Microcapsules from polylactone-based prepolymers.

Abstract

The present invention relates to a method for preparing core-shell microcapsules and core-shell microcapsule slurries comprising polylactone-based polyisocyanate prepolymers obtained by reacting polylactone polyols with polyisocyanates, the core-shell microcapsules and core-shell microcapsule slurries, and perfume compositions and consumer products containing the same.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing core-shell microcapsules and core-shell microcapsule slurries comprising polylactone-based polyisocyanate prepolymers obtained by reacting polylactone polyols with polyisocyanates, the core-shell microcapsules and core-shell microcapsule slurries, and perfume compositions and consumer products containing the same.

[0002] Background of the Invention One of the problems facing the fragrance industry is that the olfactory benefits provided by odor compounds are lost relatively quickly due to their volatility, especially that of "top notes." To control the release rate of volatile substances, delivery systems such as perfume-containing microcapsules must protect the core payload and release it later upon triggering. An important requirement from the industry for these systems is that they must withstand difficult suspension in a base without physical dissociation or decomposition. This is referred to as the storage stability of the delivery system. For example, scented personal and household cleaners containing high levels of aggressive surfactant detergents pose significant challenges to the stability of microcapsules.

[0003] Polyurea and polyurethane-based microcapsule slurries are widely used in, for example, the perfume industry, because they provide long-lasting pleasant olfactory effects after being applied to different substrates.These microcapsules have been widely disclosed in the prior art (for example, see the applicant's International Publication No. 2007 / 004166 or European Patent No. 2300146).The main drawback of polyurea and polyurethane-based microcapsules is that they have poor or no biodegradability.

[0004] There remains a need to provide novel microcapsules that do not compromise on microcapsule performance, particularly with regard to stability in challenging media such as consumer product bases, as well as on delivering good performance in terms of active ingredient delivery, e.g., good olfactory performance in the case of perfume ingredients, and that provide satisfactory or good biodegradability.

[0005] The present invention proposes a solution to the above-mentioned problems by providing novel microcapsules and methods for preparing said microcapsules.

[0006] Detailed Description of the Invention Unless otherwise specified, percentages (%) are meant to indicate weight percent of the composition.

[0007] "Active ingredient" means a single compound or a combination of ingredients.

[0008] By "perfume or flavor oil" is meant a single perfume or flavoring compound or a mixture of perfume or flavoring compounds.

[0009] "Consumer product" or "finished product" means a manufactured product that is ready for distribution, sale, and use by a consumer.

[0010] The "microcapsules" or synonyms thereof in the present invention have a morphology that can vary from a core-shell type to a matrix type. According to one embodiment, it is a core-shell type. In this case, the microcapsule comprises a core made of a hydrophobic material, typically a perfume-based material, and a shell surrounding the core.

[0011] The microcapsules have a particle size distribution in the micron range (e.g., average diameter) comprised between about 1 and 3000 microns, preferably between 1 and 1000 microns, more preferably between 1 and 500 microns, and even more preferably between 5 and 50 microns. The polymer shell of the microcapsules according to the present invention is formed by interfacial polymerization and / or interfacial reaction.

[0012] "Particle size" means the average diameter of the particles based on the size distribution measured by dynamic light scattering (DLS) using a Zetasizer Nano ZS instrument from Malvern Instruments Ltd., UK, when the particles are dispersed in an aqueous phase.

[0013] "Microcapsule size" refers to the volume average diameter (D[4,3]) of the relevant capsules, capsule suspension as obtained by laser light scattering of a diluted sample in a Malvern Mastersizer 3000.

[0014] Method for preparing core-shell microcapsules The present invention provides a method for preparing core-shell microcapsules or core-shell microcapsule slurries, comprising the steps of: a. mixing a hydrophobic material, preferably a perfume oil, and a polylactone-based polyisocyanate prepolymer obtained by reacting a polylactone polyol with a polyisocyanate to form an oil phase; b. dispersing an oil phase in a dispersed phase comprising an emulsifier or stabilizer, and optionally a cross-linking agent, to form an emulsion; c. optionally adding a cross-linking agent to the emulsion; d. applying conditions sufficient to induce crosslinking of the polylactone-based polyisocyanate prepolymer to form core-shell microcapsules or a core-shell microcapsule slurry. The present invention relates to a method, including:

[0015] In the process steps, a hydrophobic material and a polylactone-based polyisocyanate prepolymer obtained by reacting a polylactone polyol with a polyisocyanate are mixed to form an oil phase.

[0016] In the process steps, the polylactone-based polyisocyanate prepolymer is optionally dissolved in a solvent (e.g., ethyl acetate) and then mixed with a hydrophobic material to form an oil phase. In certain embodiments, the solvent may be chloroform, dichloromethane, carbon tetrachloride, benzene, toluene, xylene, cyclohexanone, and 2-nitropropane, acetone, 2-butanone, ethyl acetate, butyl acetate, e.g., n-butyl acetate, dimethylformamide, and / or acetonitrile.

[0017] Hydrophobic materials The hydrophobic material is preferably an oil.

[0018] A hydrophobic material according to the present invention may be an "inert" material such as a solvent or an active ingredient.

[0019] By "hydrophobic material" is meant any hydrophobic material that forms a two-phase dispersion when mixed with water. Hydrophobic materials are typically liquids at about 20°C.

[0020] According to one embodiment, the hydrophobic material is a hydrophobic active ingredient.

[0021] When the hydrophobic material is an active ingredient, it is preferably selected from the group consisting of flavors, flavor ingredients, fragrances, fragrance ingredients, dietary supplements, cosmetics, pest control agents, biocide active agents and mixtures thereof.

[0022] According to a particular embodiment, the hydrophobic material comprises a phase change material (PCM).

[0023] According to certain embodiments, the hydrophobic material comprises a mixture of a fragrance and another ingredient selected from the group consisting of a nutraceutical, a cosmetic, a pest control agent, and a biocidal active agent.

[0024] According to certain embodiments, the hydrophobic material comprises a mixture of a biocidal active agent and another ingredient selected from the group consisting of fragrances, dietary supplements, cosmetics, and pest control agents.

[0025] According to certain embodiments, the hydrophobic material comprises a mixture of a pest control agent and another ingredient selected from the group consisting of fragrances, dietary supplements, cosmetics, and biocide active agents.

[0026] According to certain embodiments, the hydrophobic material comprises a fragrance.

[0027] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0028] According to a particular embodiment, the hydrophobic material consists of a biocidal active agent.

[0029] According to a particular embodiment, the hydrophobic material consists of a pest control agent.

[0030] By "perfume" (or "perfume oil") in this specification is meant an ingredient or composition that is liquid at about 20°C. According to any one of the above embodiments, the perfume oil may be a single perfuming ingredient or a mixture of ingredients in the form of a perfume composition. As used herein, "perfuming ingredient" means a compound used for the primary purpose of imparting or modifying an odor. In other words, to be considered a perfuming ingredient, such an ingredient must be recognized by those skilled in the art not simply as having an odor, but as at least being able to impart or modify the odor of the composition in a positive or pleasant way. For the purposes of the present invention, perfume oil also includes combinations of perfuming ingredients with substances that together improve, enhance or modify the delivery of the perfuming ingredient, such as perfume precursors, modifiers, emulsions or dispersions, as well as combinations that impart additional benefits beyond modifying or imparting an odor, such as long-lasting properties, blooming, malodor neutralization, antibacterial effect, microbial stability, pest control, etc.

[0031] The nature and type of perfuming ingredients present in the oil phase do not warrant a more detailed description here, and would in any case be far from exhaustive; however, a person skilled in the art can select them based on his or her general knowledge according to the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming ingredients belong to various chemical classes, such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils (e.g., thyme oil), and the above perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are listed in reference texts, such as the book by S. Arctander, "Perfume and Flavor Chemicals," 1969, Montclair, New Jersey, USA, or its latest edition, or other treatises of a similar nature, as well as in the abundant patent literature in the field of perfumery.

[0032] In particular, perfuming ingredients commonly used in perfume formulations, such as: - aldehyde components: decanal, dodecanal, 2-methyl-undecanal, 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-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or alpha-pinene; - Balsamic ingredients: coumarin, ethyl vanillin and / or vanillin; - Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-menthadiene; - Floral ingredients: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (1 E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadien-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-indanemethanol, 2,6,6-trimethyl-3-cyclohexene-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, vergyl acetate, geraniol, p-mentha-1-en-8-ol , 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis-methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, vergyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, propyl (S)-2-(1,1-dimethylpropoxy)propanoate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amylcinnamaldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, vergyl isobutyrate and / or a mixture of methyl ionone isomers; - Fruit ingredients: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl[3-ethyl-2-oxiranyl]acetate and / or diethyl 1,4-cyclohexanedicarboxylate; - Green ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styrallyl 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 ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3-methyl-5-cyclo pentadecen-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 ingredients: 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[oxirane-2,9'-tricyclo[6.2.1.0 2,7 ]undec[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 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, methyl cedryl 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-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate; Other ingredients (e.g. amber, powdery spicy or watery): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, 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-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal Examples include:

[0033] It is also understood that the above ingredients may be compounds known to release in a controlled manner various types of perfuming compounds, also known as pro-perfumes or pro-fragrances. Non-limiting examples of suitable pro-perfumes 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, 2-(dodecylthio) Octan-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hex-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2 -((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec-1-en-1-yl) (1-phenyl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenoxyprop-1-en-2-yl)benzene, 2-(1-phenoxyprop-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-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-phenylvinyl)oxy)-3-methoxybenzaldehyde, or mixtures thereof.

[0034] The perfume ingredients may be dissolved in solvents currently used in the perfume industry. The solvent is preferably not alcohol. Examples of such solvents are 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 highly sterically hindered, such as Abalyn® or benzyl benzoate. Preferably, the perfume contains less than 30% solvent. More preferably, the perfume contains less than 20%, and even more preferably less than 10%, of solvent, all of which percentages are specified by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially solvent-free.

