Polydisulfide Core-Shell Microcapsules

Abstract

The present invention relates to a new method for preparing polydisulfide core-shell microcapsules. The polydisulfide core-shell microcapsules comprise an oily core comprising a hydrophobic material and a polymeric shell comprising polydisulfide bonds. The polydisulfide core-shell microcapsules are also the subject of the present invention. Perfume compositions and consumer products comprising the polydisulfide core-shell microcapsules are also the subject of the present invention.

Description

[Technical field]

[0001] The present invention relates to a new method for preparing polydisulfide core-shell microcapsules. The polydisulfide core-shell microcapsules comprise an oily core comprising a hydrophobic material and a polymeric shell comprising polydisulfide bonds. The polydisulfide core-shell microcapsules are also the subject of the present invention. Perfume compositions and consumer products comprising the polydisulfide core-shell microcapsules are also the subject of the present invention.

[0002] 2. Background of the Invention One of the problems faced by the fragrance industry is that the olfactory benefits provided by odoriferous compounds are lost relatively quickly due to their high volatility, especially the volatility of the "top notes". In order to control the release rate of volatile substances, delivery systems such as microcapsules containing active ingredients, e.g., fragrances, need to protect the core payload and release it later when triggered. A key requirement by the industry for these systems is to withstand suspension in a challenging base without physical dissociation or decomposition. This is referred to as the chemical stability of the delivery system. For example, perfumed personal and household cleaners that contain high levels of aggressive surfactant detergents are very challenging for the stability of delivery systems, e.g., microcapsules. High levels of surfactants also increase the diffusion rate of active substances from delivery systems such as microcapsules. This reduces the impact of leakage of active substances during storage and release of microcapsules.

[0003] In addition to performance in terms of stability and olfactory performance, consumer demand for environmentally friendly delivery systems is becoming increasingly important and is driving the development of new delivery systems. There remains a need in the industry to improve biodegradability while at the same time providing a degree of chemical stability to the delivery system, reducing leakage of perfume from the delivery system and preferably providing improved impact of the perfume upon release to the consumer.

[0004] There is therefore still a need to provide new microcapsules using more environmentally friendly materials, without compromising the performance of the microcapsules in terms of stability, especially in hostile media such as consumer product bases, and also in providing good performance in terms of delivery of active ingredients, e.g. olfactory performance in the case of perfumery ingredients.

[0005] The present invention fulfills these and other industry needs.

[0006] Detailed Description of the Invention Unless otherwise stated, percentages (%) are intended to refer to percentages by weight of the composition.

[0007] Room temperature is understood in this specification as a temperature between 20° C. and 25° C. or between 293 K and 298 K.

[0008] By "hydrophobic material" is meant a material that forms a two-phase dispersion when mixed with water. According to the present invention, the hydrophobic material can be an "inert" material such as a solvent or an active ingredient. According to one embodiment, the hydrophobic material is a hydrophobic active ingredient.

[0009] "Active ingredient" means a single compound or a combination of ingredients.

[0010] By "perfume oil" is meant a single perfuming compound or a mixture of perfuming compounds.

[0011] "Consumer product" or "final product" means a manufactured item that is ready for distribution, sale and use by a consumer.

[0012] A "core-shell microcapsule" or the like in this invention comprises a core based on a hydrophobic material, typically a perfume oil, and a polymeric shell surrounding the oily core.

[0013] The core-shell microcapsules have a particle size distribution in the micron range (eg average diameter) comprised between about 1 and 3000 microns, preferably between 1 and 1000 microns, more preferably between 1 and 500 microns, even more preferably between 5 and 50 microns.

[0014] "Particle size" refers to 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.

[0015] "Microcapsule size" refers to the volume average diameter of the capsules, capsule suspension as determined by laser light scattering of a diluted sample on a Malvern Mastersizer 3000.

[0016] "Core-shell microcapsule slurry" means core-shell microcapsules dispersed in a liquid. According to one embodiment, the slurry is an aqueous slurry, i.e., the core-shell microcapsules are dispersed in an aqueous phase.

[0017] "Polydisulfide core-shell microcapsule slurry" means polydisulfide core-shell microcapsules dispersed in a liquid. According to one embodiment, the slurry is an aqueous slurry, i.e., the core-shell microcapsules are dispersed in an aqueous phase.

[0018] "Multifunctional monomer" refers to a molecule that chemically reacts or bonds as a unit to form a polymer or supramolecular polymer. The multifunctional monomer of the present invention has at least two functional groups that can react or bond with functional groups of other components and / or polymerize to form a polymer shell.

[0019] Method for preparing polydisulfide core-shell microcapsule slurry The present invention relates to a method for preparing a polydisulfide core-shell microcapsule slurry, the method comprising: a) dissolving at least one polythiol monomer in a hydrophobic material, preferably a perfume oil, to form an oil phase; b) dispersing the oil phase obtained in step a) in an aqueous phase to form an oil-in-water emulsion; c) applying conditions sufficient to induce thiol oxidation at the oil-water interface to form a polydisulfide core-shell microcapsule slurry; Including, an oxidation catalyst is added to the oil phase in step a) and / or to the oil-in-water emulsion obtained after step b), A stabilizer is added to the oil phase in step a) and / or to the aqueous phase in step b), The oxidizing agent is added to the aqueous phase in step b) and / or to the oil-in-water emulsion obtained after step b).

[0020] According to one embodiment, the method comprises the steps of: a) dissolving at least one polythiol monomer in a hydrophobic material, preferably a perfume oil, to form an oil phase; b) dispersing the oil phase obtained in step a) in an aqueous phase to form an oil-in-water emulsion; c) inducing thiol oxidation at the oil-water interface by adding an oxidizing agent to the oil-in-water emulsion under stirring to form a polydisulfide core-shell microcapsule slurry; Including, an oxidation catalyst is added to the oil phase in step a) and / or to the oil-in-water emulsion obtained after step b), The stabilizer is added to the oil phase in step a) and / or to the water phase in step b).

[0021] Polythiol Monomer According to the present invention, an oil phase is formed by dissolving at least one polythiol monomer in a hydrophobic material, preferably a perfume oil.

[0022] According to one embodiment, a polythiol monomer is dissolved in a hydrophobic material.

[0023] Polythiol monomer is understood herein to be an organic molecule that contains two or more functional groups that are thiol groups. The term thiol group is understood herein to be a -SH functional group. Those skilled in the art know the definition of thiol group.

[0024] According to one embodiment, the polythiol monomer is selected in the group consisting of difunctional thiol monomers, trifunctional thiol monomers, tetrafunctional thiol monomers, pentafunctional thiol monomers, hexafunctional thiol monomers, heptafunctional thiol monomers, octafunctional thiol monomers, thiolated polysaccharides, thiolated chitosan, thiolated proteins, thiolated pectins, thiolated polyols, hydrolyzed / reduced keratin, proteins with two or more thiol groups, and mixtures thereof.

