2'-oxirane (Manufacturer: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (Manufacturer: Firmenich SA, Geneva, Switzerland), octalynol, dodecahydro-3a,6,9a-tetramethylnaphtho[2,1-b]furan, Manufacturer: Firmenich SA (located in Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]deca-3-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]deca-4-en-8-yl acetate, as well as tricyclo[5.2.1.0(2,6)]deca-3-en-8-yl propanoate and [5.2.1.0(2,6)]deca-4-en-8-yl propanoate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptan-3-spiro-2'-cyclohexen-4'-one; - Group 5: Camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]octa-5-en-2-carbaldehyde, pinene, camphene, 8-methoxysedran, 8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (manufactured by Firmenich SA, Geneva, Switzerland), cedrene, cedrenol, cedrol, 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0 2,7 Mixture with undecane-4-one (manufacturer: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (manufacturer: Firmenich SA, Geneva, Switzerland); - Group 6: Trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (Manufacturer: Firmenich SA, Geneva, Switzerland), 9-hexadecene-16-olido (Manufacturer: Firmenich SA, Geneva, Switzerland), pentadecenolide (Manufacturer: Firmenich SA, Geneva, Switzerland), 3-methyl-(4 / 5)-cyclopentadecenone (Manufacturer: Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (Manufacturer: Firmenich SA, Geneva, Switzerland), pentadecanolide (Manufacturer: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (Manufacturer: Firmenich SA, Geneva, Switzerland), (1-ethoxyethoxy)cyclododecane (Manufacturer: Firmenich SA (located in Geneva, Switzerland), 1,4-dioxacycloheptadecane-5,17-dione, 4,8-cyclododecadiene-1-one; - Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (manufacturer: Givaudan SA, Bernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0074] Preferably, the fragrance contains at least 30%, preferably at least 50%, and more preferably at least 60% of components selected from groups 1 to 7 as defined above. More preferably, the fragrance contains at least 30%, preferably at least 50%, of components from groups 3 to 7 as defined above. Most preferably, the fragrance contains at least 30%, preferably at least 50%, of components from groups 3, 4, 6, or 7 as defined above.

[0075] According to another preferred embodiment, the fragrance contains at least 30%, preferably at least 50%, and more preferably at least 60%, of a component having a logP greater than 3, preferably greater than 3.5, and even more preferably greater than 3.75.

[0076] According to certain embodiments, the fragrance used in the present invention comprises a primary alcohol in less than 10% of its weight, a secondary alcohol in less than 15% of its weight, and a tertiary alcohol in less than 20% of its weight. Advantageously, the fragrance used in the present invention may contain no primary alcohol and include less than 15% of secondary and tertiary alcohols.

[0077] According to one embodiment, the oil phase (or oily core) is - A fragrance oil containing at least 15% by weight of a high-impact fragrance raw material with LogT < -4, - 1.07 g / cm³ 3 Density-adjusting material with higher density: 0-75% by weight Includes.

[0078] "High-impact fragrance ingredients" should be understood as fragrance ingredients with LogT < -4. The olfactory threshold concentration of a chemical compound is partially determined by its shape, polarity, partial charge, and molecular weight. For convenience, the olfactory threshold concentration is presented as the common logarithm of the threshold concentration, i.e., Log[threshold] ("LogT").

[0079] The "density adjusting material" is 1.07 g / cm³. 3It is desirable to understand it as a material with a higher density, preferably one with low odor or no odor.

[0080] The olfactory threshold concentration of the fragrance compound is determined using a gas chromatograph (GC). Specifically, the gas chromatograph is calibrated to determine the precise amount of fragrance component injected by syringe, the precise division ratio, and the hydrocarbon response using hydrocarbon standards with known concentration and chain length distributions. The airflow rate is precisely measured, and the sampled volume is calculated assuming a human inhalation time of 12 seconds. Since the precise concentration at any given time is known, the mass per inhaled volume can be determined, and therefore the concentration of the fragrance compound can be determined. To determine the threshold concentration, a solution of the calculated concentration is supplied to the sniff port. Panelists smell the GC effluent and identify the retention time at which they notice the odor. The average of all panelists determines the olfactory threshold concentration of the fragrance compound. The determination of the olfactory threshold is explained in detail in C. Vuilleumier et al., Multidimensional Visualization of Physical and Perceptual Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, Vol. 33, September, 2008, pages 54-61.

[0081] Properties of high-impact fragrance raw materials with LogT < -4 and 1.07 g / cm³ 3 Density-modifying materials with higher densities are described in International Publication No. 2018 / 115250, which is included by reference.

[0082] According to one embodiment, the high-impact fragrance raw materials with LogT < -4 are (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenylacetate, pyrazobutyl, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl)pyridine, 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1- 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, a mixture of (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethylbenzo[b]furan-2-one and (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethylbenzo[b]furan-2-one, (+-)-1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one, (1'S,3'R)-1-methyl-2-[(1',2' ,2'-trimethylbicyclo[3.1.0]hexa-3'-yl)methyl]cyclopropyl}methanol, (+-)-3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-buten-1-one, H-methyl-2h-1,5-benzodioxepin-3(4H)-one, (2E,6Z)-2,6-nonadien-1-ol, (4Z)-4-dodecenal, (+-)-4-hydroxy-2,5-dimethyl-3(2H)- Lanone, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4α,8β-dimethyl-4α-naphthalenol, pacholol, 2-methoxy-4-(1-propenyl)phenol, a mixture containing (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylene-2-phenyl-2H-pyran, 4-methylene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,A mixture containing 6-dihydro-2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonylenic aldehyde, 2-methoxy-4-propylphenol, 3-methyl-5-phenyl-2-pentennitrile, 1-(spiro[4.5]deca-6 / 7-en-7-yl)-4-penten-1-one, 2-methoxynaphthalene, (-)-(3aR,5AS,9AS,9BR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 5-nonanolide, (3aR,5AS,9AS,9BR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 7- Isopropyl-2H,4H-1,5-benzodioxepin-3-one, coumarin, 4-methylphenylisobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, β,2,2,3-tetramethyl-Δ-methylene-3-cyclopenten-1-butanol, deltadamascone((2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one), (+-)-3,6-dihydro-4, 6-Dimethyl-2-phenyl-2h-pyran, anisaldehyde, paracresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2-aminobenzoate, ethyl methylphenylglycidate, octaractone γ, ethyl 3-phenyl-2-propenoate, (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, paracresol acetate, dodecalactone, tricyclon, (+)-(3R,5Z)-3-methyl-5-cyclopenten Ntadecene-1-one, undecalactone, (1R,4R)-8-mercapto-3-p-mentanone, (3S,3AS,6R,7AR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, β-ionone, (+-)-6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1,3,5-undecatriene, 10-undecenal, (9E)-9-undecenal, (9Z)-9-undecenal, (Z)-4-decenal, (+-)-2-methylpentanoate ethyl, 1,2-Dialdisulfane, 2-Tridecennitrile, 3-Tridecennitrile, (+-)-2-ethyl-4,4-dimethyl-1,3-oxatian, (+)-(3R,5Z)-3-methyl-5-cyclopentadecene-1-one, 3-(4-tert-butylphenyl)propanal, allyl acetate (cyclohexyloxy), methyl naphthyl ketone, (+-)-(4E)-3-methyl-4 -Cyclopentadecene-1-one, (+-)-5E3-methyl-5-cyclopentadecene-1-one, 3-cyclopropylmethyl hexenoate, (4E)-4-methyl-5-(4-methylphenyl)-4-pentenal, (+-)-1-(5-propyl-1,3-benzodioxol-2-yl)ethanone, 4-methyl-2-pentylpyridine, (+-)(E)-3-methyl-4-(2, 6,6-Trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan, (2S,5R)-5-methyl-2-(2-propanyl)cyclohexanone oxime, 6-Hexyltetrahydro-2H-pyran-2-one, (+-)-3-(3-isopropyl (Lu-1-phenyl)butanal, 2-(3-oxo-2-pentylcyclopentyl)methyl acetate, 1-(2,6,6-trimethyl-1-cyclohexa-2-enyl)penta-1-en-3-one, indole, 7-propyl-2H,4H-1,5-benzodioxepin-3-one, ethylpraline, (4-methylphenoxy)acetaldehyde, ethyltricyclo[5.2.1.0., 2,6]decane-2-carboxylate, (+)-(1'S,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol, (4E)-3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-isopropyl-6-methyl Tyl-bicyclo[2.2.2]octa-5-en-2-carbaldehyde, methylnonylacetaldehyde, 2-methylpropanoate 4-formyl-2-methoxyphenyl, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, (1R,5R)-4,7,7-trimethyl-6-syl Selected from the group consisting of abicyclo[3.2.1]octa-3-ene, (1R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1,6-octadiene-3-ol, (E)-3-phenyl-2-propennitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, allyl acetate (2 / 3-methylbutoxy), (+-)-(2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1-penten-3-one, and mixtures thereof.