[0035] Preferred perfuming ingredients are those with high steric hindrance, in particular those from the following group: - Group 1: Perfuming ingredients containing a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched C1-C4 alkyl or alkenyl substituent; - Group 2: Perfuming ingredients containing a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted with at least one linear or branched C4-C8 alkyl or alkenyl substituent; - Group 3: Perfuming ingredients containing a phenyl ring or 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: Perfuming ingredients containing at least two fused or linked C5 and / or C6 rings; - Group 5: Flavoring ingredients containing camphor-like ring structures; - Group 6: At least one C7-C 20 Fragrance ingredients containing ring structures; Group 7: Perfuming ingredients with a logP value above 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent It is from one of the

[0036] Examples of ingredients from each of these groups are: - Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (manufacturer: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (manufacturer: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-p-menthadien-7-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 1-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-menthanyl acetate, (1R,2S,4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (manufactured by: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanediethyl dicarboxylate (manufactured by: Firmenich SA, Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (manufactured by: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (manufactured by: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde; Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Givaudan SA, Vernier, 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-cyclopentane acetate (manufacturer: Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (manufactured by Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufactured by Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (manufactured by Givaudan SA, Vernier, 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, a 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 SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate (manufactured by Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (manufactured by International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (manufactured by Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (manufactured by Firmenich SA, 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, Geneva, Switzerland), 8-methoxy-1-p-menthene, (1S,1'R)-2-[1-(3',3'-Dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate (manufactured by Firmenich SA, Geneva, Switzerland), para-tert-butylcyclohexanone, menthenethiol, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allyl cyclohexylpropionate, cyclohexyl salicylate, 2-methoxy-4-methylphenyl methyl carbonate, ethyl 2-methoxy-4-methylphenyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate; Group 4: Methyl cedryl ketone (manufacturer: International Flavors and Fragrances, USA), (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6 ]dec-3-en-8-yl 2-methylpropanoate and (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6] in a mixture with dec-4-en-8-yl 2-methylpropanoate, 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-oxaspiro[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), a 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)]undec-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), octalinol (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan, manufacturer: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl propanoate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl propanoate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptane-3-spiro-2'-cyclohexen-4'-one; - Group 5: camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedrane, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (manufacturer: 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)]undecane-4-one. 2,7 ]mixture with undecan-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-hexadecen-16-olide (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, Geneva, Switzerland), 1,4-dioxacycloheptadecane-5,17-dione, 4,8-cyclododecadien-1-one; Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (manufacturer: Givaudan SA, Vernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate is.

[0037] Preferably, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients selected from groups 1 to 7 as defined above. More preferably, the perfume comprises at least 30%, preferably at least 50% of ingredients from groups 3 to 7 as defined above. Most preferably, the perfume comprises at least 30%, preferably at least 50% of ingredients from groups 3, 4, 6 or 7 as defined above.

[0038] According to another preferred embodiment, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients with a logP above 3, preferably above 3.5, even more preferably above 3.75.

[0039] According to a particular embodiment, the perfume used in the present invention contains less than 10% by weight of primary alcohols, less than 15% by weight of secondary alcohols and less than 20% by weight of tertiary alcohols.Advantageously, the perfume used in the present invention contains no primary alcohols and less than 15% by weight of secondary and tertiary alcohols.

[0040] According to one embodiment, the oil phase (or oil-based core) comprises: - 25 to 100% by weight of a perfume oil comprising at least 15% by weight of high-impact perfume raw materials having a Log T<-4, and - 0~75% by weight, 1.07g / cm 3 Density equilibrium material with density exceeding Includes.

[0041] A "high impact perfume raw material" should be understood as a perfume raw material with a LogT<-4. The odor threshold concentration of a chemical is determined in part by its shape, polarity, partial charge, and molecular weight. For convenience, the odor threshold concentration is presented as the base 10 logarithm of the threshold concentration, i.e., Log[Threshold] ("LogT").

[0042] "Density balanced material" means 1.07 g / cm 3By "polyethylene glycol" is meant a material that has a density of 0.1 g / cm 2 and preferably has a low or no odor.

[0043] The odor threshold concentration of a fragrance compound is determined using a gas chromatograph ("GC"). Specifically, hydrocarbon standards of known concentration and chain length distribution are used to calibrate the gas chromatograph to determine the exact volume of fragrance oil components injected from the syringe, the exact split ratio, and the hydrocarbon response. The airflow rate is accurately measured, and the sampled volume is calculated assuming a human inhalation lasts 12 seconds. Since the exact concentration at the detector at any given time is known, the mass per inhaled volume is known, and therefore the concentration of the fragrance compound. To determine the threshold concentration, a solution with the back-calculated concentration is sent to a sniff port. Panelists sniff the GC emissions and determine the residence time at which they detect an odor. The average across all panelists determines the odor threshold concentration of the fragrance compound. Determining odor thresholds is described in more 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, pp. 54-61).

[0044] High-impact fragrance ingredients with Log T<-4 and 1.07 g / cm 3 The properties of density-balanced materials having densities above 1000 MPa are described in WO 2018115250, the contents of which are incorporated by reference.

[0045] According to one embodiment, high impact perfume raw materials with a Log T<-4 are (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenylacetate, pyrazobutyle, 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-pentene-1 -one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; a mixture containing (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[b]furan-2-one and (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[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]hex-3'-yl)methyl]cyclopropyl}methanol, (+-)-3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-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)-furano methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4α,8β-dimethyl-4a-naphthalenol, patchoulol, 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,Mixture containing 6-dihydro-2H-pyran; 4-hydroxy-3-methoxybenzaldehyde, nonylene aldehyde, 2-methoxy-4-propylphenol, 3-methyl-5-phenyl-2-pentenenitrile, 1-(spiro[4.5]dec-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-methylphenyl isobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, beta,2,2,3-tetramethyl-delta-methylene-3-cyclopentene-1-butanol, delta damascone ((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, para-cresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2-aminobenzoate, ethyl methylphenylglycidate, octalactone gamma, ethyl 3-phenyl-2-propenoate, (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, para-cresyl acetate, dodecalactone, tricyclone, (+)-(3R,5Z )-3-Methyl-5-cyclopentadecen-1-one, undecalactone, (1R,4R)-8-mercapto-3-p-menthanone, (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, (+-)-ethyl 2-methylpentanoate, 1,2-Diallyldisulfane, 2-Tridecenenitrile, 3-Tridecenenitrile, (+-)-2-Ethyl-4,4-dimethyl-1,3-oxathiane, (+)-(3R,5Z)-3-Methyl-5-cyclopentadecen-1-one, 3-(4-tert-butylphenyl)propanal, Allyl(cyclohexyloxy)acetate, Methyl naphthyl ketone, (+-)-(4E)-3-Methyl -4-Cyclopentadecen-1-one, (+-)-5E3-methyl-5-cyclopentadecen-1-one, cyclopropylmethyl 3-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 (1-phenyl)butanal, methyl 2-(3-oxo-2-pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohex-2-enyl)pent-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 -Bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, methylnonylacetaldehyde, 4-formyl-2-methoxyphenyl 2-methylpropanoate, (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-thiabiphenyl Cyclo[3.2.1]oct-3-ene, (1R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1,6-octadien-3-ol, (E)-3-phenyl-2-propenenitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopentene)

[0023] The methyl cyclohexene-1-yl (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-4-penten-2-ol, allyl (2 / 3-methylbutoxy)acetate, (+-)-(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.

[0046] According to one embodiment, the perfume raw materials having a Log T<-4 are selected in the group consisting of aldehydes, ketones, alcohols, phenols, ester lactones, ethers, epoxides, nitriles, and mixtures thereof.

[0047] According to one embodiment, the perfume raw material having a Log T<-4 comprises at least one compound selected from the group consisting of alcohols, phenols, ester lactones, ethers, epoxides, nitriles and mixtures thereof, preferably in an amount comprised between 20 and 70% by weight, based on the total weight of the perfume raw material having a Log T<-4.

[0048] According to one embodiment, the perfume raw materials having a Log T<-4 comprise between 20-70% by weight of aldehydes, ketones, and mixtures thereof, based on the total weight of the perfume raw materials having a Log T<-4.

[0049] Thus, the remaining perfume raw materials contained in the oil-based core may have a Log T > -4.

[0050] According to one embodiment, the perfume raw materials having a Log T>-4 are ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal, vergyl 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-cyclohexene-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-cyclohexadecen-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, aldehyde C11, (+-)-2,6-dimethyl-7-octen-2-ol, allyl 3-cyclohexylpropanoate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, allyl heptanoate, 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)-ethyl 3-hydroxy-2-butenoate, 8-p-menthanol, 8-p-menthanyl acetate, 1-p-menthanyl acetate, (+-)-2-(4-methyl-3-cyclohexene-1-yl) (+-)-2-propanyl acetate, (+-)-2-methylbutyl butanoate, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3,5,6-trimethyl-3-cyclohexene-1-carbaldehyde, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde, 2-cyclohexylethyl acetate, octanal, ethyl butanoate, (+-)-(3E)-4-(2,6,6-trimethyl-1 / 2-cyclohexen-1-yl)-3 -Buten-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-methylcyclohex-1-ene, vergyl acetate, (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1- [(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.

[0051] According to one embodiment, the core comprises: - 0 to 60% by weight (based on the total weight of the fragrance formulation) of a hydrophobic solvent, - 40 to 100% by weight (based on the total weight of the perfume formulation) of perfume oils having the following characteristics: at least 35%, preferably at least 40%, preferably at least 50%, more preferably at least 60% of perfuming ingredients having a logP greater than 3, preferably greater than 3.5; at least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40% of bulk materials of groups 1 to 6, preferably groups 3 to 6, as defined herein; and At least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least 30% of high impact perfume materials with a Log T<-4 a perfume oil having at least two, preferably all, of Optionally, a further hydrophobic active ingredient The fragrance formulation comprises:

[0052] According to a particular embodiment, the perfume comprises 0-60% by weight of hydrophobic solvents.

[0053] According to certain embodiments, the hydrophobic solvent is preferably a density balancing material selected in the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylates, benzyl cinnamate, and mixtures thereof.

[0054] In certain embodiments, the hydrophobic solvent has a Hansen solubility parameter that is compatible with the entrapped perfume oil.

[0055] The term "Hansen solubility parameter" is understood to refer to the solubility parameter approach proposed by Charles Hansen, used to predict the solubility of polymers, and was developed on the basis that the total energy of vaporization of a liquid consists of multiple individual parts. To calculate the "weighted Hansen solubility parameter," the effects of (atomic) dispersion forces, (molecular) permanent dipole-dipole forces, and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen solubility parameter" is calculated by the δD 2 +δP 2 +δΗ 2 ) 0.5 where δD is the Hansen dispersion value (hereinafter also referred to as atomic dispersion force), δP is the Hansen polarization value (hereinafter also referred to as dipole moment), and δH is the Hansen hydrogen bonding ("h-bonding") value (hereinafter also referred to as 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).

[0056] The Euclidean difference in solubility parameters between the fragrance and the solvent is (4 * (δD solvent -δD fragrance ) 2 +(δΡ solvent -δPfragrance ) 2 +(δΗ solvent -δH fragrance ) 2 ) 0.5 where δD solvent , δP solvent , δH solvent are the Hansen dispersion value, Hansen polarization value, and Hansen h-bonding value of the solvent, respectively; δD fragrance , δP fragrance and δH fragrance are the Hansen dispersion value, Hansen polarization value, and Hansen h-cohesion value of the fragrance, respectively.