[0025] According to one embodiment, the polythiol monomer is a difunctional thiol monomer, such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, dithioerythritol, 1,4-butanediol bis(thioglycolate), 4,4'-biphenyldithiol, ethylene bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), 1,10-decanedithiol, 1,11-undecanedithiol, 1,16-hexadecanedithiol, 1,4-benzenedithiol, 3,7-dithia-1,9-dithio-1,10-dithio-1,11-dithio-1,12-dithio-1,13-dithio-1,14-dithio-1,15-dithio-1,2-dithio-1,3-dithio-1,4-dithio-1,5-dithio-1,6-dithio-1,7-dithio-1,8-dithio-1,9-dithio-1,9-dithio-1,5-dithio-1,6-dithio-1,7-dithio-1,8-dithio-1,9-dithio-1,9-dithio-1,9-dithio-1,10-dithio-1,2-dithio-1,3-dithio-1,4-dithio-1,5-dithio-1,6-dithio-1,7-dithio-1,8-dithio-1,9 ...9-dithio-1,9-dithio-1,5 -nonanedithiol, 4,4'-thiobisbenzenethiol, hexa(ethylene glycol)dithiol, bis(2-mercaptoethyl)sulfide, 3,6-dioxa-1,8-octanedithiol, 1,5-dimercaptonaphthalene, 1,3-benzenedithiol, 2,3-butanedithiol, dithiothreitol, 2,3-dimercapto-1-propanol, 2,2'-(ethylenedioxy)diethanethiol, hexa(ethylene glycol)dithiol, tetra(ethylene glycol)dithiol, polyethylene glycol dithiol, preferably ethylene glycol bis(3-mercaptopropionate), or mixtures thereof.

[0026] The polyethylene glycol dithiol has a molecular weight (M n ).

[0027] When a difunctional thiol monomer is used, it can be used in combination with at least one polythiol monomer having two or more -SH functional groups, such as, for example, a trifunctional thiol monomer, a tetrafunctional thiol monomer, a pentafunctional thiol monomer, a hexafunctional thiol monomer, a heptafunctional thiol monomer, or an octafunctional thiol monomer.

[0028] According to one embodiment, the polythiol monomer is a trifunctional thiol monomer, preferably trimethylolpropane tris(3-mercaptopropionate) or tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, preferably tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate.

[0029] According to one embodiment, the polythiol monomer is a tetrafunctional thiol monomer, preferably pentaerythritol tetrakis(3-mercaptopropionate) or 4arm-PEG-SH. 4arm-PEG-SH, as used herein, has the chemical formula C(CHO(CHCHO) n CH2CH2SH)4, and preferably n is a molecular weight (M) of the compound between 5000 g / mol and 20000 g / mol. n ) is an integer having a molecular weight (M) of 5000 g / mol to 20000 g / mol, preferably 8000 g / mol to 15000 g / mol. n ).

[0030] According to one embodiment, the polythiol monomer is a hexafunctional thiol monomer, preferably dipentaerythritol hexakis(3-mercaptopropionate).

[0031] According to one embodiment, the polythiol monomer is an octafunctional thiol monomer, preferably 8arm-PEG-SH. 8arm-PEGSH, as used herein, is a moiety of formula R(O(CH2CH2O)nCH2CH2SH)8, where R is a tripentaerythritol or hexaglycerol core structure, and preferably n is a molecular weight (M) of the compound between 10,000 g / mol and 20,000 g / mol. n ) is understood to be an integer having a molecular weight (M) of 10,000 g / mol to 20,000 g / mol, preferably 13,000 g / mol to 17,000 g / mol. n ).

[0032] According to one embodiment, the polythiol monomer is present in an amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight, more preferably from 1.0% to 15% by weight, relative to the total weight of the oil-in-water emulsion obtained in step b).

[0033] According to one embodiment, the polythiol monomer is present in an amount of 0.1% to 50% by weight, preferably 0.5% to 35% by weight, more preferably 1% to 25% by weight relative to the total amount of the oil phase.

[0034] According to one embodiment, at least one further multifunctional monomer is added to the method, where the at least one further multifunctional monomer is not a polythiol monomer. According to a preferred embodiment, the at least one further multifunctional monomer is added to the oil phase in step a).

[0035] According to one embodiment, the at least one further multifunctional monomer is selected in the group consisting of polyisocyanates, polyanhydrides such as polymaleic anhydride, polyacyl chlorides, polyepoxides, polyaldehydes, polyalkoxysilanes, alkene, alkyne, or acrylate monomers such as poly(meth)acrylate monomers, and mixtures thereof, where poly(meth)acrylates include polyacrylates, polymethacrylates, and mixtures of polyacrylates and polymethacrylates.

[0036] According to a particular embodiment, the at least one other multifunctional monomer added in step a) is at least one polyisocyanate having at least two isocyanate functional groups.

[0037] Suitable polyisocyanates for use according to the present invention include aromatic polyisocyanates, aliphatic polyisocyanates and mixtures thereof. The polyisocyanates contain at least two, preferably at least three, isocyanate functional groups, but may contain up to six, or even only four, isocyanate functional groups. According to certain embodiments, triisocyanates are used.

[0038] According to one embodiment, the polyisocyanate is an aromatic polyisocyanate.

[0039] The term "aromatic polyisocyanate" is intended herein to encompass any polyisocyanate that contains an aromatic moiety. Preferably, the aromatic polyisocyanate contains a phenyl, toluyl, xylyl, naphthyl or diphenyl moiety, more preferably a toluyl or xylyl moiety. Preferred aromatic polyisocyanates include biurets, polyisocyanurates and trimethylolpropane adducts of diisocyanates, more preferably one of the specific aromatic moieties listed above. More preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (available under the trade name Desmodur® RC from Bayer), a trimethylolpropane adduct of toluene diisocyanate (available under the trade name Desmodur® L75 from Bayer), a trimethylolpropane adduct of xylylene diisocyanate (available under the trade name Takenate® D-110N from Mitsui Chemicals, Inc.). In a most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

[0040] According to another embodiment, the polyisocyanate is an aliphatic polyisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain any aromatic moiety. Preferred aliphatic polyisocyanates are trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals, Inc.), or biuret of hexamethylene diisocyanate (available from Bayer under the trade name Desmodur® N 100), of which biuret of hexamethylene diisocyanate is more preferred.

[0041] 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 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 adduct of toluene diisocyanate. Most preferably, the polyisocyanate is a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate. Preferably, when used as a mixture, the molar ratio of aliphatic polyisocyanate to aromatic polyisocyanate is in the range of 80:20 to 10:90.

[0042] According to one embodiment, the at least one polyfunctional monomer used in the process according to the present invention is present in an amount represented by 0.1 to 35% by weight, preferably 0.5 to 10% by weight, more preferably 0.8 to 6% by weight and even more preferably 1 to 5% by weight relative to the total amount of the oil phase.

[0043] Hydrophobic Materials According to one embodiment, the core is an oily core.

[0044] A hydrophobic material according to the present invention can be an "inert" material such as a solvent or an active ingredient.

[0045] When the hydrophobic material is an active ingredient, the active ingredient is preferably selected from the group consisting of flavors, flavor ingredients, fragrances, fragrance ingredients, dietary supplements, cosmetics, pest control agents, biocidal actives, deodorant ingredients, bactericidal ingredients, fungicidal ingredients, pharmaceutical or pesticide ingredients, disinfecting ingredients, insect repellents or attractants, and mixtures thereof.

[0046] According to a particular embodiment, the hydrophobic material comprises a phase change material (PCM).

[0047] According to certain embodiments, the hydrophobic material comprises a mixture of a fragrance and another ingredient selected from the group consisting of dietary supplements, cosmetics, pest control agents and biocidal actives.

[0048] According to certain embodiments, the hydrophobic material comprises a mixture of a biocidal active and another ingredient selected from the group consisting of fragrances, dietary supplements, cosmetics, and pest control agents.

[0049] According to certain embodiments, the hydrophobic material comprises a mixture of a pesticide and another ingredient selected from the group consisting of a fragrance, a nutraceutical, a cosmetic, or a biocide active.

[0050] According to certain embodiments, the hydrophobic material comprises a fragrance.