[0083] According to one embodiment, the fragrance raw material with LogT < -4 is selected from the group consisting of aldehydes, ketones, alcohols, phenols, ester lactones, ethers, epoxides, nitriles, and mixtures thereof.

[0084] According to one embodiment, the fragrance raw material having LogT < -4 contains at least one compound selected from the group consisting of alcohols, phenols, ester lactones, ethers, epoxides, nitriles, and mixtures thereof, preferably in an amount comprising 20 to 70% by weight based on the total weight of the fragrance raw material having LogT < -4.

[0085] According to one embodiment, the fragrance raw material having LogT < -4 contains 20 to 70% by weight of aldehydes, ketones, and mixtures thereof, based on the total weight of the fragrance raw material having LogT < -4.

[0086] Therefore, the remaining fragrance ingredients in the oily core may have a LogT > -4.

[0087] According to the embodiment, the fragrance raw materials with LogT>-4 are ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal, verzyl propionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate, (+-)-(E)-4-methyl-3-decen-5-ol, 2,4-dimethyl-3-cyclohexen-1-carbaldehyde, 1,3,3-trimethyl-2-oxabicyclo[2.2.2] Octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa-12 / 13-cyclohexadecene-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, aldehyde C11, (+-)-2,6-dimethyl-7-octen-2-ol, 3-cyclohexylpropanoate allyl, (Z)-3-hexynyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, heptanoate allyl, 2-(2-methyl-2- Propanyl cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl butyrate, geranyl acetate, neryl acetate, (+-)-1-phenylethyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, ethyl 3-oxobutanoate, (2Z)-3-hydroxy-2-butenoate, 8-p-menthanol, 8-p-menthanyl acetate, 1-p-menthanyl acetate, (+-)-2-(4-methyl-3-cyclohexenyl-1-yl)-2-p Ropanyl acetate, (+-)-2-methylbutylbutanoate, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3,5,6-trimethyl-3-cyclohexen-1-carbaldehyde, 2,4,6-trimethyl-3-cyclohexen-1-carbaldehyde, 2-cyclohexylethyl acetate, octanal, ethyl butanoate, (+-)-(3E)-4-(2,6,6-trimethyl-1 / 2-cyclohexen-1-yl)-3-butenoate N-2-one, 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, ethyl hexanoate, undecanal, decanal, 2-phenylethyl acetate, (1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]Heptan-2-ol, (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2-propanylidene)cyclohexene, (+)-(R)-4-(2-methoxypropan-2-yl)-1-methylcyclohexa-1-ene, berzyl acetate, (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1-[ Selected from the group consisting of (1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3R)-1-[(1S,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (+)-(1S,1'R)-2-[1-(3',3'-dimethyl)1'-cyclohexyl]ethoxy]-2-methylpropylpropanoate, and mixtures thereof.

[0088] According to one embodiment, the fragrance compound is - 0-60% by weight of a hydrophobic solvent (based on the total weight of the fragrance mixture), - 40-100% by weight of fragrance oil (based on the total weight of the fragrance blend), - Optionally, further hydrophobic active ingredients and The fragrance oil contains at least two, preferably all, of the following properties: • Fragrance components having a logP greater than 3, preferably greater than 3.5, in amounts of at least 35%, preferably at least 40%, preferably at least 50%, and more preferably at least 60%. • At least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40%, of the bulky materials from groups 1 to 6, preferably groups 3 to 6, as defined above. • A high-impact fragrance material with LogT < -4, comprising at least 15%, preferably at least 20%, more preferably at least 25%, and even more preferably at least 30%.

[0089] According to a particular embodiment, the fragrance contains 0 to 60% by weight of a hydrophobic solvent.

[0090] According to a particular embodiment, the hydrophobic solvent is a more preferred density-modifying material from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl salicylate and ethyl salicylate, benzyl cinnamate, and mixtures thereof.

[0091] In certain embodiments, the hydrophobic solvent has a Hansen solubility parameter that is compatible with the trapped fragrance oil.

[0092] The term "Hansen solubility parameter" refers to the solubility parameter approach proposed by Charles Hansen, used to predict the solubility of polymers, and is understood to have been developed based on the principle that the total energy of vaporization of a liquid consists of several individual parts. To calculate the "weighted Hansen solubility parameter," the effects of (atomic) dispersion forces, (molecular) permanent dipole-permanent dipole forces, and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen solubility parameter" is (δD 2 +δP 2 +δH 2 ) 0.5 The coefficient is calculated as follows, where δD is the Hansen dispersion value (hereinafter also called atomic dispersion force), δP is the Hansen polarizability value (hereinafter also called dipole moment), and δH is the Hansen hydrogen bond ("h bond") value (hereinafter also called hydrogen bond). For a more detailed explanation of the parameters and values, see Charles Hansen, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, Danish Technical Press (Copenhagen, 1967).

[0093] The Euclidean difference of the solubility parameters between the fragrance and the solvent is (4 × (δD 溶媒 -δD フレグランス ) 2 +( δP 溶媒 -δPフレグランス ) 2 +(δH 溶媒 -δH フレグランス ) 2 ) 0.5 It is calculated as follows, where δD 溶媒 δP 溶媒 , and δH 溶媒 These are the Hansen dispersion value, Hansen polarization degree value, and Hansen h-bond value of the solvent, respectively, and δD フレグランス δP フレグランス , and δH フレグランス These are the Hansen dispersion value, Hansen polarizability value, and Hansen h-bond value of the fragrance, respectively.

[0094] In certain embodiments, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a first group consisting of 12–20 atomic dispersion forces (δD), 1–8 dipole moments (δP), and 2–11 hydrogen bonds (δH).

[0095] In certain embodiments, the fragrance oil and hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of an atomic dispersion force (δD) of 12-20, preferably 14-20, a dipole moment (δP) of 1-8, preferably 1-7, and hydrogen bonds (δH) of 2.5-11, preferably 4-11.

[0096] In certain embodiments, at least 90%, preferably at least 95%, and most preferably at least 98% of the fragrance oil has at least two Hansen solubility parameters selected from a first group consisting of atomic dispersion forces (δD) of 12–20, dipole moments (δP) of 1–8, and hydrogen bonds (δH) of 2.5–11.

[0097] In certain embodiments, the fragrance oil and hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of an atomic dispersion force (δD) of 12-20, preferably 14-20, a dipole moment (δP) of 1-8, preferably 1-7, and hydrogen bonds (δH) of 2.5-11, preferably 4-11.

[0098] According to one embodiment, the fragrance-adding compound includes a fragrance modifier (which can be used in addition to a hydrophobic solvent if one is present, or can be used as a substitute for a hydrophobic solvent if one is not present).