[0057] In certain embodiments, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a first group consisting of an atomic dispersion force (δD) of 12-20, a dipole moment (δP) of 1-8, and a hydrogen bond (δH) of 2.5-11.

[0058] In certain embodiments, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of an atomic dispersion force (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δΡ) of 1 to 8, preferably 1 to 7, and a hydrogen bond (δΗ) of 2.5 to 11, preferably 4 to 11.

[0059] In certain embodiments, at least 90% of the perfume oils, preferably at least 95% of the perfume oils, and most preferably at least 98% of the perfume oils have at least two Hansen Solubility Parameters selected from a first group consisting of atomic dispersion forces (δD) from 12 to 20, dipole moments (δΡ) from 1 to 8, and hydrogen bonding (δΗ) from 2.5 to 11.

[0060] In certain embodiments, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of an atomic dispersion force (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δΡ) of 1 to 8, preferably 1 to 7, and a hydrogen bond (δΗ) of 2.5 to 11, preferably 4 to 11.

[0061] According to one embodiment, the perfume formulation comprises a fragrance modifier (which may be used in addition to the hydrophobic solvent, if present, or in place of the hydrophobic solvent, if not present).

[0062] Preferably, the fragrance modifier is i. Vapor pressure less than 0.0008 Torr at 22°C; ii. a clogP of 3.5 or greater, preferably 4.0 or greater, and more preferably 4.5 iii. at least two Hansen solubility parameters selected from a first group consisting of atomic dispersion forces of 12 to 20, dipole moments of 1 to 7, and hydrogen bonds of 2.5 to 11; iv. At least two Hansen solubility parameters selected from a second group consisting of atomic dispersion forces of 14 to 20, dipole moments of 1 to 8, and hydrogen bonds of 4 to 11 when dissolved in a compound having a vapor pressure range of 0.0008 to 0.08 Torr at 22°C. is defined as a fragrance material having

[0063] Preferably, the following components can be mentioned as modifiers by way of example, but the list is not limited to the following materials: alcohol C12, oxacyclohexadec-12 / 13-en-2-one, 3-[(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecen-1-one, cyclopentadecanone , (8Z)-Oxacycloheptadec-8-en-2-one, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, muguetaldehyde, 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]heptane-3,1'-cyclohexane]-2'-en-4'-one, oxacyclohexadecan-2-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, (+)-(4R,4 aS,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amyl cinnamaldehyde, hexyl cinnamaldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadien-3-one, (9Z)-9-cycloheptadecen-1-one.

[0064] According to a particular embodiment, the hydrophobic material does not contain an active ingredient (e.g., fragrance). According to this particular embodiment, it comprises, preferably consists of, 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 has 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 ethers, and mixtures thereof.

[0065] The term "biocide" refers to a chemical substance that can kill living organisms (e.g., microorganisms) or reduce or prevent their growth and / or accumulation. Biocides are commonly used in medicine, agriculture, forestry, and in industries to prevent fouling of, for example, water, agricultural products including seeds, and oil pipelines. Biocides can be pesticides, including fungicides, herbicides, insecticides, algicides, molluscicides, acaricides, and rodenticides; and / or antimicrobials, such as bactericides, antibiotics, antibacterial agents, antivirals, antifungals, antiprotozoals, and / or antiparasitics.

[0066] As used herein, "pest control agent" refers to a substance that acts to repel or attract pests, reduce, inhibit or promote their growth, development or activity. A pest refers to any organism, whether animal, plant or fungus, that invades or harms plants or animals, and includes insects, especially arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0067] By "flavor oil" is meant herein a flavoring ingredient or a mixture of flavoring ingredients, solvents or adjuvants currently used for the preparation of flavored formulations, i.e. a specific mixture of ingredients intended to be added to an edible composition or chewable product to impart, improve or modify its organoleptic properties, in particular its flavor and / or taste. Flavoring ingredients are well known to those skilled in the art and their nature does not warrant a detailed description here and would in any case not be exhaustive, but the skilled flavorist will be able to select them on the basis of his general knowledge and depending on the intended use or application and the organoleptic effect that it is desired to achieve. Many of these flavoring ingredients are listed in reference texts, such as the book "Perfume and Flavor Chemicals" by S. Arctander, 1969, Montclair, NJ, USA, or its latest edition, or other similar works, such as "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 flavoring formulations are also well known in the art.

[0068] In particular embodiments, the flavor is a mint flavor. In more particular embodiments, the mint is selected from the group consisting of peppermint and spearmint.

[0069] In a further embodiment, the flavor is a cooling agent or mixtures thereof.

[0070] In another embodiment, the flavor is a menthol flavor.

[0071] Flavors derived from or based on fruits in which citric acid is the predominant natural acid include, but are not limited to, citrus fruits (e.g., lemon, lime), limonene, strawberry, orange, and pineapple. In one embodiment, the flavored food product is lemon, lime, or orange juice extracted directly from the fruit. Further flavor embodiments include juices or liquids extracted from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, and any other citrus fruits, or varieties or hybrids thereof. In certain embodiments, the flavors include liquids extracted or distilled from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, any other citrus fruits, or varieties or hybrids thereof, pomegranates, kiwifruits, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruit, mangoes, pears, tomatoes, and strawberries.

[0072] In certain embodiments, the flavor comprises a composition comprising limonene, and in certain embodiments, the composition is a citrus fruit further comprising limonene.

[0073] In another particular embodiment, the flavor comprises a flavor selected from the group comprising strawberry, orange, lime, tropical, berry mix, and pineapple.

[0074] The term flavor not only includes flavors that impart or modify the smell of a food product, but also ingredients that impart or modify tastes, which do not necessarily have a taste or smell of their own, but can modify the tastes imparted by other ingredients, for example ingredients that enhance saltiness, enhance sweetness, enhance umami, reduce bitterness, etc.

[0075] In further embodiments, a suitable sweetening ingredient can be included in the particles described herein. In certain embodiments, the sweetening ingredient is selected from the group consisting of sugar (such as, but not limited to, sucrose), stevia ingredients (such as, but not limited to, stevioside or rebaudioside A), sodium cyclamate, aspartame, sucralose, sodium saccharin, and acesulfame K, or mixtures thereof.

[0076] According to any one of the embodiments of the invention, the hydrophobic material represents between about 10% and 60% by weight, or even between 15% and 45% by weight, relative to the total weight of the oil phase.

[0077] Polylactone-based polyisocyanate prepolymer The polylactone-based polyisocyanate prepolymer according to the invention is obtained by reacting a polylactone polyol with a polyisocyanate, whereby it is understood that the polylactone-based polyisocyanate prepolymer is obtained in a process separate from the method according to the invention and then introduced in a step separate from the method according to the invention.

[0078] The polylactone-based polyisocyanate prepolymers according to the present invention are not understood as polymeric structures in the sense that they do not contain multiple repeats (i.e., no more than 3, preferably no more than 2, more preferably no more than 1) of monomer units such as polylactone polyols or polyisocyanates.

[0079] The polylactone-based polyisocyanate prepolymer can undergo further polymerization via reactive groups such as terminal reactive isocyanate functional groups, thereby providing two or more monomer units in at least one chain of the polymer shell.

[0080] In certain embodiments, the polylactone-based polyisocyanate is obtained by reacting only a polylactone polyol with a polyisocyanate. In certain embodiments, the polylactone-based polyisocyanate is obtained by reacting only one or more (i.e., two or three), preferably only one, polylactone polyol and one or more (i.e., two or three), preferably only one, polyisocyanate.

[0081] In certain embodiments, the polylactone-based polyisocyanate prepolymer is obtained in a process separate from the method according to the present invention in the presence of excess isocyanate groups to obtain a prepolymer having terminal isocyanate groups.

[0082] In certain embodiments, the polylactone-based polyisocyanate prepolymer is obtained by reacting a polylactone polyol with a polyisocyanate such that the polylactone-based polyisocyanate prepolymer contains at least two terminal isocyanate groups.

[0083] In certain embodiments, the polylactone-based polyisocyanate prepolymer is obtained by reacting a polylactone polyol with a polyisocyanate such that the polylactone-based polyisocyanate prepolymer contains at least three terminal isocyanate groups.

[0084] In certain embodiments, the polylactone-based polyisocyanate prepolymer is obtained by reacting a polylactone polyol with a polyisocyanate such that the polylactone-based polyisocyanate prepolymer contains no more than four terminal isocyanate groups.

[0085] In certain embodiments, the polylactone-based polyisocyanate prepolymer is obtained by reacting a polylactone polyol with a polyisocyanate such that the polylactone-based polyisocyanate prepolymer contains no more than three terminal isocyanate groups.

[0086] In certain embodiments, the polylactone-based polyisocyanate prepolymer is i. providing a polylactone polyol and optionally a solvent; ii. adding polyisocyanate to the mixture of step i. such that the isocyanate (NCO) functional groups are in excess of the hydroxy (OH) groups; iii. Applying conditions to cause a reaction between the OH functional groups of the polylactone polyol and the NCO functional groups of the polyisocyanate to form a polylactone-based polyisocyanate prepolymer. The compound is obtained by a process including:

[0087] When a solvent is used, any suitable solvent in which the polylactone polyol can be dissolved at room temperature can be used. In certain embodiments, the solvent may be chloroform, dichloromethane, carbon tetrachloride, benzene, toluene, xylene, cyclohexanone, 2-nitropropane, acetone, 2-butanone, ethyl acetate, butyl acetate (e.g., n-butyl acetate), dimethylformamide, and / or acetonitrile. In certain embodiments, the solvent is xylene or n-butyl acetate.

[0088] By excess of isocyanate (NCO) functional groups over hydroxy (OH) functional groups, it is understood that the number of reactive isocyanate (NCO) groups of the polyisocyanate must be at least equal to, and preferably greater than, the number of reactive hydroxy (OH) groups of the polylactone polyol.

[0089] In certain embodiments, the molar ratio NCO / OH is ≧2, preferably a molar ratio NCO / OH>2.

[0090] In certain embodiments, the molar ratio NCO / OH is ≧3, preferably a molar ratio NCO / OH>3.

[0091] In certain embodiments, the molar ratio NCO / OH is ≧4, preferably the molar ratio NCO / OH is >4.

[0092] In certain embodiments, the molar ratio NCO / OH is ≧5, preferably the molar ratio NCO / OH is >5.

[0093] In certain embodiments, the molar ratio NCO / OH is ≧6.5, preferably the molar ratio NCO / OH is >6.5.

[0094] Any conditions known to cause a reaction between the OH functional groups of the polylactone polyol and the NCO functional groups of the polyisocyanate can be applied.