[0051] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0052] According to a particular embodiment, the hydrophobic material consists of a biocidal active agent.

[0053] According to certain embodiments, the hydrophobic material comprises a pesticide.

[0054] By "perfume" (or also "perfume oil") herein is meant an ingredient or composition that is liquid at about 20°C. According to any one of the above embodiments, said perfume oil may be a perfuming ingredient alone or a mixture of ingredients in the form of a perfume composition. By "perfuming ingredient" herein is meant a compound that is used for the primary purpose of imparting or modulating an odor. In other words, such an ingredient, in order to be considered a perfuming ingredient, must not only have an odor but must be recognized by the skilled artisan as being at least capable of imparting or modifying 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 any substance that both improves, enhances or modifies the delivery of the perfuming ingredient, such as perfume precursors, modifiers, emulsions or dispersions, and combinations that provide additional benefits beyond modifying or imparting an odor, such as persistence, blooming, deodorization, antibacterial action, microbial stability and / or pest control.

[0055] The nature and type of perfume ingredients present in the oil phase do not require a more detailed description here, and are in any case not comprehensive, and 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, these perfume ingredients belong to various chemical classes, such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds, and essential oils (e.g. thyme oil), and said perfume co-ingredients can be of natural or synthetic origin.Many of these co-ingredients are described in any case in reference literature, for example in the book Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, by S. Arctander, or its more recent editions, or other treatises of the same kind, and in the abundant patent literature in the field of perfumery.

[0056] Mention may in particular be made of 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 α-pinene; - Balsam components: 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 components: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamaldehyde, 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, (1E)-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-indanethanol, 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-dimethylphenyl)propanal, 1,2-dimethylphenylacetate, 1,3-dimethylphenylacetate, 1,4-dimethylphenylacetate, 1,5-dimethylphenylacetate, 1,6-dimethylphenylacetate ...6-dimethylphenylacetate, 1,7-dimethylphenylacetate, 1,6-dimethylphenylacetate, 1,7-dimethylphenylacetate, 1,8-dimethylphenylacetate, 1,8-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9-dimethylphenylacetate, 1,9 ethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, cis-high methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, vergyl proprionate, 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 methyl ionone isomeric mixture;, - Fruity ingredients: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanolide, ethyl 2-methylpentanoate, 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, styralyl 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 stereoisomers thereof, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal.

[0057] It is also understood that the ingredient may be a compound known to provide a controlled release of various types of perfuming compounds, also known as properfumes or profragrances. Non-limiting examples of suitable properfumes 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)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 3-(dodecylthio)-4-(2,6,6-trimethyl-2 ... O)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-ylhexadecanoate, 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) )oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-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.

[0058] The perfuming ingredients can 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® (a rosin-based resin available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is very 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% solvent, all these percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially solvent-free.

[0059] Preferred perfuming ingredients are those with high steric hindrance (bulky materials), in particular from one of the following groups: - 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 substituted with 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: Odour components containing camphor-like ring structures; - Group 6: at least one C7-C 20 Fragrance components containing ring structures; - Group 7: Perfuming ingredients having a logP value of more than 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent; Examples of components from each of these groups are as follows: - group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (supplier: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (supplier: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylates, rose oxide, (S)-1,8-p-menthadien-7-ol (supplier: 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 (Supplied by: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanediethyl dicarboxylate (Supplied by: Firmenich SA, Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (Supplied by: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (supplied 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 (supplied by Givaudan SA, Vernier, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (supplied by Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol (supplied by Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentane acetate (supplied by Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (supplied by Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (supplied by Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (supplied by Givaudan SA, Vernier, Switzerland); - group 3: damascone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (supplied by 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 (supplied by Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (supplied by Firmenich SA, Geneva, Switzerland); SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate (Supplied by: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (Supplied by: International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (Supplied by: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (Supplied 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 (Supplied by Firmenich SA, Geneva, Switzerland), 8-Methoxy-1-p-menthene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate (Supplied by Firmenich SA, Geneva, Switzerland).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 (Supplier: 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]dec-4-en-8-yl 2-methylpropanoate, vetiverol, vetiveron, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone (supplied 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) isomer, 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 (supplied by International Flavors and Fragrances, USA). Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (Supplied by Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undec-4-ene-9-spiro-2'-oxirane (Supplied by Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (Supplied by Firmenich SA, Geneva, Switzerland), octalinol, (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan (Supplied by 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 (supplier: 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 ]undecane-4-one (supplied by Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (supplied by Firmenich SA, Geneva, Switzerland); - group 6: (trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (supplier: Firmenich SA, Geneva, Switzerland), 9-hexadecen-16-olide (supplier: Firmenich SA, Geneva, Switzerland), pentadecenolide (supplier: Firmenich SA, Geneva, Switzerland), 3-methyl-(4 / 5)-cyclopentadecenone, (supplier: Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (supplier: Firmenich SA, Geneva, Switzerland), pentadecanolide (supplier: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (supplier: Firmenich SA, Geneva, Switzerland), (1-ethoxyethoxy)cyclododecane (Supplier: 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 (Supplier: Givaudan SA, Vernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0060] 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, said perfume comprises at least 30%, preferably at least 50% of ingredients from groups 3 to 7 as defined above. Most preferably, said perfume comprises at least 30%, preferably at least 50% of ingredients from groups 3, 4, 6 or 7 as defined above.

[0061] According to another preferred embodiment, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients having a logP greater than 3, preferably greater than 3.5, even more preferably greater than 3.75.

[0062] 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 does not contain any primary alcohols and contains less than 15% of secondary and tertiary alcohols.

[0063] According to one embodiment, the oily phase (or oily core) comprises: - 25 to 100% by weight, preferably 25 to 98% by weight, of perfume oil containing at least 15% by weight of high impact perfume raw materials having a LogT of less than -4, and - 1.07g / cm 3 0 to 75% by weight, preferably 2 to 75% by weight, of a density adjusting material having a density of greater than Includes.

[0064] A "high impact perfume raw material" is to be understood as a perfume raw material having a LogT of less than -4. The odor threshold concentration of a chemical compound is determined in part by its shape, polarity, partial charge and molecular mass. For convenience, the odor threshold concentration is expressed as the base 10 logarithm of the threshold concentration, i.e., Log[Threshold] ("LogT").

[0065] "Density adjustment material" is 1.07g / cm 3 By this is meant a material which has a density of 0.1 to 100% and which is preferably low-odor or odorless.

[0066] The odor threshold concentration of the fragrance compound is determined using a gas chromatograph ("GC"). Specifically, the gas chromatograph is calibrated with the exact amount of fragrance oil component injected by syringe, the exact split ratio, and hydrocarbon standards of known concentration and chain length distribution to determine the hydrocarbon response. The air flow rate is precisely measured and the sampling volume is calculated, assuming a human inhalation time lasts 12 seconds. Since the exact concentration at the detector at any time is known, the mass per inhalation volume and therefore the concentration of the fragrance compound is known. To determine the threshold concentration, a solution of the back-calculated concentration is sent to a sniff port. Panelists sniff the GC eluate and identify the retention time when they notice an odor. The average of all panelists determines the odor threshold concentration of the fragrance compound. Determination of 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, pages 54-61.

[0067] High impact fragrance ingredients with LogT less than -4 and 1.07 g / cm 3The properties of density adjusting materials having a density of greater than 1000 nm are described in WO2018115250, the contents of which are incorporated by reference.