[0099] Preferably, a fragrance modifier is defined as a fragrance material having the following: i. Vapor pressure less than 0.0008 Torr at 22°C; ii. clogP of 3.5 or higher, preferably 4.0 or higher, more preferably 4.5; iii. At least two Hansen solubility parameters selected from the first group consisting of atomic dispersion forces of 12-20, dipole moments of 1-7, and hydrogen bonds of 2.5-11; iv. At least two Hansen solubility parameters selected from a second group consisting of 14-20 atomic dispersion forces, 1-8 dipole moments, and 4-11 hydrogen bonds, when a compound having a vapor pressure range of 0.0008-0.08 Torr at 22°C is in a dissolved state.

[0100] Preferably, the following components may be listed as modifiers, for example, but the list is not limited to the following materials: C12 alcohol, oxacyclohexadeca-12 / 13-en-2-one, 3-[(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecene-1-one, cyclopentadecanone, (8Z)-oxacycloheptadeca-8-en-2-one, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, mugaldehyde, 1,5,8-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene, (+-)-4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8 -Hexahydrocyclopenta[g]isochromene, (+)-(1S,2S,3S,5R)-2,6,6-trimethylspiro[bicyclo[3.1.1]heptan-3,1'-cyclohexane]-2'-en-4'-one, oxacyclohexadecan-2-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, (+)-(4R,4a S,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amyl cinnamic aldehyde, hexyl cinnamic aldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadien-3-one, (9Z)-9-cycloheptadecene-1-one.

[0101] According to a particular embodiment, the hydrophobic material does not contain any active ingredients (e.g., fragrances). According to this particular embodiment, the hydrophobic material preferably comprises a hydrophobic solvent, preferably selected from the group consisting of isopropyl myristate, triglycerides (e.g., Neobee® MCT oil, vegetable oil), D-limonene, silicone oil, mineral oil, and mixtures thereof, and optionally a hydrophilic solvent, preferably selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol, glycol ether, and mixtures thereof.

[0102] The term "biocide" refers to a chemical substance that can kill or reduce or prevent the growth and / or accumulation of living organisms (e.g., microorganisms). Biocides are commonly used in medicine, agriculture, forestry, and industries that prevent contamination of water, agricultural products including seeds, and oil pipelines. Biocides may include fungicides, herbicides, insecticides, algaecides, mollusk repellents, acaricides, and rodenticides; and / or antimicrobial substances such as fungicides, antibiotics, antimicrobial agents, antiviral agents, antifungal agents, antiprotozoal agents, and / or antiparasitic agents.

[0103] As used herein, “pesticide” refers to a substance that helps to repel or attract pests, and to reduce, suppress, or promote their growth, development, or activity. Pests are any organisms, whether animals, plants, or fungi, that invade or cause trouble to plants or animals, and pests include insects, especially arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0104] "Flavor oil" here means a specific mixture of flavoring ingredients or mixtures of flavoring ingredients, solvents, or adjuvants currently used in the preparation of flavor formulations, i.e., ingredients intended to be added to edible compositions or chewable products to impart, improve, or modify their sensory properties, particularly their flavor and / or aroma. Flavoring ingredients are well known to those skilled in the art, and their properties are not exhaustive, although this detailed description is not guaranteed. Those skilled in the art can select them based on their general knowledge, according to the intended use or application and the desired sensory effect. Many of these flavoring ingredients are listed in reference texts such as S. Arctander's book, *Perfume and Flavor Chemicals*, 1969, Montclair, NJ, USA, or its latest edition, or other similar works, e.g., *Fenaroli's Handbook of Flavor Ingredients*, 1975, CRC Press, or *Synthetic Food Adjuncts*, 1947, by MB Jacobs, van Nostrand Co., Inc. The solvents and adjuvants currently used for the preparation of fragrance formulations are also well known in the art.

[0105] In certain embodiments, the flavor is mint. In more specific embodiments, the mint is selected from the group consisting of peppermint and spearmint.

[0106] In further embodiments, the flavor is a coolant or a mixture thereof.

[0107] In another embodiment, the flavor is menthol flavor.

[0108] Flavors derived from or based on fruits in which citric acid is the dominant naturally occurring acid include, but are not limited to, citrus fruits (e.g., lemons, limes), limonene, strawberries, oranges, and pineapples. In one embodiment, the flavored food is lemon, lime, or orange juice extracted directly from the fruit. Further embodiments of the flavor include juices or liquids extracted from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, and any other citrus fruits, or their variations or hybrids. In certain embodiments, the flavor includes liquids extracted or distilled from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, any other citrus fruits, or their variations or hybrids, pomegranates, kiwifruits, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruit, mangoes, pears, tomatoes, and strawberries.

[0109] In certain embodiments, the flavor comprises a composition containing limonene, and in certain embodiments, the composition further comprises citrus fruits containing limonene.

[0110] In another specific embodiment, the flavor includes a flavor selected from the group consisting of strawberry, orange, lime, tropical, berry mix, and pineapple.

[0111] The term "flavor" includes not only flavors that impart or alter the smell of food, but also components that impart or alter the flavor. The latter do not necessarily have flavor or smell themselves, but can alter the flavor provided by other components, such as saltiness-enhancing components, sweetness-enhancing components, umami-enhancing components, and bitterness-blocking components.

[0112] In further embodiments, suitable sweeteners may be included in the particles described herein. In certain embodiments, the sweetener is selected from the group consisting of sugar (e.g., sucrose, but not limited to this), stevia components (e.g., stevioside or rebaudioside A, but not limited to these), sodium cyclamate, aspartame, sucralose, sodium saccharin, and acesulfame K or mixtures thereof.

[0113] According to any one embodiment of the present invention, the hydrophobic material is approximately 10% to 60% w / w, and even more specifically 15% to 45% w / w, relative to the total weight of the dispersion obtained after step ii).

[0114] According to a particular embodiment, shellac is added to the oil phase.

[0115] According to the present invention, at least one silicon precursor is added in step (i) and / or step (ii) and / or step (iii).

[0116] The silicon precursor may be selected from the group consisting of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), triethoxymethylsilane, dimethyldimethoxysilane, ethyltriethoxysilane, amine-functionalized silane, (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-dimethyl-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltriethoxysilane, and mixtures thereof.

[0117] According to a particular embodiment, at least one silicon precursor, preferably tetraethyl orthosilicate, is added to the dispersion, preferably to the two-phase dispersion obtained in step (ii).

[0118] According to certain embodiments, the silicon precursor is pre-hydrolyzed (typically by mixing the silicon precursor with 1-5 mM HCl) so that it readily interacts with the biopolymer membrane.

[0119] According to certain embodiments, the silicon precursor is added directly to the oil phase.

[0120] According to a particular embodiment, at least a first silicon precursor S1 is added to the dispersion, preferably to the two-phase dispersion obtained in step (ii), and at least a second silicon precursor S2 is added in step (iii).

[0121] According to a particular embodiment, at least a first silicon precursor S1 is added to the dispersion, preferably to the two-phase dispersion obtained in step (ii), and at least a second silicon precursor S2 is added in or after step (iii).

[0122] According to a particular embodiment, the first silicon precursor S1 is tetraethyl orthosilicate, and the second silicon precursor S2 is (3-aminopropyl)triethoxysilane.

[0123] According to one embodiment, if present, the first silicon precursor S1 is added in an amount consisting of more than 0% by weight and 20% by weight or less, preferably 5% to 15% by weight, based on the total weight of the dispersion.

[0124] According to the embodiment, if present, the second silicon precursor S2 is added in an amount consisting of more than 0% by weight and 10% by weight or less, preferably 1% to 6% by weight, based on the total weight of the dispersion.

[0125] According to the embodiment, a long-chain and / or medium-chain silane or a mixture of silanes is added to the oil phase. A long-chain and / or medium-chain silane or a mixture of silanes can be defined as a silane having more than three carbon organic chain substitutions. Silanes having more than three carbon organic chain substitutions can be selected from the group of silanes having more than three carbon organic chain substitutions, such as triethoxy-n-octylsilane, dodecyltriethoxysilane, octadecyltriethoxysilane, decyltriethoxysilane, n-hexyltriethoxysilane, and hexadecyltriethoxysilane, and mixtures thereof.