[0095] In certain embodiments, any conditions known to effect an addition reaction between the OH functional groups of the polylactone polyol and the NCO functional groups of the polyisocyanate can be applied.

[0096] In certain embodiments, the reaction temperature may be greater than 40°C, preferably greater than 60°C, more preferably greater than 80°C, more preferably greater than 100°C, and most preferably 120°C.

[0097] In certain embodiments, the reaction time can be greater than 1 hour, preferably greater than 1 hour 30 minutes, and more preferably 2 hours or more.

[0098] In certain embodiments, the reaction can be applied in the presence of a catalyst, such as a base, preferably an amine base (eg, a tertiary amine) and an organometallic (eg, an alkyltin carboxylate or an organobismuth).

[0099] Polylactone Polyol Polylactone polyols are understood herein as polyols derived from polylactones, whereas polylactones are understood herein as (cyclic) polyester polymers in which the monomers are aliphatic hydroxy acids. Polylactone polyols may be the reaction product of a dicarboxylic acid, preferably azelaic acid, with a polyol, preferably ethylene glycol.

[0100] In certain embodiments, the polylactone polyol is a biodegradable polylactone polyol.

[0101] In certain embodiments, the polylactone polyol is polylactide (PLA), polyglycolide (PGA), polycaprolactone (PCL), copolylactones such as poly(lactide-co-glycolide) (PLGA), poly(glycolide-co-lactide-co-caprolactone), ternary copolymers (PGLC), triblock and multiblock polylactide / poly(ethylene oxide) copolymers (TPLE and BPLE), and polycaprolactone / polylactide / poly(ethylene oxide) copolymer (PCEL), or ethylene glycol azelaate (which is the reaction product of azelaic acid and ethylene glycol).

[0102] In certain preferred embodiments, the polylactone polyol is a polycaprolactone polyol.

[0103] In certain preferred embodiments, the polylactone polyol is a polycaprolactone diol or triol.

[0104] In certain embodiments, the polylactone polyol has a molecular weight in the range of 200 g / mol to 10,000 g / mol, preferably 220 g / mol to 2,000 g / mol, and more preferably 240 g / mol to 550 g / mol.

[0105] The polylactone polyol used in the process for preparing the polylactone-based polyisocyanate prepolymer may be present in an amount greater than 60% by weight of the preparation of the polylactone-based polyisocyanate prepolymer reaction mixture, preferably greater than 40% by weight, more preferably greater than 20% by weight, more preferably greater than 10% by weight.

[0106] The polylactone polyol portion of the polylactone-based polyisocyanate prepolymer may be present in the process according to the invention in an amount corresponding to 0.1 to 10% by weight of the microcapsule slurry, preferably 0.5 to 7% by weight, more preferably 1 to 5% by weight.

[0107] Polyisocyanate The polyisocyanate may contain at least two, or even at least three, isocyanate functional groups.

[0108] The polyisocyanate may contain up to six, or even up to four, isocyanate functional groups.

[0109] Low volatility polyisocyanates are preferred due to their low toxicity.

[0110] The at least one polyisocyanate may be aliphatic, aromatic, or a mixture of both aromatic and aliphatic polyisocyanates, where each member of the mixture has at least two isocyanate functional groups.

[0111] According to one embodiment, the at least one polyisocyanate is an aromatic polyisocyanate.

[0112] The term "aromatic polyisocyanate" is intended herein to encompass any polyisocyanate containing an aromatic moiety. Preferably, it contains a phenyl, toluyl, xylyl, naphthyl, or diphenyl moiety, more preferably a toluyl or xylyl moiety. Preferred aromatic polyisocyanates are biurets and polyisocyanurates, more preferably containing one of the specific aromatic moieties listed above. More preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (available from Bayer under the trade name Desmodur® RC), a trimethylolpropane (TMP) adduct of toluene diisocyanate (available from Bayer under the trade name Desmodur® L75), or a trimethylolpropane (TMP) adduct of xylylene diisocyanate (available from Mitsui Chemicals under the trade name Takenate® D-110N). In a most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane (TMP) adduct of xylylene diisocyanate.

[0113] According to another embodiment, the polyisocyanate is an aliphatic polyisocyanate.

[0114] The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain any aromatic moieties. Preferred aliphatic polyisocyanates are the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, the trimethylolpropane (TMP) adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or the biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N 100), with the biuret of hexamethylene diisocyanate being even more preferred.

[0115] In certain embodiments, the polyisocyanate comprises an aliphatic polyisocyanate, an aromatic polyisocyanate, or a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate, preferably an aromatic polyisocyanate.

[0116] According to another embodiment, the at least one 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, such as a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane (TMP) adduct of xylylene diisocyanate, a mixture of a biuret of hexamethylene diisocyanate and a polyisocyanurate of toluene diisocyanate, and a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane (TMP) adduct of toluene diisocyanate. Most preferably, this is a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane (TMP) adduct of xylylene diisocyanate.

[0117] In certain embodiments, the polyisocyanate is xylylene diisocyanate, toluene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, L-lysine diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, L-lysine diisocyanate ethyl ester, lysine triisocyanate, an aliphatic isocyanate biuret, an aliphatic or aromatic isocyanate trimethylolpropane (TMP) adduct, an aromatic isocyanate trimethylolpropane (TMP) adduct, preferably xylylene diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, and an aromatic isocyanate trimethylolpropane (TMP) adduct, more preferably xylylene diisocyanate, toluene diisocyanate, and an aromatic isocyanate trimethylolpropane (TMP) adduct.

[0118] In a preferred embodiment, the at least one aliphatic polyisocyanate and the at least one aromatic polyisocyanate are used in a respective molar ratio comprised between 80:20 and 10:90, preferably between 75:25 and 20:80, more preferably between 60:40 and 20:80, even more preferably between 60:40 and 30:70, and most preferably between 45:55 and 30:70.

[0119] The polyisocyanate used in the process for preparing the polylactone-based polyisocyanate prepolymer may be present in an amount greater than 40%, preferably greater than 60%, more preferably greater than 80%, more preferably greater than 90% by weight of the prepared polylactone-based polyisocyanate prepolymer reaction mixture.

[0120] The polyisocyanate portion of the polylactone-based polyisocyanate prepolymer may be present in the process according to the invention in an amount corresponding to 0.1 to 15% by weight of the microcapsule slurry, preferably 0.5 to 8% by weight, more preferably 1 to 6% by weight.

[0121] In another step of the process, the oil phase is dispersed in a dispersed phase comprising an emulsifier or colloidal stabilizer and, optionally, a cross-linking agent to form an emulsion.

[0122] dispersed phase There are no restrictions regarding the nature of the solvent that can be used for the dispersed phase, provided that it is capable of dissolving or dispersing the emulsifier or colloidal stabilizer.

[0123] According to a particular embodiment, the dispersed phase comprises, and preferably consists of, water, i.e., the dispersed phase is an aqueous phase.

[0124] According to another particular embodiment, the water content is less than or equal to 10% by weight, preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, based on the total weight of the aqueous phase.

[0125] According to certain embodiments, the dispersed phase does not comprise water.

[0126] According to one embodiment, the dispersed phase comprises a solvent selected in the group consisting of glycerol, 1,4-butanediol, ethylene glycol and mixtures thereof.

[0127] Emulsifiers / Stabilizers According to the present invention, the emulsifier or stabilizer may be ionic or non-ionic.

[0128] According to one embodiment, the stabilizer is a colloidal stabilizer.

[0129] According to one embodiment, the stabilizer is a solid particle (Pickering emulsion).

[0130] According to the invention, the ionic emulsifier or stabilizer is selected from the group consisting of gum arabic, carboxymethylcellulose, soy protein, sodium caseinate, gelatin, bovine serum albumin, sugar beet pectin, hydrolyzed soy protein, hydrolyzed sericin, pseudo-collagen, Biopolymer SA-N (INCI name: hyaluronic acid (and) serum albumin (and) dextran sulfate), Pentacare-NA PF (hydrolyzed wheat gluten (and) carob (Ceratonia siliqua) (carob) gum (and) water (Aqua) (and) dextran sulfate sodium (and) bishydroxyethyl tromethamine (and) phenoxyethanol (and) ethylhexylglycerin), and mixtures thereof.

[0131] According to a preferred embodiment, the ionic emulsifier or stabilizer is selected in the group consisting of gum arabic, carboxymethylcellulose, sodium caseinate, sugar beet pectin and mixtures thereof.

[0132] According to the present invention, the non-ionic emulsifier or stabilizer is selected in the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, modified starch, modified cellulose, polysaccharides and mixtures thereof.

[0133] According to a particular embodiment, the non-ionic emulsifier or stabilizer is selected in the group consisting of polyvinyl alcohol, modified starch and mixtures thereof.

[0134] According to certain embodiments, the emulsifier or stabilizer is a polymeric stabilizer such as polyvinyl alcohol, cellulose derivatives, polyethylene oxide, copolymers of polyethylene oxide and polyethylene or polypropylene oxide, copolymers of acrylamide and acrylic acid, copolymers of vinylpyrrolidone and quaternized vinylimidazole, and sodium dodecyl sulfate; an inorganic colloidal stabilizer such as hydroxyapatite, calcium carbonate, kaolin, laponite, silica, amine-functionalized silica, clay, sericite mica, tricalcium phosphate; a polysaccharide such as gum arabic, starch, modified starch, chitosan, sodium alginate, alginic acid, cellulose, chitin, pectin, sugar beet pectin, or a colloidal stabilizer comprising these polysaccharides; a protein such as silk fibroin, sericin, gelatin, sodium caseinate, casein, bovine serum albumin, isolated whey protein, potato protein, isolated soy protein, and mixtures thereof, or a colloidal stabilizer comprising these proteins.

[0135] For clarity, the term "derivative" is generally understood herein as a modification of the referenced compound by chemical and / or biotechnological modification.

[0136] For clarity, the term "cellulose derivative" is understood herein to mean cellulose modified by chemical and / or biotechnological modification, particularly chemical modification. In certain embodiments, "cellulose derivatives" are characterized by modifications such as esterification, etherification, or other chemical reactions that impart specific changes to the original cellulose molecule. Specific cellulose derivatives include materials such as cellulose acetate, cellulose ethers (e.g., methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and / or hydroxypropylmethyl cellulose), and carboxymethyl cellulose.

[0137] According to any one of the above embodiments of the invention, the emulsion comprises about 0.1% to 5% by weight of at least an emulsifier or stabilizer, the percentages being expressed on a weight / weight basis relative to the total weight of the dispersion obtained after step b). In yet another aspect of the invention, the emulsion comprises about 0.1% to 2% by weight of at least an emulsifier or stabilizer. In yet another aspect of the invention, the emulsion comprises about 0.1% to 1% by weight of at least an emulsifier or stabilizer.