[0068] According to one embodiment, the high impact perfume raw materials having a LogT of less than -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-Penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[b]furan-2-one and a mixture containing (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)-furanium Mixture containing non, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4α,8aβ-dimethyl-4a-naphthalenol, patchoulol, 2-methoxy-4-(1-propenyl)phenol, (+-)-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, β,2,2,3-tetramethyl-δ-methylene-3-cyclopentene-1-butanol, δ-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, paracresol, 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, paracresyl acetate, dodecalactone, tricyclone, (+)-(3R,5Z)-3-methyl 1-5-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-hexyl Tetrahydro-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, ethyl praline, (4-methylphenoxy)acetaldehyde, ethyl tricyclo[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-thiabicyclo[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-cyclopenten-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.

[0069] According to one embodiment, the perfume raw materials having a LogT of less than -4 are selected in the group consisting of aldehydes, ketones, alcohols, phenols, esters, lactones, ethers, epoxides, nitriles and mixtures thereof.

[0070] According to one embodiment, the perfume raw material having a LogT less than -4 comprises at least one compound selected from the group consisting of alcohols, phenols, esters, lactones, ethers, epoxides, nitriles and mixtures thereof, preferably in an amount of 20-70% by weight based on the total weight of the perfume raw material having a LogT less than -4.

[0071] According to one embodiment, the perfume raw materials having a LogT less than -4 comprise 20-70% by weight of aldehydes, ketones and mixtures thereof based on the total weight of the perfume raw materials having a LogT less than -4.

[0072] Therefore, the remaining perfume raw materials contained in the oily core may have a LogT greater than -4.

[0073] According to one embodiment, the perfume raw materials having a LogT greater than -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, 3-cyclohexylpropanoic acid allyl, (Z)-3-hexenyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, heptanoic acid allyl, 2-(2-methyl-2-propanyl)cyclohexanone lopanyl)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-cyclohexen-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-butanoate Ten-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.

[0074] According to one embodiment, the fragrance formulation comprises: - 0 to 60% by weight (based on the total weight of the fragrance formulation) of a hydrophobic solvent, - 40 to 100% by weight of perfume oil (based on the total weight of the perfume formulation) and the perfume oil has at least two, and preferably all, of the following properties: 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 bulky materials of groups 1 to 6, preferably 3 to 6, as defined above, and at least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least 30% of high impact perfume materials having a LogT below -4, Optionally, a further hydrophobic active ingredient.

[0075] According to a particular embodiment, the perfume comprises 0-60% by weight of hydrophobic solvent.

[0076] According to a particular embodiment, the hydrophobic solvent is a density adjusting material, preferably 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.

[0077] In certain embodiments, the hydrophobic solvent has a Hansen Solubility Parameter that is compatible with the encapsulated perfume oil.

[0078] 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, developed on the basis that the total energy of vaporization of a liquid consists of several individual parts. To calculate the "weighted Hansen Solubility Parameter", it is necessary to combine the effects of (atomic) dispersion forces, (molecular) permanent dipole-dipole forces and (molecular) hydrogen bonding (electron exchange). The "weighted Hansen Solubility Parameter" is calculated by the weighting factor (δD 2 +δP 2 +δH 2 ) 0.5 where δD is the Hansen dispersion value (hereinafter also referred to as atomic dispersion force), δP is the Hansen polarizability value (hereinafter also referred to as dipole moment), and δH is the Hansen hydrogen bond ("h-bond") value (hereinafter also referred to as hydrogen bond). For a more detailed description of the parameters and values, see Charles Hansen, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, Danish Technical Press (Copenhagen, 1967).

[0079] The Euclidean difference in solubility parameters between the fragrance and the solvent is (4 × (δD 溶媒 -δD フレグランス ) 2 +(δP 溶媒 -δP フレグランス )2 +(δH 溶媒 -δH フレグランス ) 2 ) 0.5 where δDsolvent, δPsolvent and δHsolvent are the Hansen dispersion, Hansen polarizability and Hansen h-bonding values ​​of the solvent, respectively, and δDfragrance, δP フレグランス and δH フレグランス are the Hansen dispersion value, Hansen polarizability value and Hansen h-bonding value of the fragrance, respectively.

[0080] 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.

[0081] 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 (δP) of 1 to 8, preferably 1 to 7, and a hydrogen bond (δH) of 2.5 to 11, preferably 4 to 11.

[0082] 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 an atomic dispersion force (δD) of 12-20, a dipole moment (δP) of 1-8, and a hydrogen bond (δH) of 2.5-11.

[0083] 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 (δP) of 1 to 8, preferably 1 to 7, and a hydrogen bond (δH) of 2.5 to 11, preferably 4 to 11.

[0084] According to one embodiment, the fragrance formulation comprises an odor modifier (which can be used in addition to the hydrophobic solvent, if one is present, or instead of the hydrophobic solvent, if one is not present).

[0085] Preferably, odor control agents are defined as odoriferous materials having: i. A vapor pressure of less than 0.0008 Torr at 22°C; ii. a clogP of 3.5 or greater, preferably 4.0 or greater, more preferably 4.5; iii. at least two Hansen solubility parameters selected from a first group consisting of atomic dispersion forces of 12-20, dipole moments of 1-7, and hydrogen bonds of 2.5-11; iv. at least two Hansen solubility parameters selected from a second group consisting of atomic dispersion forces of 14-20, dipole moments of 1-8, and hydrogen bonds of 4-11 in a solution with a compound having a vapor pressure range of 0.0008-0.08 Torr at 22 °C.

[0086] Preferably, the following ingredients can be mentioned as regulators 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)-oxacycloheptadeca-8-en-2-one, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, muguetaldehyde (muguet aldehyde), 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,4aS,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amylcinnamaldehyde, hexylcinnamaldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadiene-3-one, (9Z)-9-cycloheptadecen-1-one.

[0087] According to a particular embodiment, the hydrophobic material does not include any active ingredient (such as fragrances). According to this particular embodiment, the hydrophobic material comprises, preferably consists of, a hydrophobic solvent, preferably isopropyl myristate, triglycerides (e.g. Neobee® MCT oil, vegetable oils), D-limonene, silicone oils, mineral oils and mixtures thereof, and optionally a hydrophilic solvent, preferably selected in 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.

[0088] The term "biocide" refers to a chemical that can kill or reduce or prevent the growth and / or accumulation of living organisms (e.g., microorganisms). Biocides are commonly used in the medical, agricultural, forestry, and forestry industries to prevent fouling of, for example, water, agricultural products including seeds, and oil pipelines. Biocides can be pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides, and rodenticides, and / or antimicrobials, such as bactericides, antibiotics, antibacterial agents, antivirals, antifungals, antiprotozoals, and / or antiparasitics.

[0089] As used herein, "pesticide" 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 is a nuisance to plants or animals, and includes insects, particularly arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0090] According to any one of the embodiments of the present invention, the hydrophobic material represents about 10% to 90% by weight, preferably 12% to 60% by weight, and even more preferably 15% to 45% by weight, based on the total weight of the oil phase.

[0091] Stabilizer According to the invention, the stabilizer is added to the oil phase in step a) and / or to the water phase in step b).

[0092] A stabilizer is understood herein to be a compound suitable for stabilizing an oil-in-water emulsion. A stabilizer is also understood herein to be an emulsifier or dispersant.

[0093] According to one embodiment, the stabilizer is a colloidal stabilizer.

[0094] According to a preferred embodiment, the colloidal stabilizer is polyvinyl alcohol or polyvinylpyrrolidone, or a mixture thereof.

[0095] According to one embodiment, the stabilizer is an anionic or amphiphilic biopolymer, preferably selected from the group consisting of whey protein isolate, sodium caseinate, gum arabic, sugar beet pectin, gelatin, proteins and / or combinations thereof.