[0126] According to certain embodiments, the oil phase does not contain any polyfunctional monomers, preferably selected from the group consisting of at least one polyisocyanate, polyanhydride (e.g., polymaleic anhydride), polyacyl chloride (i.e., acyl chloride), polyepoxide, acrylate monomer, and mixtures thereof.

[0127] According to another embodiment, a polyfunctional monomer preferably selected from the group consisting of at least one polyisocyanate, polyanhydride (e.g., polymaleic anhydride), polyacid chloride (i.e., acyl chloride), polyepoxide, acrylate monomer, and mixtures thereof is added to the oil phase.

[0128] According to a particular embodiment, the monomer added in step i) is at least one polyisocyanate having at least two isocyanate functional groups.

[0129] Suitable polyisocyanates used in accordance with the present invention include aromatic polyisocyanates, aliphatic polyisocyanates, and mixtures thereof. The aforementioned polyisocyanates contain at least two, preferably at least three, isocyanate functional groups, but may contain up to six, or even as few as four, isocyanate functional groups. According to certain embodiments, triisocyanates (three isocyanate functional groups) are used.

[0130] According to one embodiment, the aforementioned polyisocyanate is an aromatic polyisocyanate.

[0131] The term “aromatic polyisocyanate” is used here to encompass any polyisocyanate containing an aromatic moiety. Preferably, the term includes a phenyl, toluyl, xylyl, naphthyl, or diphenyl moiety, and more preferably a toluyl or xylyl moiety. Preferred aromatic polyisocyanates are trimethylolpropane adducts of biuret, polyisocyanurates, and diisocyanates, and more preferably contain one of the particular aromatic moieties described above. More preferably, aromatic polyisocyanates include polyisocyanurates of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® RC), trimethylolpropane adducts of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® L75), and trimethylolpropane adducts of xylylene diisocyanate (commercially available from Mitsui Chemicals, Inc. under the trade name Takenate® D-110N). In the most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

[0132] According to another embodiment, the aforementioned polyisocyanate is an aliphatic polyisocyanate. The term “aliphatic polyisocyanate” is defined as a polyisocyanate that does not contain any aromatic moiety. Preferred aliphatic polyisocyanates are trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate (available from Mitsui Chemicals, Inc.), or biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N 100), with biuret of hexamethylene diisocyanate being even more preferred.

[0133] According to another embodiment, the polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both containing at least two or three isocyanate functional groups, and examples include a mixture of hexamethylene diisocyanate biuret and xylylene diisocyanate trimethylolpropane adduct, a mixture of hexamethylene diisocyanate biuret and toluene diisocyanate polyisocyanurate, and a mixture of hexamethylene diisocyanate biuret and toluene diisocyanate trimethylolpropane adduct. Most preferably, the polyisocyanate is a mixture of hexamethylene diisocyanate biuret and xylylene diisocyanate trimethylolpropane adduct. Preferably, when used as a mixture, the molar ratio of aliphatic polyisocyanate to aromatic polyisocyanate is in the range of 80:20 to 10:90.

[0134] According to the embodiments, the monomer used in the method of the present invention is present in an amount of 0.1 to 15% by weight, preferably 0.5 to 3% by weight, based on the total amount of the oil phase.

[0135] In another step of the method, curing step iii) is performed, which ultimately allows for the formation of microcapsules in the form of a slurry.

[0136] According to one embodiment, in step iii) of the method, a heating step is performed.

[0137] The purpose of this heating step is to denature the proteins, induce aggregation of the protein / polycation complex at the oil-water interface, and thermally anneal the shell.

[0138] The heating step is performed at a temperature of preferably 50°C to 100°C, more preferably 70°C to 90°C T den This can be carried out at the protein denaturation temperature. The duration of the heating step depends on the heating temperature. Typically, the heating step lasts from 60 to 180 minutes.

[0139] Depending on the properties of the protein, a person skilled in the art will be able to find a suitable temperature for inducing the aforementioned protein denaturation.

[0140] As a non-limiting example, the denaturation temperature T den The following applies: - For whey protein, the optimal temperature is 70-90°C. - For soy protein, the optimal temperature is 70-90°C. - For bovine serum albumin, the temperature range is 50-82°C. - For ovalbumin, the temperature range is 68-80°C. - For potato protein, the optimal temperature is 50-90°C.

[0141] This heating step can also enhance the further hydrolysis of the silicon precursor and its interaction with the biopolymer film.

[0142] During the curing step, the silicon precursor penetrates the biopolymer film, silicifies the film, and further condenses silicon on the shell. As a result, the formed shell is considered to be a composite biopolymer silicon shell with a gradient of different organic materials and silicon throughout the shell.

[0143] The heating step is preferably carried out at a pH of 4 to 6, more preferably 4.5 to 5.5.

[0144] According to a particular embodiment, the crosslinking agent is added in at least one of the steps of the method. According to a particular embodiment, the crosslinking agent may be added during and / or after curing step iii).

[0145] The crosslinking agent may be an enzymatic crosslinking agent such as an enzyme, or a non-enzymatic crosslinking agent such as glutaraldehyde or genipine.

[0146] According to certain embodiments, the crosslinking agent is an enzyme.

[0147] According to certain embodiments, the enzyme is transglutaminase.

[0148] The enzyme may be used in an amount of 0.001 to 5%, preferably 0.001 to 1%, preferably 0.001 to 0.1%, and preferably 0.005 to 0.02%, based on the total weight of the slurry in step c).

[0149] According to certain embodiments of the present invention, at the end of or during step iii), a polymer selected from the group consisting of nonionic polysaccharides, cationic polymers, polyscinimide derivatives (e.g., described in International Publication No. 2021185724) and mixtures thereof may be added to the slurry of the present invention to form an outer coating for the microcapsules.

[0150] Nonionic polysaccharide polymers are well known to those skilled in the art and are described, for example, on page 29, lines 1-25 of International Publication No. 2012 / 007438, and on page 2, lines 12-19 and page 4, lines 3-12 of International Publication No. 2013 / 026657. Preferred nonionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose, and hydroxypropyl methylcellulose.

[0151] Cationic polymers are well known to those skilled in the art. Preferred cationic polymers have a cationic charge density of at least 0.5 meq / g, more preferably at least about 1.5 meq / g, but preferably less than about 7 meq / g, more preferably less than about 6.2 meq / g. The cationic charge density of a cationic polymer can be determined by the Kjeldahl method, as described in the United States Pharmacopeia, under chemical testing for nitrogen measurement. Preferred cationic polymers are selected from those containing units comprising primary, secondary, tertiary, and / or quaternary amine groups, which may be present in lateral substituents that form part of the main polymer chain or are directly attached thereto. The weight-average (Mw) molecular weight of the cationic polymer is preferably 10,000 daltons to 3.5 M daltons, more preferably 50,000 daltons to 1.5 M daltons. According to certain embodiments, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylaminomethacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-imidazole-3-ium chloride), vinylpyrrolidone, acrylamidopropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride, or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride, and cellulose hydroxypropyltrimonium chloride may be used. Preferably, the copolymer will be selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride, and cellulose hydroxypropyltrimonium chloride.Specific examples of commercially available products include Salcare® SC60 (a cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, manufactured by BASF) or Luviquat®, for example, PQ 11N, FC 550 or Style (quaternary copolymer of polyquaternium-11~68 or vinylpyrrolidone, manufactured by BASF), or Jaguar® (C13S or C17, manufactured by Rhodia).

[0152] According to any one of the above embodiments of the present invention, the above-mentioned amount of polymer is added, consisting of about 0% to 5% w / w, and even more specifically, about 0.1% to 2% w / w, the percentage being expressed on a w / w basis relative to the total weight of the slurry obtained after step iii). Those skilled in the art will clearly understand that only a portion of the aforementioned added polymer is incorporated into / deposited in the microcapsule shell.

[0153] Multiple microcapsule systems According to the embodiment, the microcapsules of the present invention (first microcapsule slurry) can be used in combination with a second microcapsule slurry.