[0138] In certain embodiments, the crosslinker can be added to the dispersed phase.

[0139] Any compound capable of reacting with the isocyanate functional groups of the polylactone-based polyisocyanate prepolymer to further crosslink the polylactone-based polyisocyanate prepolymer can be used as the crosslinker.

[0140] In certain embodiments, the crosslinker may be a polyfunctionalized amine, a polyfunctionalized alcohol, and / or a polyfunctionalized thiol.

[0141] In certain embodiments, the crosslinker is a polyfunctionalized amine, such as ethylenediamine, diethylenetriamine, triethylenetetraamine, guanidine, 1,5-pentanediamine, 1,8-diaminooctane, 1,12-diaminododecane, 3,5-diamino-1,2,4-triazole, urea; an amino acid, such as l-lysine, l-tryptophan, l-cystine, cystamine and their hydrochlorides; a polyfunctionalized polyol, such as 1,5-pentanediol, 1,6-hexanediol, and a polylactone-based polyol; or a polyfunctionalized thiol.

[0142] In certain embodiments, the cross-linking agent may be an amino acid, such as l-lysine, l-tryptophan, l-cystine, cystamine and their hydrochloride salts, more preferably l-lysine.

[0143] In certain embodiments, the crosslinker may be present in an amount greater than 0.5 wt. %, preferably greater than 1.0 wt. %, and even more preferably 1.2 wt. % or greater, based on the weight of the emulsion.

[0144] In a separate step of the process, a cross-linking agent can optionally be added to the emulsion.

[0145] In another step of the method, conditions sufficient to induce crosslinking of the polylactone-based polyisocyanate prepolymer to form core-shell microcapsules or a core-shell microcapsule slurry are applied.

[0146] By this, it is understood that any conditions may be applied which will induce crosslinking of the polylactone-based polyisocyanate prepolymer to form core-shell microcapsules.

[0147] In certain embodiments, conditions sufficient to induce crosslinking include heating the oil-in-water emulsion at elevated temperatures, preferably at least 30°C, preferably above 45°C, more preferably above 60°C, even more preferably above 70°C, for example 80°C.

[0148] In certain embodiments, conditions sufficient to induce crosslinking include heating the oil-in-water emulsion at elevated temperature for at least 30 minutes, preferably at least 1 hour, and even more preferably at least 2 hours, e.g., 3 hours.

[0149] In certain embodiments, the conditions sufficient to induce crosslinking include heating the oil-in-water emulsion at elevated temperature and a pH of 4-10.

[0150] Any outer coating According to certain embodiments of the present invention, at the end of or during step d), a polymer selected from the group consisting of non-ionic polysaccharides, cationic polymers, polysuccinimide derivatives (e.g. as described in WO2021185724) and mixtures thereof may be added to the microcapsule slurry to form an outer coating on the microcapsules.

[0151] Nonionic polysaccharide polymers are well known to those skilled in the art and are described, for example, in WO 2012 / 007438, page 29, lines 1 to 25, and in WO 2013 / 026657, page 2, lines 12 to 19 and page 4, lines 3 to 12. Preferred nonionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

[0152] 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 the cationic polymer can be measured by the Kjeldahl method under the chemical test for nitrogen determination, as described in the United States Pharmacopeia. Preferred cationic polymers are selected from those containing units containing primary, secondary, tertiary, and / or quaternary amine groups, which may form part of the polymer backbone or may have side-chain substituents directly attached thereto. The weight-average (Mw) molecular weight of the cationic polymer is preferably between 10,000 and 3.5 Mdaltons, more preferably between 50,000 and 1.5 Mdaltons. According to particular embodiments, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylamino methacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-imidazol-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 will be used. Preferred copolymers are those 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 that may be mentioned are Salcare® SC60 (cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, supplier: BASF) or Luviquat®, such as PQ 11N, FC 550 or Style (quaternized copolymer of polyquaternium-11-68 or vinylpyrrolidone, supplier: BASF), or even Jaguar® (C13S or C17, supplier: Rhodia).

[0153] According to any one of the above embodiments of the present invention, said polymer is added in an amount comprised between about 0-5 wt.%, or even between about 0.1-2 wt.%, wherein the percentage is expressed on a weight / weight basis relative to the total weight of the slurry obtained after step d). It is clearly understood by those skilled in the art that only a portion of said added polymer will be incorporated into / deposited on the microcapsule shell.

[0154] Method for preparing microcapsule powder Another subject of the present invention is a method for preparing a microcapsule powder, comprising the steps defined above and the additional step of subjecting the microcapsule slurry to a drying process such as spray drying, to provide the microcapsules as such, i.e. in powder form.

[0155] It is understood that any standard method known to those skilled in the art for carrying out such drying is applicable. In particular, the slurry may be spray dried, preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gum, pectin, xanthan, alginate, carrageenan or a cellulose derivative, to provide the microcapsules in powder form.

[0156] However, other drying methods such as extrusion, plating, spray granulation, fluidized bed or even drying at room temperature may also be mentioned, using materials (carriers, desiccants) that meet certain criteria as disclosed in WO 2017 / 134179.

[0157] According to a particular embodiment, the carrier material contains free perfume oil, which may be the same as or different from the perfume from the core of the microcapsules.

[0158] Core-shell microcapsules The present invention also relates to core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention.

[0159] The present invention relates to a core-shell microcapsule, a core comprising a hydrophobic material, preferably a perfume oil, preferably an oil core, - a crosslinked polymer shell surrounding the oil core, obtained by reacting a polylactone-based polyisocyanate prepolymer obtained by reacting a polylactone polyol with a polyisocyanate, and optionally with a crosslinking agent; The present invention also relates to a core-shell microcapsule or a core-shell microcapsule slurry comprising:

[0160] The polylactone-based polyisocyanate prepolymer can undergo further polymerization via reactive groups such as terminal reactive isocyanate functional groups, thereby providing two or more monomer units in at least one chain of the polymer shell.

[0161] The definitions and embodiments for the hydrophobic material, the polylactone-based polyisocyanate prepolymer, the polylactone polyol, the polyisocyanate, and the crosslinker are the same as those described above.

[0162] In certain embodiments, the shell material is a biodegradable material.

[0163] In certain embodiments, the shell is at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradable within 60 days according to OECD 301F.

[0164] In certain embodiments, the core-shell microcapsules are at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradable within 60 days according to OECD 301F.

[0165] It is thereby understood that core-shell microcapsules, including all components such as core, shell and optionally coating, may be at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradable within 60 days according to OECD 301F.

[0166] In certain embodiments, the oil core, preferably the perfume oil, is at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradable within 60 days according to OECD 301F.

[0167] OECD 301F is a standard test method for biodegradability from the Organization for Economic Co-operation and Development.

[0168] A typical method for extracting shells to measure biodegradability is disclosed in Gasparini and all in Molecules 2020, 25,718.

[0169] Perfuming compositions and consumer products The present invention provides - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above, - at least one ingredient selected from the group consisting of a perfume carrier and a perfume base, and optionally at least one flavoring adjuvant The present invention also relates to a fragrance composition comprising:

[0170] In certain embodiments, the composition comprises: (i) core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above; (ii) an active ingredient, preferably selected from the group consisting of a cosmetic ingredient, a skin care ingredient, a fragrance ingredient, a flavor ingredient, a malodor-neutralizing ingredient, a bactericide ingredient, a fungicide ingredient, a pharmaceutical or pesticide ingredient, a disinfectant ingredient, an insect repellent or attractant, and mixtures thereof; Includes.

[0171] In certain embodiments, the core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above may also be added to various perfumed consumer products.

[0172] In certain embodiments, the present invention provides a method for producing a pharmaceutical composition comprising: - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above, and - optionally, free perfume oil The present invention relates to a fragrance composition comprising:

[0173] Preferably, the perfuming composition according to the invention comprises 0.1 to 30% by weight of core-shell microcapsules or core-shell microcapsule slurry obtainable by the method according to the invention or as described above.

[0174] By "free perfume" is herein understood a perfume or perfume oil that is contained in a perfuming composition and that is not entrapped in a core-shell microcapsule or a core-shell microcapsule slurry obtained by the method according to the invention or as described above.

[0175] In a particular embodiment, the total amount of core-shell microcapsules or core-shell microcapsule slurry obtainable by the method according to the invention or as described above is between 0.05 and 5% by weight (based on the total weight of the perfuming composition) and the total amount of free perfume oil is between 0.05 and 5% by weight (based on the total weight of the perfuming composition).

[0176] In a particular embodiment, the total perfume oils and the total free perfume oils of the perfume formulation obtained by the method according to the invention or entrapped in core-shell microcapsules or core-shell microcapsule slurries as described above are present in the perfume composition in a weight ratio of 1:20 to 20:1, preferably 10:1 to 1:10.

[0177] The perfuming composition may further comprise at least one perfuming co-ingredient and, optionally, a perfume adjuvant.

[0178] "Perfuming co-ingredient" is understood herein to mean a compound used in a perfume preparation or composition to impart a hedonic effect, but which is not a microcapsule as defined above. In other words, to be considered a perfuming ingredient, such a co-ingredient must be recognized by those skilled in the art not simply as having an odor, but as being able to impart or modify the odor of the composition in a positive or pleasant way. The nature and type of perfuming co-ingredients present in a perfume composition do not warrant a detailed description herein, and would in any case be far from exhaustive, but those skilled in the art can select them based on their general knowledge according to the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming co-ingredients belong to various chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and the perfuming co-ingredients may be of natural or synthetic origin. Many of these auxiliary ingredients are in any case listed in references, for example in the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest edition, or other treatises of a similar nature, as well as in the abundant patent literature in the field of perfumery.It is also understood that the above-mentioned auxiliary ingredients may be compounds known to release, in a controlled manner, various types of perfuming compounds.

[0179] By "perfuming adjuvants" is understood herein ingredients capable of imparting additional benefits such as color, particular lightfastness, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfuming bases cannot be exhaustive, but it must be mentioned that said ingredients are well known to those skilled in the art.

[0180] According to one embodiment, the core-shell microcapsules or core-shell microcapsule slurries (first type of delivery system) obtainable by the method according to the invention or as described above may be used in combination with a second type of delivery system.

[0181] Thus, according to a particular embodiment, the perfuming composition comprises: - core-shell microcapsules or core-shell microcapsule slurries as a first type of delivery system, obtainable by the method according to the invention or as described above, and - a second type of delivery system, The first type of delivery system and the second type of delivery system differ in their perfume formulation and / or carrier material (shell or matrix) and / or outer coating.

[0182] The core-shell microcapsules or core-shell microcapsule slurries obtainable by the method according to the invention or as described above can be used advantageously in many fields of application and can be used in consumer products.