[0096] According to one embodiment, the stabilizer is a protein selected in the group consisting of soy protein, hydrolyzed silk protein, potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten protein, lupin protein and mixtures thereof.

[0097] According to a preferred embodiment, the stabilizer is a combination of sodium caseinate and whey protein isolate.

[0098] According to one embodiment, the stabilizer is a cationic stabilizer.

[0099] According to one embodiment, the stabilizer is combined with a salt. According to a preferred embodiment, the anionic or amphiphilic biopolymer is combined with a salt. According to one embodiment, the salt is selected from the group consisting of calcium salts, sodium salts, potassium salts, lithium salts, magnesium salts, sulfates, phosphates, nitrates, bromides, chlorides, iodides, and ammonium salts. According to a preferred embodiment, the salt is selected from the group consisting of CaCl2, NaCl, KCl, LiCl, Ca(NO3)2, MgCl2, CaBr2, CaI2, NaBr, NaI, NaNO3, KBr, KI, KNO3, LiBr, LiI, MgBr2, and mixtures thereof. According to a more preferred embodiment, the salt is selected from the group consisting of CaCl2, NaCl, KCl, LiCl, Ca(NO3)2, MgCl2, and mixtures thereof.

[0100] Even more preferably, the stabiliser is selected from the group of polyvinyl alcohol, whey protein isolate, sodium caseinate, cellulose polymers, polyvinylpyrrolidone, anionic polyelectrolytes and / or bovine serum albumin.

[0101] According to a particular embodiment, the stabilizer is 0.1% to 8.0% by weight, preferably 0.5% to 4.0% by weight, more preferably 1.0% to 2.0% by weight of the aqueous phase of polyvinyl alcohol.

[0102] According to certain embodiments, the stabilizer is dispersed directly in the oil phase.

[0103] According to certain embodiments, the stabilizers are 0.01% to 2.0% by weight calcium chloride dihydrate, 0.1% to 5.0% by weight sodium caseinate, and 0.1% to 5.0% by weight of the aqueous phase of whey protein isolate.

[0104] According to a preferred embodiment, the stabilizers are 0.1% to 1.5% by weight of calcium chloride dihydrate, 0.2% to 3.0% by weight of sodium caseinate, and 0.2% to 3.0% by weight of the aqueous phase of whey protein isolate.

[0105] According to a more preferred embodiment, the stabilizers are 0.25% to 0.75% by weight calcium chloride dihydrate, 0.43% to 2.0% by weight sodium caseinate, and 0.3% to 2.0% by weight of the aqueous phase of whey protein isolate.

[0106] According to another embodiment, the stabilizer is a surfactant.Surfactant is understood herein as a compound suitable for reducing the surface or interfacial tension between oil and water phases.Surfactant is understood herein as an amphiphilic organic compound that comprises a hydrophilic or water-soluble portion and a hydrophobic or oil-soluble portion.

[0107] According to one embodiment, the stabilizer is present in an amount ranging from 0.1% to 20% by weight, preferably from 0.3% to 7% by weight, more preferably from 0.5% to 5% by weight relative to the total weight of the emulsion obtained in step b) of the process of the invention.

[0108] According to one embodiment, the dispersion of the oil phase in the aqueous phase is homogenized at a speed between 2000 rpm and 20000 rpm, preferably between 6000 rpm and 12000 rpm, for a time between 30 seconds and 10 minutes, preferably between 1 minute and 5 minutes. The skilled person knows suitable methods for homogenizing the oil-in-water dispersion, for example using a T25 Ultra Turrax homogenizer.

[0109] According to one embodiment, the oil phase is a water-in-oil emulsion comprising dispersed droplets of a second aqueous phase. According to a particular embodiment, the second aqueous phase comprises water and at least one water-soluble oxidizing agent and / or oxidation catalyst as defined herein.

[0110] Oxidizing agent According to the invention, an oxidizing agent is added to the aqueous phase in step b) and / or to the oil-in-water emulsion obtained after step b).

[0111] According to one embodiment, an oxidizing agent is added to the oil-in-water emulsion under stirring to induce thiol oxidation at the oil-water interface.

[0112] By oxidizing agent, it is understood herein to mean a redox-active compound.By oxidizing agent, it is understood herein to mean a redox-active compound suitable for oxidizing thiol groups to disulfide groups.Those skilled in the art know that disulfide groups are formed by the oxidation of two thiol groups by reaction with an oxidizing agent.

[0113] According to one embodiment, the oxidizing agent is an inorganic redox-active compound. According to another embodiment, the oxidizing agent is an organic redox-active compound.

[0114] According to one embodiment, the oxidizing agent is iodine, iodide salts, iron(II) sulfate, hydrogen peroxide, iodobenzene diacetate, ammonium persulfate, potassium ferricyanide, ammonium perborate, iron(III) chloride, potassium dichromate, sodium bromide, potassium bromide, bromine, triiodide salts, copper(II) sulfate, N-bromosuccinimide, or mixtures thereof. According to a preferred embodiment, the oxidizing agent is hydrogen peroxide.

[0115] According to one embodiment, the oxidizing agent is iodine, iodide salts, iron (II) sulfate, hydrogen peroxide, iodobenzene diacetate, ammonium persulfate, potassium ferricyanide, ammonium perborate, ferric chloride, potassium dichromate, potassium bromide, bromine, triiodide salts, copper (II) sulfate, N-bromosuccinimide, or mixtures thereof, preferably hydrogen peroxide.

[0116] According to one embodiment, the oxidizing agent is used in a molar ratio of thiol functional groups to oxidizing agent of 1:10 to 1:0.01, preferably 1:6 to 1:0.5, more preferably 1:2 to 1:1.

[0117] Oxidation Catalyst According to the present invention, the oxidation catalyst is used in combination with an oxidizing agent to oxidize thiol groups to disulfide groups. According to the present invention, the oxidation catalyst is suitable for catalyzing the reaction of oxidizing thiol groups to disulfide groups, preferably at the oil-water interface.

[0118] According to the invention, an oxidation catalyst is added to the oil phase in step a) and / or to the oil-in-water emulsion obtained after step b).

[0119] According to one embodiment, the oxidation catalyst is added to the oil phase in step a). The oxidation catalyst added to the oil phase in step a) can optionally be dissolved in a co-solvent.

[0120] According to one embodiment, the oxidation catalyst is dissolved in a co-solvent and added to the oil phase in step a).

[0121] According to one embodiment, an oxidation catalyst is added to the oil-in-water emulsion obtained after step b). The oxidation catalyst added to the oil-in-water emulsion obtained after step b) can optionally be dissolved in water.

[0122] According to another embodiment, the oxidation catalyst is dissolved in water and added to the oil-in-water emulsion obtained after step b).

[0123] According to one embodiment, a first oxidation catalyst, optionally dissolved in a co-solvent, is added to the oil phase in step a) and a second oxidation catalyst, optionally dissolved in water, is added to the oil-in-water emulsion obtained after step b).

[0124] According to a preferred embodiment, the first oxidation catalyst and the second oxidation catalyst are different oxidation catalysts.

[0125] According to one embodiment, the first and second oxidation catalysts are the same oxidation catalyst, which are added to the oil phase in step a) and to the oil-in-water emulsion obtained after step b).

[0126] According to one embodiment, the oxidation catalyst is iodine, iodobenzene diacetate, a bromide salt, or an iodide salt. The iodide salt can be in the form of an n-hydrate, where n is in the range of 1 to 10 (e.g., when n=2, it is an iodide salt dihydrate).