[0154] Another subject of the present invention is, - The microcapsule slurry of the present invention as a first microcapsule slurry, - Second microcapsule slurry and A microcapsule delivery system comprising the first microcapsule slurry and the second microcapsule slurry, wherein the microcapsules contained in the first and second microcapsule slurry differ in respect to their hydrophobic material and / or their wall material and / or their coating material.

[0155] Method for preparing microcapsule powder Another subject of the present invention is a method for preparing microcapsule powder, comprising the steps defined above and an additional step of subjecting the microcapsule slurry obtained in step iii) to drying, such as spray drying, to provide the microcapsules as they are, i.e., in powder form. It is understood that any standard method known to those skilled in the art for performing such drying is also applicable. In particular, the slurry may be preferably spray-dried in the presence of a polymer carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, gum arabic, vegetable gum, pectin, xanthan gum, alginate, carrageenan, or cellulose derivative to provide microcapsules in powder form.

[0156] According to certain embodiments, the carrier material includes free fragrance oils, which may be the same as or different from the fragrance from the core of the microcapsule.

[0157] Microcapsule slurry / Microcapsule powder The microcapsule slurry and microcapsule powder obtained by the above method are also subjects of the present invention.

[0158] In another embodiment, the present invention relates to a core-shell microcapsule, - An oily core containing a hydrophobic material, - It is a composite shell, (i) A biopolymer material containing a complex of protein and polycation, (ii) Silicon-based materials and A composite shell including This relates to core-shell microcapsules, including those mentioned above.

[0159] According to the embodiment, the microcapsule has a positive zeta potential greater than 10 mV, preferably between 10 and 80 mV, and more preferably between 10 and 65 mV.

[0160] All previous embodiments described earlier regarding methods for preparing microcapsule slurries also apply to the microcapsule slurries described above.

[0161] The definitions of hydrophobic materials, proteins, and polycations are the same as those described herein.

[0162] According to one embodiment, the silicon-based material is derived from a compound selected from the group consisting of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), triethoxymethylsilane, dimethyldimethoxysilane, ethyltriethoxysilane, amine-functionalized silane, (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-dimethyl-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltriethoxylan, and mixtures thereof.

[0163] According to the present invention, the oily core includes a hydrophobic material as defined above.

[0164] In certain embodiments, the shell material includes a biodegradable material.

[0165] In certain embodiments, the shell is biodegradable to at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98% within 60 days in accordance with OECD 301F.

[0166] In certain embodiments, the core-shell microcapsules are biodegradable within 60 days according to OECD 301F, with a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98%.

[0167] It is understood that, in accordance with OECD 301F, core-shell microcapsules, including all components such as the core, shell, and optionally the coating, can have at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98% biodegradability within 60 days.

[0168] OECD 301F is a standard test method for biodegradability developed by the Organisation for Economic Co-operation and Development (OECD).

[0169] A typical method for extracting shells to measure biodegradability is disclosed in Gasparini and all in Molecules 2020, 25,718.

[0170] Flavoring compositions / consumer products The microcapsules of the present invention can be used in combination with an active ingredient. Therefore, the subject of the present invention is (i) Microcapsules as defined above and (ii) A more preferred active ingredient consisting of cosmetic ingredients, skincare ingredients, fragrance ingredients, flavor ingredients, odor neutralizing ingredients, antibacterial ingredients, fungal ingredients, pharmaceutical or agricultural chemical ingredients, disinfectant ingredients, insect repellents or insect attractants, and mixtures thereof. It is a composition containing [the specified ingredient].

[0171] The microcapsules of the present invention can be used in the preparation of fragrance-adding compositions or flavor-imparting compositions, which are also the subject of the present invention.

[0172] Another subject of the present invention is, (i) Microcapsules as defined above, wherein the oil is a microcapsule containing a fragrance, (ii) at least one component selected from the group consisting of fragrance carriers, fragrance co-components, and mixtures thereof, (iii) at least one fragrance adjuvant and It is a fragranced composition containing [the specified ingredient].

[0173] Examples of liquid fragrance carriers, in non-limiting terms, include emulsions, i.e., systems of solvent and surfactant, or solvents commonly used in fragrances. A detailed description of the properties and types of solvents commonly used in fragrances cannot be exhaustive. However, examples of solvents, in non-limiting terms, include dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol, or ethyl citrate, which are among the most commonly used. For compositions containing both fragrance carriers and fragrance co-components, other suitable fragrance carriers beyond those previously specified may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known by trade name Isopar® (manufactured by Exxon Chemical), or glycol ethers and glycol ether esters such as those known by trade name Dowanol® (manufactured by Dow Chemical Company). “Fragrance co-components” here refers to compounds used in fragrance preparations or compositions to impart a hedonic effect, and which are not microcapsules as defined above. In other words, for such an ingredient to be considered a fragrance-adding ingredient, it must not merely have an odor, but must be recognized by those skilled in the art as being able to impart or alter the odor of a composition in a positive or pleasant manner.

[0174] The properties and types of fragrance co-components present in fragrance compositions are not guaranteed to be more detailed here, nor are they exhaustive in any case; those skilled in the art can select them based on general knowledge according to the intended use or application and the desired organic effect. Generally speaking, these fragrance co-components belong to a diverse range of chemical classes, including alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and the aforementioned fragrance co-components may be of natural or synthetic origin. Many of these co-components are listed in reference texts such as S. Arctander's book *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its latest edition, or other works of similar nature, as well as in the extensive patent literature in the field of fragrances. It is also understood that the aforementioned co-components may be compounds known to release various types of fragrance compounds, also known as pro-fragrances, in a controlled manner. Non-limiting examples of suitable professional fragrances include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, and trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone. Non, 2-(dodecylthio)octan-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-diene-1-yloxo(phenyl)acetate, (Z)-hexa-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadiene-1-ylhexadecanoate, bis(3,7-dimethylocta-2,6-Dienyl) succinate, (2-((2-methylundeca-1-en-1-yl)oxy)ethyl)benzene, 1-Methoxy-4-(3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, (3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, 1-(((Z)-hexa-1-yl)oxy)-2-methylundeca-1-ene, (2-((2-methylundeca -1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undeca-1-ene, 1-methoxy-4-(1-phenethoxypropa-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxypropa-1-en-2-yl)benzene, 2-(1-phenethoxypropa-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene Examples include 2-(1-((3,7-dimethylocta-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylbyl)oxy)-3-methoxybenzaldehyde, or mixtures thereof.

[0175] "Fragrance adjuvant" here refers to an ingredient that can impart additional benefits such as color, specific lightfastness, and chemical stability. While it is not possible to provide a detailed description of the properties and types of adjuvants commonly used in fragrance bases, it should be noted that the aforementioned ingredients are well known to those skilled in the art.

[0176] Preferably, the fragrance composition according to the present invention contains 0.01 to 30% by weight of microcapsules as defined above.

[0177] The microcapsules of the present invention can be advantageously used in many application fields and can be used in consumer products. The microcapsules can be used not only in liquid form applicable to liquid consumer products, but also in powder form applicable to powder consumer products.

[0178] According to certain embodiments, the consumer product as defined above is a liquid, a) At least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, b) Water or a water-miscible hydrophilic organic solvent, c) A microcapsule slurry as defined above, d) Optionally, non-encapsulated fragrances and Includes.

[0179] According to a particular embodiment, the consumer product as defined above is in the form of a powder, a) At least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, b) Microcapsule powder as defined above, c) Optionally, a fragrance powder different from the microcapsules defined above. Includes.

[0180] In the case of microcapsules containing an oil-based core, the products of the present invention can be used in particular in scented consumer products such as fine fragrances or products belonging to "functional" fragrances. Functional fragrances include, in particular, personal care products including hair care, body cleansing, skin care, and hygiene care, as well as home care products including laundry care and air care. Thus, another subject of the present invention is scented consumer products containing, as defined above, microcapsules or fragrance compositions as defined above as fragrance components. The fragrance elements of the aforementioned consumer products may be a combination of fragrance microcapsules as defined above and free or unencapsulated fragrances, as well as types of fragrance microcapsules other than those disclosed herein.