[0183] The present invention provides - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above, and - Personal care, home care or fabric care active base The present invention also relates to scented consumer products, including

[0184] The consumer products of the present invention may be used in perfumed consumer products, such as those belonging to fine fragrances or "functional" perfumery, including in particular personal care products, including hair care, body cleansing, skin care, hygiene care, and home care products, including laundry care and air care.

[0185] In particular, liquid consumer products - 2 to 65% by weight of at least one surfactant, based on the total weight of the consumer product; water or a water-miscible hydrophilic organic solvent, and a perfuming composition, or a core-shell microcapsule or a core-shell microcapsule slurry obtainable by the process according to the invention or as described above; Includes.

[0186] In addition, powdered consumer products include - 2 to 65% by weight, based on the total weight of the consumer product, of at least one surfactant, and a perfuming composition, or a core-shell microcapsule or a core-shell microcapsule slurry obtainable by the process according to the invention or as described above; Includes.

[0187] For the sake of clarity, it should be mentioned that "perfumed consumer product" means a consumer product that is expected to deliver, among other benefits, a fragrance effect to the surface to which it is applied (e.g., skin, hair, textiles, paper, or household surfaces) or in the air (air fresheners, deodorants, etc.). In other words, a perfumed consumer product according to the present invention is a manufactured product that includes a functional formulation, also called a "base", together with benefit agents, especially an effective amount of the microcapsules according to the present invention.

[0188] The nature and type of other ingredients of the perfumed consumer product do not warrant a more detailed description herein, and would in any case not be comprehensive, but a person skilled in the art can select them based on his general knowledge according to the nature and desired effect of the product. The base formulations of consumer products into which the microcapsules of the present invention can be incorporated can be found in the abundant literature related to such products. A detailed description of these formulations does not warrant a more detailed description herein, and would in any case not be comprehensive. A person skilled in the art of formulating such consumer products can fully select the appropriate ingredients based on his general knowledge and the available literature.

[0189] Non-limiting examples of suitable perfumed consumer products include fine perfumes, splashes or eau de parfums, colognes, shave or aftershave lotions, liquid or solid detergents, mono or multi-chamber unidose detergents, fabric softeners, fabric refreshers, liquid or solid fragrance enhancers (PEG / urea or salts), dryer sheets, ironing water, paper, bleach, carpet cleaners, curtain care products, shampoos, color preparations, color care products, hair styling products, dental care products, disinfectants, intimate care products, hairsprays, hair conditioning products, vanishing creams, deodorants or antiperspirants, hair removers, tanning or sun products, nail products, skin cleansers, makeup products, perfumed soaps, shower or bath mousses, oils or gels, or foot / hand care products, hygiene products, air fresheners, "ready to use" powder air fresheners, mold removers, furniture care products, etc. care), wipes, dishwashing or hard surface cleaners, leather care products, car care products.

[0190] In certain embodiments, the perfumed consumer product is preferably selected from the group consisting of a personal care composition, a home care composition or a fabric care composition, most preferably in the form of an antiperspirant, a hair care product, e.g., a shampoo or a hair conditioner, a body care product, e.g., a shower gel, an oral care product, a laundry care product, preferably a detergent or a fabric softener.

[0191] Another subject of the present invention is - Personal care active bases, and - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above, or perfuming compositions as defined above. and is in the form of a personal care composition.

[0192] The personal care active bases into which the delivery system of the present invention can be incorporated can be found in the abundant literature relating to such products. A more detailed description of these formulations is not warranted here, and would not be exhaustive in any case. Those skilled in the art of formulating such consumer products are entirely capable of selecting the appropriate ingredients based on their general knowledge and the available literature.

[0193] The personal care composition is preferably selected in the group consisting of a hair care product (e.g. shampoo, hair conditioner, color preparation or hairspray), a cosmetic preparation (e.g. vanishing cream, body lotion or deodorant or antiperspirant), a skin care product (e.g. perfumed soap, shower or bath mousse, body wash, oil or gel, bath salts or hygiene product), an oral care product (toothpaste or mouthwash composition) or a fine fragrance product (e.g. Eau de Toilette-EdT).

[0194] Another subject of the present invention is - Home care or fabric care active bases, and - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above, or perfuming compositions as defined above. and is in the form of a home care or fabric care composition.

[0195] Home care or fabric care bases into which the delivery system of the present invention can be incorporated can be found in the abundant literature relating to such products. A more detailed description of these formulations is not warranted here, and would not be exhaustive in any case. Those skilled in the art of formulating such consumer products are entirely capable of selecting appropriate ingredients based on their general knowledge and the available literature.

[0196] The home or fabric care composition is preferably selected in the group consisting of fabric softeners, liquid detergents, powder detergents, liquid fragrance boosters and solid fragrance boosters.

[0197] Fabric softener The subject of the present invention is a fabric softener active base, preferably 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, cationic guar and mixtures thereof, preferably in an amount comprised between 85 and 99.95% by weight (excluding water), based on the total weight of the composition; - core-shell microcapsules or core-shell microcapsule slurry obtainable by the process according to the invention or as described above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. and a consumer product in the form of a fabric softener composition comprising:

[0198] Liquid detergent The subject of the present invention is - a liquid detergent active base, preferably selected from the group consisting of anionic surfactants such as alkylbenzenesulfonates (ABS), secondary alkylsulfonates (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, alkyl polyglucosamides, preferably in an amount comprised between 85 and 99.95% by weight (excluding water), based on the total weight of the composition; - core-shell microcapsules or core-shell microcapsule slurry obtainable by the process according to the invention or as described above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. and a consumer product in the form of a liquid detergent composition comprising:

[0199] Solid detergent The subject of the present invention is - a solid detergent active base, preferably selected from the group consisting of anionic surfactants, such as alkylbenzenesulfonates (ABS), secondary alkylsulfonates (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, alkyl polyglucosamides, preferably in an amount comprised between 85 and 99.95% by weight, based on the total weight of the composition, - core-shell microcapsules or core-shell microcapsule slurry obtainable by the process according to the invention or as described above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. and a consumer product in the form of a solid detergent composition comprising:

[0200] Solid aroma enhancer The subject of the present invention is - solid carriers, preferably selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolites, 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, polysaccharides such as sucrose, monosaccharides, disaccharides and polysaccharides and derivatives such as starch, 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. - core-shell microcapsules or core-shell microcapsule slurry obtainable by the process according to the invention or as described above, in powder form, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition; and a consumer product in the form of a solid fragrance enhancer comprising:

[0201] Liquid aroma enhancer The subject of the present invention is - aqueous phase, - a surfactant system consisting essentially of one or more nonionic surfactants, having an average HLB between 10 and 14, preferably selected in the group consisting of ethoxylated fatty alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono- and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxyl esters, alkyl polyglucosides, amine oxides and combinations thereof, a linker 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 with an HLB of less than 10 and mixtures thereof, and - core-shell microcapsules or core-shell microcapsule slurries obtained by the process according to the invention or as described above, preferably in the form of a slurry, in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. and a consumer product in the form of a liquid fragrance enhancer comprising:

[0202] Shampoo / Shower gel The subject of the present invention is a shampoo or shower gel active base, preferably selected from the group consisting of sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside and amino acid surfactants and mixtures thereof, preferably in an amount comprised between 85 and 99.95% by weight (excluding water), based on the total weight of the composition, - core-shell microcapsules or core-shell microcapsule slurry obtainable by the process according to the invention or as described above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. and a consumer product in the form of a shampoo or shower gel composition comprising:

[0203] Rinse-off conditioner The subject of the present invention is a rinse-off conditioner active base, preferably selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, preferably in an amount comprised between 85 and 99.95% by weight (excluding water), based on the total weight of the composition; - core-shell microcapsules or core-shell microcapsule slurry obtainable by the process according to the invention or as described above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. and a consumer product in the form of a rinse-off conditioner composition comprising:

[0204] Perfuming composition According to certain embodiments, the consumer product comprises: - 0.1 to 30%, preferably 0.1 to 20%, of core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to the invention or as described above, - 0 to 40%, preferably 3 to 40%, of fragrances, and 20 to 90% by weight, preferably 40 to 90% by weight, of ethanol based on the total weight of the fragrance composition The fragrance composition is in the form of a fragrance composition comprising:

[0205] The invention will now be further illustrated by examples. It will be understood that the invention as claimed is not intended to be limited in any way by these examples.

[0206] Example Example 1 Preparation of microcapsules from polycaprolactone (PCL) polyol. i) Preparation of PCL-based polyisocyanate prepolymer (catalyst-free): PCL-diol or PCL-triol was dissolved in butyl acetate (5 mL) to obtain a solution, which was then added dropwise to a flask containing excess m-xylylene diisocyanate dissolved in butyl acetate (10 mL) at a molar ratio of -NCO / -OH > 4 via a syringe pump over 1 h with stirring at 120 °C. This was then heated for an additional 1 h to obtain a PCL-based multifunctionalized isocyanate prepolymer solution. The butyl acetate was first removed under vacuum, and the excess m-xylylene diisocyanate was removed by liquid-liquid extraction with hexane. After washing and extraction with hexane, the solution was removed under vacuum to yield a clear, viscous product.

[0207] [Table 1]

[0208] [Table 2]

[0209] ii) Preparation of microcapsules The PCL-based polyisocyanate prepolymer was dissolved in ethyl acetate and mixed with perfume oil, to which the colloidal stabilizer suspension was mixed using an overhead disperser to form an emulsion.

[0210] The emulsion was transferred to a reactor, and the interfacial reaction was carried out at 45°C for 15 min, 60°C for 15 min, and 80°C for 2 h.

[0211] Microcapsules with PCL incorporated into the shell were obtained.

[0212] [Table 3]

[0213] [Table 4]

[0214] [Table 5]

[0215] [Table 6]

[0216] iii) Stability Results Microcapsules according to Table 4 above were used for stability.

[0217] Storage stability test: The microcapsules were added to a fabric softener base (see Table 6) at a perfume oil dosage of 0.2% in the base and stored for 3 days at 37° C. The microcapsules showed an oil leakage of 18.5%.

[0218] Example 2 Preparation of microcapsules from PCL-triol i) Preparation of PCL-based polyisocyanate prepolymers in the presence of catalysts 1,3-Bis(isocyanatomethyl)benzene (1.80 mL, 11.50 mmol) and tin(II) 2-ethylhexanoate in ethyl acetate (0.1 mL, 0.34 mmol) were added to a 25 mL round-bottom three-neck flask to give a colorless solution.