[0127] According to a preferred embodiment, the oxidation catalyst is selected from the group consisting of sodium iodide, potassium iodide, tridodecylmethylammonium iodide, ethyltriphenylphosphonium iodide, propionylthiocholine iodide, isopropyltriphenylphosphonium iodide, tin(IV) iodide, aluminum iodide, acetylthiocholine iodide, butyrylcholine iodide, butyrylthiocholine iodide, tetraethylammonium iodide, phenyltriethylammonium iodide, methyltriphenoxyphosphonium iodide, manganese(II) iodide, iron(II) iodide, zinc iodide, Perfluorohexyl iodide, tetramethylammonium iodide, nickel(II) iodide, magnesium iodide, ruthenium iodide, ammonium iodide, tributyltin iodide, lithium iodide, methyltriphenylphosphonium iodide, trimethylsulfonium iodide, tetrapentylammonium iodide, tetraphenylphosphonium iodide, acetylcholine iodide, copper(I) iodide, lead(II) iodide, strontium iodide, cadmium iodide, tetrabutylammonium iodide, calcium iodide, rubidium iodide, cesium iodide, iodine Palladium(II) iodide, (iodomethyl)triphenylphosphonium iodide, arsenic(III) iodide, tetrahexylammonium iodide, benzyltributylammonium iodide, bis[(tetrabutylammonium iodide)copper(I)] iodide, 3,3′-diethylthiatricarbocyanine iodide, methylammonium iodide, formamidinium iodide, 1-dodecyl-3-methylimidazolium iodide, 1-aminopyridinium iodide, tetraheptylammonium iodide, guanidinium iodide, n-octylammonium iodide, tetraisopropylammonium iodide, Hexylammonium, 1,4-dimethylpyridinium iodide, 3,3′-diethylthiacarbocyanine iodide, 1-butyl-3-methylimidazolium iodide, 1-methyl-3-propylimidazolium iodide, N,N-dimethylmethyleneiminium iodide, 2-chloro-1-methylpyridinium iodide, (N,N-dimethyl)methyleneammonium iodide, 1-ethylquinolinium iodide, benzoylcholine iodide, trimethylphenylammonium iodide, triethylphenylammonium iodide, 2-phenylethylamine hydroiodide, N,N-Dimethyl-N-(methylsulfanylmethylene)ammonium, Dimethylamine hydroiodide, Isobutylamine hydroiodide, Tributylsulfonium iodide, Butylamine hydroiodide, tert-Butylamine hydroiodide, 1-Ethyl-2-methylquinolinium iodide, Aniline hydroiodide, Pyrrolidine hydroiodide, Propylamine hydroiodide, Phenyltrimethylammonium iodide, 1,1-Dimethyl iodide The iodide salt is selected from the group consisting of iodide salts of 1,1'-diethyl-2,2'-carbocyanine iodide, 3,3'-diethylthiadicarbocyanine iodide, 1,1'-diethyl-2,2'-carbocyanine iodide, 3,3'-diethylthiadicarbocyanine iodide, or mixtures thereof. According to a preferred embodiment, the oxidation catalyst is sodium iodide.

[0128] According to one embodiment, the oxidation catalyst and the oxidant are the same compound, in which case the same compound thus acts as both the oxidation catalyst and the oxidant simultaneously.

[0129] According to one embodiment, the oxidation catalyst and the oxidant are different compounds.

[0130] According to one embodiment, the oxidation catalyst is used in a molar ratio of thiol functional groups to oxidation catalyst of 1:1 to 1:0.0001, preferably 1:0.5 to 1:0.005, more preferably 1:0.1 to 1:0.01.

[0131] Co-solvent According to one embodiment, a co-solvent is used to dissolve the oxidation catalyst added to the oil phase in step a).

[0132] Without wishing to be bound by theory, the co-solvent increases the solubility of the oxidation catalyst in the oil phase.

[0133] According to one embodiment, the co-solvent is an organic solvent. Organic solvent is understood herein to be a solvent that is soluble in the oil phase of step a) of the method of the present invention. According to one embodiment, the organic solvent is polar and hydrophilic. According to another embodiment, the organic solvent is non-polar and hydrophobic.

[0134] According to a preferred embodiment, the co-solvent is ethyl acetate, ethanol, isopropanol alcohol, dimethylsulfoxide, acetone, glycerol, or a fragrance ingredient, preferably benzyl benzoate or isopropyl myristate, or a mixture thereof.

[0135] According to one embodiment, the cosolvent is used in an amount between 0.01% and 30% by weight, preferably between 0.5% and 15% by weight, more preferably between 1.0% and 5% by weight, relative to the total weight of the emulsion obtained in step b).

[0136] In certain embodiments, the shell material comprises a biodegradable material.

[0137] A typical method for extraction of shells to measure biodegradability is disclosed in Gasparini et al., Molecules 2020, 25 (3), 718.

[0138] 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.

[0139] 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.

[0140] Thereby, it is understood that according to one embodiment, the core-shell microcapsules, including all components such as the core, shell and optionally the coating, have a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD 301F.

[0141] In certain embodiments, the oil core, preferably the perfume oil, has a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD 301F.

[0142] OECD301F is a standard test method for biodegradability established by the Organization for Economic Cooperation and Development.

[0143] Drying process According to one embodiment, the method of the present invention comprises an additional drying step d) of drying the polydisulfide core-shell microcapsule slurry to form a polydisulfide core-shell microcapsule powder.

[0144] Those skilled in the art know suitable methods for producing polydisulfide core-shell microcapsule powders by drying the polydisulfide core-shell microcapsule slurry. Non-limiting examples for drying are spray drying or freeze drying.

[0145] According to a preferred embodiment, the polydisulfide core-shell microcapsule powder is produced by spray drying a polydisulfide core-shell microcapsule slurry.

[0146] Another subject of the present invention is a carrier material, preferably a polymeric carrier material selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gums, such as gum arabic, pectin, xanthan, alginates, carrageenans, cellulose derivatives and mixtures thereof, - microcapsules as defined above encapsulated in said carrier material; - optionally, a non-encapsulated flavoring agent is encapsulated in said carrier material; are solid particles comprising:

[0147] The solid particles and microcapsule powders defined above can be used interchangeably in the present invention.

[0148] Method parameters According to one embodiment, the reaction temperature in step c) is kept at 0°C to 70°C, preferably 10°C to 65°C, more preferably 15°C to 60°C.

[0149] According to one embodiment, in step b) and / or step c), the pH is adjusted to 1-12, preferably 3-8.

[0150] According to one embodiment, the mixture of step c) is stirred for a reaction time ranging from 1 min to 48 h, preferably from 10 min to 24 h.

[0151] Optional Ingredients According to one embodiment, when the microcapsules are in the form of a slurry, the microcapsule slurry may comprise auxiliary components selected from the group of thickeners / rheology modifiers, antimicrobial agents, opacity enhancers, mica particles, salts, pH stabilizers / buffer components, preferably in an amount comprised between 0.1% and 15% by weight, preferably between 5% and 10% by weight, based on the total weight of the slurry.

[0152] According to another embodiment, the microcapsule slurry of the present invention comprises additional non-encapsulated (i.e. non-encapsulated) flavoring, preferably in an amount comprised between 5% and 50% by weight, preferably between 15% and 35% by weight, relative to the total weight of the slurry.