[0181] In particular, liquid consumer products, a) At least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, b) Water or a water-miscible hydrophilic organic solvent, c) A fragrance composition as defined above and Liquid consumer products containing the same are another subject of the present invention.

[0182] Furthermore, it is a powdered consumer product, (a) at least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, (b) A fragrance composition as defined above and Powdered consumer products containing the same are also part of the present invention.

[0183] Therefore, the microcapsules of the present invention can be added either by themselves or as part of the fragrance composition of the present invention in a fragranced consumer product.

[0184] To clarify, it should be noted that “fragrance-containing consumer products” refer to consumer products that are expected to provide a fragrance effect, among various benefits, to the surface to which they are applied (e.g., skin, hair, textiles, paper, or household surfaces) or to the air (e.g., air fresheners, deodorizers). In other words, the fragrance-containing consumer products according to the present invention are manufactured products that contain a functional compound, also called a “base,” together with a fragrance agent, in particular an effective amount of microcapsules according to the present invention.

[0185] The properties and types of other ingredients in fragranced consumer products are not guaranteed to be described in more detail here, nor are they exhaustive in any way; those skilled in the art can select them based on general knowledge according to the aforementioned product properties and desired effects. Base formulations for consumer products that can incorporate the microcapsules of the present invention can be found in the abundant literature relating to such products. These formulations are not guaranteed to be described in more detail here, nor are they exhaustive in any way; anyone familiar with the technology of formulating such consumer products can, based on general knowledge and available literature, select appropriate ingredients.

[0186] Appropriate fragranced consumer products include, but are not limited to, fragrances, e.g., fine fragrances, colognes, aftershave lotions, body splashes; fabric care products, e.g., liquid or solid detergents, tablets and unit doses (single-chamber or multi-chamber), fabric softeners, dryer sheets, fabric refreshers, ironing water, or bleach; personal care products, e.g., hair care products (e.g., shampoos, hair conditioners, prepared colorants, or hairsprays), cosmetics (e.g., vanishing creams, body lotions, deodorants, or antiperspirants), or skincare products (e.g., fragranced soaps, showers, or bath mousses, body washes, oils, or gels, bath salts, or hygiene products); air care products, e.g., air fresheners or "ready to use" products. (Use) Powdered fragrances; or home care products, such as all-purpose cleaners, liquid or powder or tablet dish soaps, toilet cleaners, or products for cleaning various surfaces, such as sprays and wipes for treating / restoring textiles or hard surfaces (floors, tiles, stone floors, etc.); hygiene products, such as sanitary napkins, diapers, and toilet paper.

[0187] Another subject of the present invention is, - Personal care active base, - Microcapsules as defined above or fragrance compositions as defined above Consumer products that include, Consumer products are in the form of personal care compositions.

[0188] Personal care active ingredients that can incorporate the microcapsules of the present invention can be found in the extensive literature on such products. These formulations are not exhaustive and do not warrant further detailed explanation. Anyone familiar with the technology of such consumer product formulations can, based on general knowledge and available literature, select appropriate ingredients.

[0189] The personal care composition is preferably selected from the group consisting of hair care products (e.g., shampoo, hair conditioner, prepared colorants or hairspray), cosmetics (e.g., vanishing cream, body lotion or deodorant or antiperspirant), skin care products (e.g., scented soap (e.g., bar soap), shower or bath mousse, body wash, oil or gel, bath salt or hygiene product); or oral care products, such as toothpaste, toothpaste, or oral whitening products.

[0190] Another subject of the present invention is, - Home care or fabric care active base, - A consumer product comprising microcapsules as defined above or a fragrance composition as defined above, Consumer products are in the form of home care or fabric care compositions.

[0191] Home care or fabric care active ingredients that can incorporate the microcapsules of the present invention can be found in the extensive literature on such products. These formulations are not exhaustive and do not warrant further detailed descriptions. Anyone familiar with the technology of such consumer product formulations can, based on general knowledge and available literature, select appropriate ingredients.

[0192] Preferably, the consumer product contains 0.1 to 15% by weight, more preferably 0.2 to 5% by weight, of the microcapsules of the present invention, where these percentages are defined by weight relative to the total weight of the consumer product. Of course, the above concentrations can be adapted according to the desired benefits and effects for each product.

[0193] According to certain embodiments, consumer products incorporating microcapsules have a pH of less than 4.5.

[0194] In the case of liquid consumer products described later, the term "active base" should be understood to mean that the active base includes an active material (typically a surfactant) and water.

[0195] In the case of solid consumer products described below, the term "active base" should be understood to mean that the active base includes active materials (typically including surfactants) and auxiliary agents (e.g., bleaches, buffers; builders; dirt-releasing or dirt-suspending polymers, granular enzyme particles, corrosion inhibitors, defoamers, sud-suppressing agents, dyes, fillers, and mixtures thereof).

[0196] Fabric softener The present invention relates to consumer products in the form of fabric softeners, including the following: - A fabric softener active base, preferably comprising at least one active material selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (ester quats), Hamburg ester quats (HEQ), TEAQ (triethanolamine quats), silicones, and mixtures thereof, wherein the active base is preferably used in an amount comprising 85 to 99.95% by weight based on the total weight of the composition, - A microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0197] Liquid detergent The present invention relates to a consumer product in the form of a liquid detergent composition comprising the following: - A liquid detergent active base, preferably comprising an anionic surfactant, such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants, such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, and alkyl polyglucosamides, wherein the active base is preferably used in an amount comprising 85 to 99.95% of the total weight of the composition. - A microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0198] Solid detergent The present invention relates to a consumer product in the form of a solid detergent composition comprising the following: - A solid detergent active base, preferably comprising an anionic surfactant, such as alkylbenzene sulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES), and a nonionic surfactant, such as alkylamine, alkanolamide, fatty alcohol poly(ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymer, amine oxide, alkyl polyglucoside, and alkyl polyglucosamide, wherein the active base is preferably used in an amount comprising 85 to 99.95% of the total weight of the composition. A microcapsule powder or microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0199] Shampoo / Shower Gel The present invention relates to consumer products in the form of shampoo or shower gel compositions comprising the following: - A shampoo or shower gel active base, preferably comprising at least one active material selected from the group consisting of sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside, amino acid-based surfactants and mixtures thereof, wherein the active base is preferably used in an amount comprising 85 to 99.95% by weight based on the total weight of the composition, - A microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0200] Rinse-off conditioner The subject of this invention is a consumer product in the form of a rinse-off conditioner composition comprising the following: - Rinse-off conditioner active base, preferably comprising at least one active material selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, wherein the active base is preferably used in an amount comprising 85 to 99.95% by weight based on the total weight of the composition, rinse-off conditioner active base, - A microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0201] Solid scent booster The present invention relates to a consumer product in the form of a solid scent booster composition comprising the following: - Preferably a solid carrier selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, sugars such as sucrose, monosaccharides, disaccharides, polysaccharides and starch derivatives, cellulose, methylcellulose, ethylcellulose, propylcellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol and isomalt, PEG, PVP, citric acid or any water-soluble solid acid, fatty alcohol or fatty acid and mixtures thereof. - A microcapsule slurry in powder form as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0202] Liquid scent booster The subject of this invention is a consumer product in the form of a liquid scent booster composition comprising the following: - aqueous phase, - A surfactant system comprising essentially one or more nonionic surfactants, wherein the surfactant system has an average HLB of 10 to 14 and is preferably selected from the group consisting of ethoxylated aliphatic alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxylesters, alkyl polyglucosides, amine oxides, and combinations thereof. - Linkers selected from the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxylcarboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants having an HLB of less than 10, and mixtures thereof, and - A microcapsule slurry in the form of a slurry, as defined above, preferably consisting of an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0203] Hair coloring The present invention relates to a consumer product in the form of an oxidizing hair coloring composition comprising the following: - An oxidation phase containing an oxidizing agent, and an alkali phase containing an alkalizing agent, a dye precursor, and a coupling compound, wherein the aforementioned dye precursor and the aforementioned coupling compound form an oxidizing hair dye in the presence of the oxidizing agent, preferably in an amount comprising 85 to 99.95% by weight based on the total weight of the composition. - A microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition. - Optional free fragrance oil.