[0219] CAPA3050 (540 MW polycaprolactone triol initiated with trimethylolpropane (TMP); 2.01 g, 3.64 mmol) was added to ethyl acetate (4.60 mL, 3.64 mmol) in a second 25 mL round-bottom flask to give a colorless solution. The latter was added dropwise to the diisocyanate solution over 5 minutes. The reaction mixture was stirred at 50° C. for 3 hours and then slowly cooled to room temperature under stirring. The product was recovered by solvent evaporation to give a white, pasty solid.

[0220] [ka]

[0221] ii) Preparation of microcapsules PCL-based polyisocyanate prepolymer (4.96 g, 2.22 mmol NCO) was dissolved in perfume oil B (see Table A, 20 g) in a 150 mL beaker to obtain a yellow solution. The solution was stirred for 5 minutes. A 1% solution of PVOH in water (46.30 g) was added to the beaker and an emulsion was prepared using an Ultra Turrax (S25N 10G) at 20,000 rpm for 2 minutes. The droplet size was controlled by optical microscopy and a pH of 5.01 was measured. The reaction mixture was transferred to a 250 mL reactor and stirred at 350 rpm for 1 hour at room temperature. The temperature was increased to 70°C over 1 hour and the reaction mixture was stirred at 70°C for 2 hours. At the end of the process, the dispersion was cooled to room temperature and a pH of 5.71 was measured.

[0222] [Table 7]

[0223] The microcapsule slurry was dried and the shells were recovered by solvent extraction of the perfume with ethyl acetate (5 times), filtration, washing with 0.5% water for 24 hours, filtration, and extraction a second time with ethyl acetate (5 times). The white solid was recovered by filtration and dried.

[0224] Example 3 Preparation of microcapsules from polylactone polyol-based polyisocyanate prepolymers. i) Preparation of polylactone polyol-based polyisocyanate prepolymers Emerox 14555 (azelaic acid ethylene glycol (EG)-based linear diol polyol; 5.03 g, 2.31 mmol, diol from azelaic acid and ethylene glycol) and titanium IV isopropoxide (0.1 mL, 0.04 mmol) in ethyl acetate were dissolved in anhydrous ethyl acetate (6.5 mL) in a 25 mL round-bottom flask to give a colorless solution. This solution was added to a 50 mL round-bottom three-neck flask in the presence of 1,3-bis(isocyanatomethyl)benzene (0.76 mL, 4.85 mmol), giving a colorless solution. The reaction mixture was stirred at 50 °C for 3 h and then slowly cooled to room temperature under stirring to give a yellow viscous oil.

[0225] ii) Preparation of microcapsules A polylactone polyol-based polyisocyanate prepolymer (4.81 g) was dissolved in perfume oil B (Table A, 20 g) in a 150 mL beaker to obtain a yellow solution. The solution was stirred for 3 minutes. A 1% solution of PVOH in water (46.10 g) was added to the beaker, and an emulsion was prepared using an Ultra Turrax (S25N 10G) at 21,500 rpm for 2 minutes. The droplet size was controlled by optical microscopy, and a pH of 4.89 was measured. The reaction mixture was transferred to a 250 mL reactor and stirred at 350 rpm for 1 hour at room temperature. The temperature was increased to 70°C over 1 hour, and the reaction mixture was stirred at 70°C for 2 hours. At the end of the process, the dispersion was cooled to room temperature, and a pH of 5.68 was measured.

[0226] The microcapsule slurry was dried and the shells were recovered by solvent extraction of the perfume with ethyl acetate (5 times), filtration, washing with 0.5% water for 24 hours, filtration, and extraction a second time with ethyl acetate (5 times). The white solid was recovered by filtration and dried.

[0227] Example 4 Fabric softener composition A sufficient amount of the inventive microcapsules from Examples 1 and 3 are dispersed in a liquid detergent base as described in Table 6 to obtain a concentration of 0.22% encapsulated perfume oil.

[0228] [Table 8]

[0229] Example 5 Liquid detergent composition A sufficient amount of the microcapsules of the present invention according to Examples 1-3 are dispersed in a liquid detergent base as described in Table 7 to obtain a concentration of 0.22% encapsulated perfume oil.

[0230] [Table 9]

[0231] Example 6 Rinse-off hair conditioner composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are incorporated into a rinse-off base at the required dosage (equivalent to 0.5% encapsulated perfume oil) (see Table 8).

[0232] [Table 10]

[0233] The ingredients of Phase A are mixed until a homogeneous mixture is obtained. The tylose is completely dissolved. The mixture is then heated to 70-75°C. The ingredients of Phase B are combined and melted at 70-75°C. The ingredients of Phase B are then added to Phase A with good mixing and mixing is continued until the mixture has cooled to 60°C. The ingredients of Phase C are then added with stirring and mixing is continued until the mixture has cooled to 40°C. The pH is adjusted with citric acid solution to pH 3.5-4.0.

[0234] Example 7 Preparation of spray-dried microcapsules Emulsions 1 to 5 are prepared having the following components:

[0235] [Table 11-1] [Table 11-2]

[0236] The ingredients of the polymer matrix (maltodextrin and capsul™, or capsul™, citric acid and tripotassium citrate) are added to water at 45-50°C until completely dissolved.

[0237] For emulsion 4, add free perfume C to the water phase.

[0238] To the resulting mixture, add the microcapsules according to Examples 1 to 3. Then, the resulting mixture is gently mixed at 25°C (room temperature).

[0239] Granular powders 1 to 5 are prepared by spray drying emulsions A to E using a Sodeva Spray Dryer (France) with an inlet temperature set to 215°C and a throughput set to 500 ml per hour. The outlet temperature is 105°C. The emulsions are at room temperature before atomization.

[0240] Example 8 Liquid fragrance enhancer composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the liquid fragrance enhancer to add the equivalent of 0.2% fragrance.

[0241] [Table 12]

[0242] Prepare various ringing gel compositions according to the following protocol (compositions 1-6).

[0243] In the first step, the aqueous phase (water), the solvent (propylene glycol), if present, and the surfactant are mixed under magnetic stirring at 300 rpm at room temperature for 5 minutes.

[0244] In the second step, the linker is dissolved in the hydrophobic active ingredient (fragrance) while stirring with a magnetic stirrer at 300 rpm at room temperature. The resulting mixture is mixed for 5 minutes.

[0245] The water and oil phases are then mixed at room temperature for 5 minutes to form a clear or milky ringing gel.

[0246] Example 9 Powder detergent composition A sufficient amount of granules 1-5 according to Example 7 is weighed and mixed into a powder detergent composition to add the equivalent of 0.2% perfume.

[0247] [Table 13]

[0248] Example 10 Concentrated multipurpose cleaning composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into a concentrated all-purpose cleaning composition to add the equivalent of 0.2% perfume.

[0249] [Table 14]

[0250] After all ingredients were mixed, the mixture was diluted to 100% with water.

[0251] Example 11 Solid fragrance enhancer composition A sufficient amount of microcapsules in dry form according to Example 7 is weighed and mixed with the solid fragrance enhancer composition to add the equivalent of 0.2% fragrance.

[0252] [Table 15]

[0253] [Table 16]

[0254] Example 12 Shampoo composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into a shampoo composition to add the equivalent of 0.2% perfume.

[0255] [Table 17]

[0256] Disperse Polyquaternium-10 in water. Mix the remaining ingredients of Phase A separately by adding them in order, mixing well after each addition. This premix is ​​then added to the Polyquaternium-10 dispersion and mixed for 5 minutes. Then add Phase B and premix Phase C (heat to melt Monomuls 90L-12 in Texapon NSO IS). Mix the mixture well. Then add Phase D and Phase E with stirring. Adjust the pH with citric acid solution until it reaches pH 5.5-6.0.

[0257] Example 13 Shampoo composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into a shampoo composition to add the equivalent of 0.2% perfume.

[0258] [Table 18-1] [Table 18-2]

[0259] Add the premix containing guar hydroxypropyltrimonium chloride and polyquaternium-10 to the water and tetrasodium EDTA while mixing. Once the mixture is uniform, add NaOH. Then, add the ingredients of Phase C and heat the mixture to 75°C. Add the ingredients of Phase D and mix until uniform. Stop heating and allow the mixture to cool to room temperature. At 45°C, add the ingredients of Phase E while mixing, adjusting the final viscosity with 25% NaCl solution and the pH to 5.5-6 with 10% NaOH solution.

[0260] Example 14 Antiperspirant spray anhydrous composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into an antiperspirant spray anhydrous composition to add the equivalent of 0.2% perfume.

[0261] [Table 19]

[0262] Using a high-speed stirrer, add the silica and quaternium-18-hectorite to the isopropyl myristate and cyclomethicone mixture. Once fully swollen, add the aluminum chlorohydrate in small portions under stirring until the mixture is homogeneous and free of lumps. Fill an aerosol can with 25% of the suspension and 75% propane / butane (2.5 bar).

[0263] Example 15 Antiperspirant spray emulsion composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into an antiperspirant spray emulsion composition to add the equivalent of 0.2% perfume.

[0264] [Table 20]

[0265] The ingredients of Part A and Part B are weighed out separately. The ingredients of Part A are heated to 60°C and the ingredients of Part B are heated to 55°C. The ingredients of Part B are poured into A in small parts with continuous stirring. The mixture is stirred well until it reaches room temperature. Then the ingredients of Part C are added. The emulsion is mixed and introduced into an aerosol can. The propellant is added by compression.

[0266] Aerosol filling: 30% emulsion: 70% propane / butane 2.5bar

[0267] Example 16 Deodorizing spray composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into an antiperspirant deodorant spray composition to add the equivalent of 0.2% perfume.

[0268] [Table 21]

[0269] All ingredients are mixed and dissolved in the order shown in the table above. The aerosol can is then filled, crimped and the propellant added (aerosol fill: 40% active solution 60% propane / butane 2.5 bar).

[0270] Example 17 Antiperspirant roll-on emulsion composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into an antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.

[0271] [Table 22]

[0272] Part A and Part B are heated separately to 75°C, Part A is added to Part B under stirring, and the mixture is homogenized for 10 minutes. The mixture is then cooled under stirring, and when the mixture reaches 45°C, Part C is added slowly with stirring, and when the mixture reaches 35°C, Part D is added slowly with stirring. The mixture is then cooled to room temperature.

[0273] Example 18 Antiperspirant roll-on composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into an antiperspirant roll-on composition to add the equivalent of 0.2% perfume.

[0274] [Table 23]

[0275] The ingredients of Part B are mixed in a container, then the ingredients of Part A are added. Part C is then dissolved in Parts A and B. One part Cremophor RH40 along with the fragrance is added to one part fragrance with good mixing.

[0276] Example 19 Antiperspirant roll-on composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into an antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.