[0153] Polydisulfide Core-Shell Microcapsules The present invention also provides - an oily core comprising a hydrophobic material, preferably a perfume oil; - a polymer shell comprising disulfide bonds formed by oxidizing at least one polythiol monomer with an oxidizing agent in the presence of an oxidation catalyst; Also of interest is a polydisulfide core-shell microcapsule prepared by the method of the present invention, comprising:

[0154] The embodiments and definitions relating to the oily core comprising the hydrophobic material, the disulfide bond, the polythiol monomer, the oxidizing agent and the oxidation catalyst described herein above apply mutatis mutandis.

[0155] According to one embodiment, the polydisulfide core-shell microcapsules are in the liquid form of a polydisulfide core-shell microcapsule slurry.

[0156] According to one embodiment, the polydisulfide core-shell microcapsules are in the powder form of a polydisulfide core-shell microcapsule powder.

[0157] According to the present invention, a polymer shell is a shell that comprises at least one polymer that forms a surrounding structure around the oily core.

[0158] According to the present invention, the polymer shell of the polydisulfide core-shell microcapsule comprises at least one polymer containing a disulfide bond. A disulfide bond is understood herein to be a sulfur-sulfur single bond. According to the present invention, the polymer shell of the polydisulfide core-shell microcapsule is formed by the formation of a disulfide bond accompanied by the oxidation of at least one polythiol monomer.

[0159] According to one embodiment, disulfide bonds crosslink the polymer shell of the polydisulfide core-shell microcapsules.

[0160] Biomineralization Process The microcapsules of the present invention may be coated with an inorganic layer, typically comprising a material selected from the group consisting of iron oxide, iron oxyhydroxide, titanium oxide, zinc oxide, calcium carbonate, calcium phosphate and mixtures thereof.

[0161] Multiple microcapsule system According to one embodiment, the microcapsules of the present invention (a first type of microcapsule) may be used in combination with a second type of microcapsule.

[0162] Another subject of the present invention is - microcapsules of the invention as a first type of microcapsule, - a second type of microcapsule; wherein the first type of microcapsules and the second type of microcapsules differ in their hydrophobic material and / or their wall material and / or their coating material.

[0163] composition The microcapsules of the invention can be used in combination with active ingredients. The subject of the invention is therefore (i) a microcapsule of the present invention; (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 deodorant ingredient, a bactericidal ingredient, a fungicidal ingredient, a pharmaceutical or pesticide ingredient, a disinfectant ingredient, an insect repellent or attractant, and mixtures thereof; A composition comprising:

[0164] Perfuming composition The present invention also relates to a perfume composition comprising polydisulfide core-shell microcapsules as defined herein, at least one ingredient selected from the group consisting of a perfume carrier and a perfume base, optionally at least one active ingredient, and optionally at least one perfume adjuvant.

[0165] The embodiments and definitions relating to the polydisulfide core-shell microcapsules, polymer shell, oily core comprising hydrophobic material, disulfide bond, polythiol monomer, oxidizing agent and oxidation catalyst described herein above apply mutatis mutandis.

[0166] The fragrance composition may contain 0.1% to 30% by weight, preferably 0.3% to 15% by weight, and more preferably 0.5% to 5% by weight of the core-shell microcapsule slurry or core-shell microcapsules, relative to the total weight of the fragrance composition.

[0167] The perfume carrier may be a liquid perfume carrier. The liquid perfume carrier may include, as a non-limiting example, an emulsion system, i.e., a solvent and surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvent commonly used in perfumery cannot be comprehensive. However, as a non-limiting example, the most commonly used solvents may be dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate.

[0168] For compositions containing both a perfume carrier and a perfume co-ingredient, suitable perfume carriers other than those specified above can also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (supplied by Exxon Chemical), or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (supplied by Dow Chemical Company).

[0169] The perfuming composition may further comprise an active ingredient, which may preferably be selected from the group consisting of cosmetic ingredients, skin care ingredients, perfume ingredients, flavor ingredients, deodorant ingredients, germicidal ingredients, fungicidal ingredients, medicinal or pesticide ingredients, disinfecting ingredients, insect repellents or attractants, and mixtures thereof.

[0170] In certain embodiments, the active ingredient is an unencapsulated fragrance. The unencapsulated fragrance may be an unencapsulated fragrance oil.

[0171] By "unencapsulated perfume" herein is meant a perfume or perfume oil that is included in a perfume composition and is not encapsulated in a polydisulfide core-shell microcapsule.

[0172] The fragrance composition may contain from 0.1% to 30% by weight, preferably from 0.3% to 15% by weight, more preferably from 0.5% to 5% by weight of an active ingredient, preferably an unencapsulated fragrance, relative to the total weight of the fragrance composition.

[0173] In a particular embodiment, the total amount of the polydisulfide core-shell microcapsule slurry or polydisulfide core-shell microcapsules is 0.5% by weight to 5% by weight based on the total weight of the fragrance composition, and the total amount of unencapsulated fragrance is 0.5% by weight to 5% by weight based on the total weight of the fragrance composition.

[0174] In a particular embodiment, the total amount of perfume of the perfume formulation encapsulated in the polydisulfide core-shell microcapsules and the total amount of non-encapsulated perfume are present in the perfume composition in a weight ratio of 1:20 to 20:1, preferably 10:1 to 1:10.

[0175] According to one embodiment, the perfuming composition further comprises at least one perfuming co-ingredient.

[0176] By "perfuming co-ingredient" is understood herein a compound that is used in a perfuming preparation or composition to impart a hedonic effect and is not a microcapsule as defined above. In other words, such a co-ingredient must be recognized by the skilled person as not only having an odor, but also capable of imparting or modifying the odor of the composition in a positive or pleasant way, in order to be considered as a perfuming co-ingredient. The nature and type of perfuming co-ingredients present in the perfuming composition do not require a more detailed description here and are in any case not comprehensive, but the skilled person can select them on the basis of his general knowledge, depending on the intended use or application and the desired organoleptic effect. Generally, these perfuming co-ingredients belong to chemical classes as diverse as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and said perfuming co-ingredients may be of natural or synthetic origin. Many of these co-ingredients are in each case described in references, for example in the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its newer editions, or other treatises of the same kind, and in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may be compounds known to controllably release various types of perfuming compounds, such as propurfumes. Non-limiting examples of suitable propargines 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, trans-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-ylhexadecanoate, 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)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2-phenethoxy 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.

[0177] According to one embodiment, the perfuming composition further comprises at least one perfume adjuvant.

[0178] By "perfuming adjuvants" is understood herein ingredients capable of imparting additional added benefits such as color, specific light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfuming bases cannot be comprehensive, but it is necessary to mention that said ingredients are well known to the person skilled in the art.

[0179] consumer products The polydisulfide core-shell microcapsules according to the present invention can be advantageously used in many applications and can be used in consumer products.

[0180] The polydisulfide core-shell microcapsules or the perfume composition can be used in liquid form for application in liquid consumer products, as well as in powder form for application in powdered consumer products.

[0181] The present invention also relates to a consumer product comprising a personal care active base or a fabric care active base and a polydisulfide core-shell microcapsule or a perfume composition.

[0182] The embodiments and definitions relating to polydisulfide core-shell microcapsules, polymer shell, oily core comprising hydrophobic material, disulfide bond, polythiol monomer, oxidizing agent, oxidation catalyst, perfume carrier, perfuming composition, perfume base, perfuming co-ingredient and perfume adjuvant described above in this specification apply mutatis mutandis.

[0183] According to one embodiment, the consumer product is in the form of a personal care composition, a home care composition or a fabric care composition, preferably a hair care product, such as a shampoo or a hair conditioner, a shower gel, a soap bar, a lotion, an antiperspirant, such as an antiperspirant roll-on stick or an antiperspirant deodorant, an oral care product, a laundry care product, such as a rinse-off conditioner, a leave-on conditioner, a fabric softener, a liquid or solid detergent, preferably a liquid fabric detergent or a powder fabric detergent, most preferably a shower gel or a fabric softener.