[0204] Flavoring composition According to a particular embodiment, the consumer product is in the form of a fragrance composition comprising the following: - 0.1 to 30%, preferably 0.1 to 20%, of microcapsules, preferably in the form of a slurry as defined above. - 0-40%, preferably 3-40%, of fragrance, and - 20-90%, preferably 40-90%, of ethanol based on the total weight of the fragrance composition.

[0205] The present invention will be further described below with reference to examples. It should be understood that the claims of the present invention are not intended to be limited in any way by these examples. [Examples]

[0206] [Example 1: Preparation of microcapsules by the method of the present invention] (material and method) Electron microscopy of the capsule: A diluted microcapsule slurry was dried on carbon tape, attached to an aluminum stub, and sputter-coated with gold-palladium plasma. This stub was then placed in a scanning electron microscope (JOEL 6010 PLUS LA) and analyzed. Energy-dispersive spectroscopy (EDS) was used to determine the elemental composition of the sample region through point analysis, mapping, and spectral generation of the target area.

[0207] Optical microscopy examination of capsules: The diluted microcapsule slurry was dried on a glass slide and imaged using an optical microscope (Olympus EX51) with 10x and 20x objective lenses.

[0208] (General protocol) 1) Add the whey protein isolate and / or chitosan oligosaccharide to deionized water at room temperature and stir at room temperature for about 30 minutes until no dry powder or dry material is observed in the solution; 2) Optionally, dissolve CaCl2·2H2O in deionized water and slowly add it to the whey protein isolate solution while stirring; 3) Combine the fragrance oil with a WPI / chitosan oligosaccharide (or CaCl2·2H2O) solution and homogenize (10,000 rpm, 2 minutes) to prepare an oil-in-water emulsion; 4) Transfer the emulsion to the reactor and stir at room temperature; 5) Meanwhile, add TEOS to a 1 mM HCl solution in a separate vial and sonicate for 20 minutes; 6) Add the pre-hydrolyzed TEOS solution to the reactor and stir the emulsion at room temperature for 30 minutes; 7) Next, heat the reactor to 80°C, maintain it at 80°C for 2 hours, and then cool it to room temperature; 8) Optionally, add APTES to the reactor and stir the emulsion at room temperature for 20 hours.

[0209] Microcapsules A to D were prepared according to the protocol described above, using the following components. [Table 1]

[0210] [Table 2]

[0211] As can be seen from Figures 1 to 6, microcapsules were obtained. Figure 2 shows the SEM-EDS silicon (Si) element mapping and EDS spectrum of the region in Figure 1, which shows that the microcapsule shell is made of silicon-based material (composed of silicon-based material). The microcapsules are stable during drying on the glass slide and during SEM imaging.

[0212] [Example 2: Preparation of microcapsules by the method of the present invention] Microcapsules E-G were prepared using the same protocol as described in Example 1, except for the following: - Sample E: TEOS was directly added to the emulsion.

[0213] - Sample F: TEOS was directly added to the oil phase.

[0214] - Sample G: TEOS was added to the oil phase (5%) and the emulsion (10%, pre-hydrolyzed with 1 mM HCl).

Table 3

[0215] [Example 3 Preparation of Microcapsules by the Method of the Present Invention] Microcapsules H and I were prepared according to the following protocol.

[0216] Reaction steps: 1) Dissolve shellac in ethanol and stir at 50 °C. If the concentration is appropriate, shellac will dissolve completely in ethanol and remain a clear solution at room temperature; 2) At room temperature, pipette the shellac / ethanol solution into sesame oil while stirring. While continuing to stir, heat the mixture to 80 °C to make a homogeneous solution and then cool to room temperature; 3) Add whey protein isolate and chitosan oligosaccharide to deionized water at room temperature and stir at room temperature for about 30 minutes until no dry powder or dry matter is observed in the solution; 4) Combine the shellac / ethanol / sesame oil with the WPI / chitosan oligosaccharide solution and homogenize (10,000 rpm, 2 minutes) to prepare a water-in-oil emulsion; 5) Transfer the emulsion to the reactor and stir at room temperature; 6) Heat the reactor to 80 °C, hold for 2 hours, and then cool to room temperature; 7) On the other hand, add TEOS to a 1 mM HCl solution in a vial and sonicate for 20 minutes; 8) Add the pre-hydrolyzed TEOS solution to the reactor and stir the emulsion at room temperature for 2.5 hours; 9) Optionally, add APTES to the reactor and stir the emulsion at room temperature for 20 hours. [Table 4]

[0217] Microcapsule H is shown in Figure 7.

[0218] [Example 4: Preparation of spray-dried microcapsules] Microcapsules J were prepared using the same protocol as described in Example 1, except that Uvinul A Plus was added and dissolved in the fragrance oil before emulsification, and a chitosan oligosaccharide with a molecular weight of 1052 was used. [Table 5]

[0219] First, wash and rinse the microcapsules J with deionized water.

[0220] The spray drying procedure is as follows: 1) Dissolve Capsul® (modified starch) and maltodextrin 10DE in water at 600 rpm and 50°C for 2 hours. 2) Add the capsule slurry to the carrier solution and stir gently. 3) Turn on the spray dryer and allow it to reach the operating temperature. 4) Pass 50 mL of high-temperature deionized water through a spray dryer. 5) Place the capsule and carrier mixture in a spray dryer while stirring. 6) After spray drying is complete, clean the line with high-temperature deionized water. 7) Cool the spray dryer and remove the samples from the coarse and fine powder collectors.

[0221] Figures 8 to 10 show SEM electron microscope images of microcapsules J after washing, spray drying (coarse collection fraction), and rehydration to dissolve the carrier, clearly demonstrating that the microcapsules remained intact after the spray drying and resuspension processes.

[0222] [Example 5 Preparation of Microcapsules by the Method of the Present Invention (Long-Chain Silane in Oil Phase)] Microcapsules K to L were prepared using the following components according to the following protocol. [Table 6]

[0223] 1) Add isolated whey protein to deionized water at room temperature and stir to dissolve, then add chitosan oligosaccharide and stir at room temperature for about 30 minutes until no dry powder or dry material is observed in the solution. Adjust the pH of the mixed solution to 5.5 using 0.1 M HCl; 2) Add long-chain silane (triethoxy-n-octylsilane or dodecyltriethoxysilane) to the flavor oil and stir to form a homogeneous mixture; 3) Combine the flavor oil with the long-chain silane with the WPI / chitosan oligosaccharide solution and homogenize (10,000 rpm, 2 minutes) to prepare an oil-in-water emulsion; 4) Transfer the emulsion to a reactor and stir at room temperature; 5) On the other hand, add TEOS to a 1 mM HCl solution in a separate vial and sonicate for 20 minutes; 6) Add the pre-hydrolyzed TEOS solution to the reactor and stir the emulsion at room temperature for 30 minutes; 7) Then, heat the reactor to 80 °C, hold at 80 °C for 2 hours, and then cool to room temperature; 8) Add APTES to the reactor and stir the emulsion at room temperature for 20 hours.

[0224] Figures 11 to 14 are the optical images of Microcapsules K and L dried on a slide glass and the SEM electron images of Microcapsules K and L (the microcapsules are stable during drying on the slide glass and SEM imaging).