[0277] [Table 24]

[0278] Prepare Part A by gradually sprinkling hydroxyethyl cellulose into water while rapidly stirring with a turbine. Continue stirring until the hydroxyethyl cellulose is completely swollen and a clear gel is obtained. Then, gradually pour Part B into Part A while continuing to stir until the mixture is homogenous. Add Part C.

[0279] Example 20 Alcohol-free deodorizing pump A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0280] [Table 25]

[0281] Mix all ingredients in the order listed and heat the mixture slightly to dissolve the cetyl lactate.

[0282] Example 21 Deodorizing pump containing alcohol A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0283] [Table 26]

[0284] Mix the ingredients of Part B. Dissolve the ingredients of Part A in the order shown and pour into Part B.

[0285] Example 22 Alcohol-free deodorizing stick A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0286] [Table 27]

[0287] Weigh out all ingredients for Part A and heat to 70-75°C. Mix the other Part A ingredients and once heated, add Ceteareth-25. Once Ceteareth-25 has dissolved, add stearic acid. Prepare Part B by dissolving triclosan in 1,2 propylene glycol. Add evaporated water. Slowly pour Part B into Part A while mixing. Place plastic bag in a bucket for storage and seal after cooling. Fill into molds at approximately 70°C.

[0288] Example 23 Antiperspirant stick A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0289] [Table 28]

[0290] Weigh out all the ingredients of Part A, heat to 70-75°C and mix well. Disperse the ingredients of Part B into Part A. Mix the mixture and form into a stick at 65°C.

[0291] Example 24 Day cream A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0292] [Table 29]

[0293] Example 25 Talc Compound A sufficient amount of granules 1 to 5 according to Example 7 is weighed and introduced into a standard talc base: 100% talc, very slight characteristic odor, white powder, manufacturer: LUZENAC, mixed, and an equivalent amount of 0.2% of fragrance is added.

[0294] Example 26 Shower gel composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0295] [Table 30]

[0296] Mix the ingredients and adjust the pH to 6-6.3 (viscosity: 4500 cPo ± 1500 cPo (Brookfield RV / spindle #4 / 20 RPM)).

[0297] Example 27 Shower gel composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0298] [Table 31]

[0299] The ingredients are mixed and the pH is adjusted to 4.5 (viscosity: 3000 cPo ± 1500 cPo (Brookfield RV / spindle #4 / 20 RPM)).

[0300] Example 28 Shower gel composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0301] [Table 32]

[0302] The ingredients are mixed and the pH is adjusted to 4.5 (viscosity: 4000 cPo ± 1500 cPo (Brookfield RV / spindle #4 / 20 RPM)).

[0303] Example 29 hair coloring composition A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed with alkaline base A and an equivalent amount of 0.2% perfume is added.

[0304] Then, 2 g of alkaline base A is mixed with 2 g of oxide base B.

[0305] [Table 33-1] [Table 33-2]

[0306] procedure: All ingredients of Phase A were mixed and heated to 75°C. All ingredients of Phase B were combined and melted at 70-75°C. Phase B was added to Phase A with good stirring (both at 70-75°C). Phase C was added and mixing was continued until cooled to room temperature. At room temperature, the ingredients of Phase D were added with mixing. The remaining ingredients of Phase C were added under stirring.

[0307] [Table 34]

[0308] procedure: All ingredients of Phase A were mixed and heated to 75°C. All ingredients of Phase B were combined and melted at 70-75°C. Phase B was added to Phase A with good mixing (both at 70-75°C) and mixing was continued until cooled to room temperature. At room temperature, the ingredients of Phase C were added with mixing.

[0309] Example 30 Hand-washing dish detergent A sufficient amount of the inventive microcapsules according to Examples 1 and 3 are weighed and mixed into the following composition to add the equivalent of 0.2% perfume.

[0310] [Table 35]

[0311] Mix water containing sodium hydroxide and diethanolamide. Add LAS. After LAS is neutralized, add remaining ingredients. Check pH (7-8) and adjust if necessary.

[0312] Example 31 Toothpaste formulations A sufficient amount of Microcapsule Slurry R (corresponding to the microcapsules of the present invention according to Examples 1 and 3, except that a flavor is encapsulated instead of a fragrance) is weighed and mixed into the following composition to add the equivalent of 0.2% of the flavor:

[0313] [Table 36]

[0314] Example 32 Dicalcium phosphate-based toothpaste formulations A sufficient amount of Microcapsule Slurry R (corresponding to the microcapsules of the present invention according to Examples 1 and 3, except that a flavor is encapsulated instead of a fragrance) is weighed and mixed into the following composition to add the equivalent of 0.2% of the flavor:

[0315] [Table 37]

[0316] Example 33 Alcohol-free mouthwash formulation A sufficient amount of Microcapsule Slurry R (corresponding to the microcapsules of the present invention according to Examples 1 and 3, except that a flavor is encapsulated instead of a fragrance) is weighed and mixed into the following composition to add the equivalent of 0.2% of the flavor:

[0317] [Table 38]

[0318] Example 34 Mouthwash formulations A sufficient amount of Microcapsule Slurry R (corresponding to the microcapsules of the present invention according to Examples 1 and 3, except that a flavor is encapsulated instead of a fragrance) is weighed and mixed into the following composition to add the equivalent of 0.2% of the flavor:

[0319] [Table 39]

Claims

1. 1. A method for preparing core-shell microcapsules or a core-shell microcapsule slurry, comprising: a. mixing a hydrophobic material, preferably a perfume oil, and a polylactone-based polyisocyanate prepolymer obtained by reacting a polylactone polyol with a polyisocyanate to form an oil phase; b. dispersing the oil phase in a dispersed phase comprising an emulsifier or stabilizer, and optionally a cross-linking agent, to form an emulsion; c. Optionally, adding a cross-linking agent to the emulsion; d. applying conditions sufficient to induce crosslinking of said polylactone-based polyisocyanate prepolymer to form said core-shell microcapsules or core-shell microcapsule slurry. A method comprising:

2. Polylactone-based polyisocyanate prepolymers i. providing a polylactone polyol and optionally a solvent; ii. adding polyisocyanate to the mixture of step i. so that NCO functional groups are in excess of OH groups, preferably in a molar ratio of NCO / OH > 2, preferably in a molar ratio of NCO / OH > 4; iii. Applying conditions to cause a reaction between the OH functional groups of the polylactone polyol and the NCO functional groups of the polyisocyanate to form the polylactone-based polyisocyanate prepolymer. The method of claim 1 obtained by a process comprising:

3. 3. The method of claim 1 or 2, wherein the polylactone polyol is a polycaprolactone, preferably a polycaprolactone diol or triol.

4. 4. The method of any one of claims 1 to 3, wherein the polylactone polyol has a molecular weight in the range of 200 g / mol to 10,000 g / mol, preferably 220 g / mol to 2,000 g / mol, more preferably 240 g / mol to 550 g / mol.

5. 5. The method of claim 1, wherein the polyisocyanate comprises an aliphatic polyisocyanate, an aromatic polyisocyanate, or a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate, preferably an aromatic polyisocyanate.

6. 6. The method according to any one of claims 1 to 5, wherein the polyisocyanate is xylylene diisocyanate, toluene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, L-lysine diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, L-lysine diisocyanate ethyl ester, lysine triisocyanate, an aliphatic isocyanate biuret, an aliphatic or aromatic isocyanate trimethylolpropane (TMP) adduct, an aromatic isocyanate trimethylolpropane (TMP) adduct, preferably xylylene diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate and an aromatic isocyanate trimethylolpropane (TMP) adduct, more preferably xylylene diisocyanate, toluene diisocyanate and an aromatic isocyanate trimethylolpropane (TMP) adduct.

7. 7. The method according to claim 1, wherein the emulsifier or stabilizer is a polymeric stabilizer such as polyvinyl alcohol, cellulose derivatives, polyethylene oxide, copolymers of polyethylene oxide and polyethylene or polypropylene oxide, copolymers of acrylamide and acrylic acid, copolymers of vinylpyrrolidone and quaternized vinylimidazole, and sodium dodecyl sulfate; an inorganic colloidal stabilizer such as hydroxyapatite, calcium carbonate, kaolin, laponite, silica, amine-functionalized silica, clay, sericite mica, or tricalcium phosphate; a polysaccharide such as gum arabic, starch, modified starch, chitosan, sodium alginate, alginic acid, cellulose, chitin, pectin, sugar beet pectin, or a colloidal stabilizer comprising such a polysaccharide; a protein such as silk fibroin, sericin, gelatin, sodium caseinate, casein, bovine serum albumin, isolated whey protein, potato protein, isolated soy protein, and mixtures thereof, or a colloidal stabilizer comprising such a protein.

8. 8. The method of any one of claims 1 to 7, wherein the crosslinking agent is a polyfunctionalized amine, such as ethylenediamine, diethylenetriamine, triethylenetetraamine, guanidine, 1,5-pentanediamine, 1,8-diaminooctane, 1,12-diaminododecane, 3,5-diamino-1,2,4-triazole, urea; an amino acid, such as l-lysine, l-tryptophan, l-cystine, cystamine and their hydrochlorides; a polyfunctionalized polyol, such as 1,5-pentanediol, 1,6-hexanediol, and a polylactone-based polyol; or a polyfunctionalized thiol.

9. 9. The method of any one of claims 1 to 8, wherein the conditions sufficient to induce crosslinking comprise heating the oil-in-water emulsion at elevated temperature, preferably at a temperature of at least 30°C, for at least 30 minutes.

10. 10. Core-shell microcapsules or core-shell microcapsule slurry obtainable by the method according to any one of claims 1 to 9.

11. The core-shell microcapsules are a core comprising a hydrophobic material, preferably a perfume oil, preferably an oil core, - a crosslinked polymer shell surrounding said oil core, obtained by reacting a polylactone-based polyisocyanate prepolymer obtained by reacting a polylactone polyol with a polyisocyanate, and optionally with a crosslinking agent; The core-shell microcapsule or core-shell microcapsule of claim 10, comprising:

12. - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to any one of claims 1 to 9 or as defined in claims 10 and 11, at least one ingredient selected from the group consisting of perfume carriers and perfume bases, and optionally at least one perfume adjuvant A fragrance composition comprising:

13. - core-shell microcapsules or core-shell microcapsule slurries obtainable by the process according to any one of claims 1 to 9 or as defined in claims 10 and 11, and - Personal care, home care or fabric care active base and flavored consumer products, including

14. 14. The perfumed consumer product of claim 13, wherein the perfumed consumer product is preferably selected from the group consisting of a personal care composition, a home care composition or a fabric care composition, most preferably in the form of an antiperspirant, a hair care product, such as a shampoo or a hair conditioner, a body care product, such as a shower gel, an oral care product, a laundry care product, preferably a detergent or a fabric softener.

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