[0225] [Example 6 Preparation of Microcapsules by the Method of the Present Invention] Microcapsules M-O were prepared using the same protocol as described in Example 1, except for the following: 1) First, dissolve the WPI in deionized water, then add the chitosan oligosaccharide to the solution and stir for 30 minutes until all the dry powder in the solution is gone. Adjust the pH of the mixed solution to 5.5 using dilute hydrochloric acid (0.1 M HCl solution). (Use chitosan oligosaccharide with a molecular weight of 1480). [Table 7]

[0226] [Example 7: Dynamic headspace is used to evaluate microcapsule encapsulation and popping effect] To evaluate the popping effect of capsules after friction, dynamic headspace intensity measurements were performed on blotter paper loaded with a 1% microcapsule slurry. After drying, the intensity was evaluated before and after friction was applied by rubbing with a gloved finger. 100 μL of a 1% capsule slurry of microcapsules L, M, and O (containing 0.2% fragrance oil from a five-compound fragrance mixture [equal mass of each of the five compounds listed in Table 2]) was pipetteed onto 0.5-inch × 1.5-inch rectangular blotter paper strips and dried under ambient conditions for 24 hours. The supplied and dried blotter strips were carefully placed into 20 mL glass dynamic headspace vials and then capped. For the "after rubbing" samples, the blotter strips were vigorously rubbed three times with a gloved index finger. The rubbed blotters were then placed into vials and capped. Headspace measurements of the fragrance intensity of the blotters before and after friction were performed using a Shimadzu GC-MS instrument with DHS (Dynamic Headspace) functionality. Following the sampling stage, 20 ml of HS was trapped in a Tenax tube for desorption and observation.

[0227] For five fragrance components, the ratio of headspace signal peaks before and after friction was measured. As shown in Figure 15, selected characteristic headspace signal ratios for Dorisyl (fragrance compound 1) and Verdox (fragrance compound 2) were chosen to illustrate the effect of friction. The ratio values ​​(ratio = headspace intensity value after friction / headspace intensity value before friction) were significantly higher than 1 for microcapsules L, M, and O, indicating a stronger signal after friction and a significant popping effect when the fragrance oil is released from the capsule core due to friction. The burst effect due to friction was particularly pronounced for microcapsules L and M, with headspace intensity ratios greater than 2.

[0228] Figure 15 shows plots of headspace intensity ratios to explain the popping effect, evaluated before and after friction is applied to a paper blotter with microcapsules L, M, and O.

[0229] [Example 8: Zeta potential measurement] The zeta potentials of the microcapsules (M, N, L, and O) according to the present invention were measured in 1 mM KCl at pH 3, 5.5, and 9 using a Malvern ZetaSizer Nano ZS-90. The results showed that the microcapsules M, N, and O prepared by APTES had positively charged zeta potentials exceeding +40 mV at pH 5.5. [Table 8]

[0230] [Example 9: Microcapsule A after incubation with fabric softener] Microcapsule A was incubated in a sealed jar at 37°C for 2 months in a fabric softener (see composition in Table 10). [Table 9]

[0231] Figure 16 is an SEM electron microscope image of microcapsule A after incubation, showing that microcapsule A can maintain its capsule structure in the fabric softener during the incubation period.

[0232] [Example 10] To demonstrate that the shell structure can be maintained even after prolonged heat exposure (500°C), microcapsule A was subjected to extreme heat treatment. Further elemental analysis of these microcapsules revealed the presence of elemental silicon after heating.

[0233] Thermal exposure tests were performed using a TGA Q50 manufactured by TA Instruments. Microcapsule A slurry was loaded into a TGA sample pan and heated to 500°C according to the following protocol: initial equilibration at 30°C, followed by heating to 50°C at a rate of 5°C / min, isothermal heating at 50°C for 250 minutes, heating to 500°C at a rate of 10°C / min, and isothermal heating at 500°C for 60 minutes.

[0234] Figure 17 shows backscatter electron microscope images, silicon (Si) element EDS mapping, and SEM-EDS (energy-dispersive spectroscopy) spectra of microcapsule A after exposure to 500°C, demonstrating that the microcapsule can maintain its physical structure even after extreme heat treatment.

[0235] [Example 11: Liquid detergent composition] A microcapsule slurry (see Examples 1-6) is dispersed in a liquid detergent composition to obtain a concentration of 0.15% encapsulated fragrance. [Table 10]

[0236] [Example 12: Rinse-off Conditioner] The microcapsule slurry (see Examples 1-6) is dispersed in the rinse-off conditioner base described in Table 10 to obtain a concentration of 0.5% encapsulated fragrance oil. [Table 11]

[0237] [Example 13: Shampoo Composition] The microcapsule slurry (see Examples 1-6) is dispersed in the shampoo composition, and a fragrance equivalent to 0.2% is added. [Table 12]

[0238] [Example 14: Antiperspirant Roll-on Emulsion Composition] A microcapsule slurry (see Examples 1-6) is dispersed in an antiperspirant roll-on emulsion composition, and a fragrance equivalent to 0.2% is added. [Table 13]

[0239] Parts A and B are heated separately to 75°C. Part A is added to part B while stirring, and the mixture is homogenized for 10 minutes. Then, the mixture is cooled while stirring, and when the mixture reaches 45°C, part C is slowly added while stirring, and when the mixture reaches 35°C, part D is added slowly while stirring. Then, the mixture is cooled to room temperature.

[0240] [Example 15: Composition of Shower Gel] The microcapsule slurry (see Examples 1-6) is dispersed in the following composition, and a fragrance equivalent to 0.2% is added. [Table 14]

Claims

1. A method for preparing a core-shell microcapsule slurry, (i) A step of mixing the protein and polycation in a dispersed phase, (ii) The step of adding an oil phase containing a hydrophobic material to the dispersed phase to form a dispersion, (iii) A step of curing to form a microcapsule slurry and Includes, Add at least one silicon precursor in step (i) and / or step (ii) and / or step (iii). method.

2. The method according to claim 1, wherein the protein is selected from the group consisting of potato protein, chickpea protein, algae protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, whey protein, milk protein, casein salt, casein, hydrolyzed protein, gelatin, gluten, pea protein, soy protein, silk protein, β-lactoglobulin, ovalbumin, bovine serum albumin, and mixtures thereof.

3. The aforementioned polycation is chitosan, chitosan oligomer, chitosan oligosaccharide, Ca ２＋ Mg ２＋ , Zn ２＋ Ba ２＋ , Sr ２＋ The method according to claim 1 or 2, selected from the group consisting of, and mixtures thereof.

4. The method according to claim 3, wherein the polycation is a chitosan oligosaccharide having a molecular weight of less than 5000.

5. The method according to any one of claims 1 to 4, wherein the weight ratio of the protein to the polycation is 5:1 to 1:

3.

6. The method according to any one of claims 1 to 5, wherein the protein is a whey protein and the polycation is a chitosan oligosaccharide.

7. The method according to any one of claims 1 to 6, wherein the at least one silicon precursor is selected from the group consisting of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), triethoxymethylsilane, dimethyldimethoxysilane, ethyltriethoxysilane, amine-functionalized silane, and mixtures thereof.

8. The method according to any one of claims 1 to 7, wherein at least one silicon precursor is added to the dispersion obtained in step ii).

9. The method according to any one of claims 1 to 8, wherein at least a first silicon precursor is added to the dispersion obtained in step (ii), and at least a second silicon precursor is added during or after step (iii).

10. The method according to claim 9, wherein the first silicon precursor is tetraethyl orthosilicate and the second silicon precursor is (3-aminopropyl)triethoxysilane.

11. The method according to any one of claims 1 to 10, wherein a long-chain and / or medium-chain silane or a mixture of silanes is added to the oil phase.

12. The method according to any one of claims 1 to 11, wherein no polyfunctional monomer is added at any stage of the method.

13. Core-shell microcapsules, - An oily core containing a hydrophobic material, - It is a composite shell, (i) A biopolymer material containing a complex of protein and polycation, (ii) Silicon-based materials and A composite shell including Core-shell microcapsules containing these capsules.

14. The core-shell microcapsule according to claim 13, wherein the protein is a whey protein and the polycation is a chitosan oligosaccharide.

15. A consumer product in the form of a flavored or aromatic consumer product, comprising microcapsules as defined in claim 13 or 14.

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