[0184] The personal care or fabric care active bases in which the polydisulfide core-shell microcapsules of the present invention can be incorporated can be found in the abundant literature on such products.These formulations do not require detailed description here, and are in any case not comprehensive.Those skilled in the formulation of such consumer products are entirely capable of selecting suitable ingredients based on general knowledge and available literature.

[0185] According to one embodiment, the polydisulfide core-shell microcapsules or the perfume composition can be dispersed in a personal care active base or a fabric care active base without visibly affecting the color of the personal care active base or the fabric care active base.

[0186] According to one embodiment, the consumer product comprises: a) 2 to 65% by weight, based on the total weight of the consumer product, of at least one surfactant; b) water or a water-miscible hydrophilic organic solvent; c) microcapsules or a microcapsule slurry as defined above, d) optionally, a non-encapsulated flavoring; Includes.

[0187] According to one embodiment, the consumer product comprises 0.1 to 15% by weight, more preferably 0.2 to 5% by weight, of the microcapsules of the invention, these percentages being defined by weight relative to the total weight of the consumer product. Of course, the above concentrations can be adapted depending on the beneficial effect desired for each product.

[0188] For the liquid consumer products described below, by "active base" it should be understood that the active base comprises active ingredients (typically including surfactants) and water.

[0189] With respect to the solid consumer products described below, by "active base" it should be understood that the active base includes active materials (which typically include surfactants) and adjuvants (such as bleaches, buffers; builders; stain removing or stain suspending polymers; granular enzyme particles, rust inhibitors, antifoam agents, suds suppressors; dyes, fillers and mixtures thereof).

[0190] Fabric softener The subject of the present invention is - a fabric softener active base, preferably comprising at least one active material selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (ester quats), Hamburg esterquats (HEQ), TEAQ (triethanolamine quats), silicones and mixtures thereof, preferably used in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition; - a microcapsule slurry or microcapsules as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil and a fabric softener composition comprising:

[0191] Liquid detergent The subject of the present invention is a liquid detergent active base, preferably comprising at least one active material chosen 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 non-ionic 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 used in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - a microcapsule slurry or microcapsules as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil A consumer product in the form of a liquid detergent composition comprising:

[0192] Solid detergent The subject of the present invention is a solid detergent active base, preferably comprising at least one active material chosen 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 non-ionic 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 used in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - a microcapsule powder or a microcapsule slurry or microcapsules as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition, - optionally with non-encapsulated perfume oil and a solid detergent composition comprising:

[0193] Shampoo / Shower gel The subject of the present invention is a shampoo or shower gel active base, preferably comprising at least one active material selected from the group consisting of sodium alkyl ether sulfates, ammonium alkyl ether sulfates, alkyl amphoacetates, cocamidopropyl betaine, cocamide MEA, alkyl glucosides and amino acid surfactants, and mixtures thereof, preferably used in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition; - a microcapsule slurry or microcapsules as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil A consumer product in the form of a shampoo or shower gel composition comprising:

[0194] Rinse-off conditioner The subject of the present invention is a rinse-off conditioner active base, preferably comprising at least one active material selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, preferably used in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition; - a microcapsule slurry or microcapsules as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil and a rinse-off conditioner composition comprising:

[0195] Solid fragrance enhancer The subject of the present invention is - a solid carrier, 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, sugars, such as sucrose, mono-, di- 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, - microcapsules or a microcapsule slurry as defined above, preferably in powder form, in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil A consumer product in the form of a solid fragrance enhancer composition comprising:

[0196] Liquid fragrance enhancer The subject of the present invention is an aqueous phase; - a surfactant system consisting essentially of one or more non-ionic 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 hydroxyesters, 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 hydroxyl carboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants with an HLB of less than 10, and mixtures thereof; - a microcapsule slurry or microcapsules as defined 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, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil and a liquid fragrance enhancer composition comprising:

[0197] Hair Coloring The subject of the present invention is - an oxidizing phase comprising an oxidizing agent and an alkaline phase comprising an alkalizing agent, a dye precursor and a coupling compound, said dye precursor and said coupling compound forming an oxidizing hair dye in the presence of an oxidizing agent, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; - optionally with non-encapsulated perfume oil and a consumer product in the form of an oxidative hair coloring composition comprising:

[0198] Perfuming composition According to certain embodiments, the consumer product comprises: - 0.1 to 30%, preferably 0.1 to 20%, of microcapsules or a microcapsule slurry as defined above, preferably in the form of a slurry, - 0-40%, preferably 3-40% of fragrance, - 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:

[0199] The invention will now be further illustrated by examples, it being understood that the invention as claimed is not intended to be limited in any way by these examples. [Brief description of the drawings]

[0200] [Figure 1] FIG. 1 shows an SEM image of the hexathiol-based polydisulfide microcapsule slurry prepared in Example 1B. [Diagram 2] FIG. 1 shows an SEM image of the hexathiol polydisulfide microcapsule slurry prepared in Example 1B diluted 20-fold with fabric softener (Stepantex VL 90A (8.8%), calcium chloride solution 10% (0.36%), Proxel GXL (0.04%), fragrance (1%), water (89.72%) and collected after 20 days. [Diagram 3] FIG. 1 shows an SEM image of the trithiol-based polydisulfide microcapsule slurry prepared in Example 1I. [Figure 4] FIG. 1 shows the deposition efficiency of the hexathiol-based disulfide microcapsule slurry prepared in Example 1Q onto hair with or without a calcium phosphate biomineral layer. [Diagram 5] FIG. 1 shows dynamic headspace (DHS) analysis of polydisulfide core-shell microcapsules of Example 1B before rubbing and Example 1P before rubbing diluted 1:100 with demineralized water and dried on blotter paper for 24 hours, compared with dynamic headspace analysis of Example 1B after rubbing with friction and Example 1P after rubbing.

[0201] Working Example Example 1: Preparation method of polydisulfide core-shell microcapsules Perfume composition used: [Table 1]

[0202] [Table 2]

[0203] To prepare disulfide microcapsules, the following reactants are used: - Uses ethylene glycol bis(3-mercaptopropionate) as the dithiol monomer. - Using tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate as the trithiol monomer. - Using pentaerythritol hexakis(3-mercaptopropionate) as the hexathiol monomer.

[0204] Room temperature is understood in this specification as a temperature between 20° C. and 25° C. or between 293 K and 298 K.

[0205] Example 1B: The oil phase was obtained by dissolving 1.8 g of hexathiol monomer in 18 g of perfume oil composition 1 with vortexing at room temperature for 1 min. 0.85 g of polyvinyl alcohol (PVA, Mowiol 18-88) was added to 60 g of demineralized (DI) water and dissolved after stirring at 70°C for 1 h. The oil phase was then added to the PVA / DI water phase and mixed by homogenization at 8400 rpm for 2 min. Once the oil-in-water emulsion was obtained, 0.21 g of NaI dissolved in a minimum amount of DI water was added to the oil-in-water emulsion with stirring. Then, 1.6 g of hydrogen peroxide (H2O2 (30 wt% aqueous solution)) was added to the oil-in-water emulsion in two portions (0.8 g each, 30 min apart). The slurry was then stirred at room temperature overnight.

[0206] Example 1F: The oil phase was obtained by dissolving 1 g of dithiol monomer and 1.08 g of hexathiol monomer in 18 g of perfume oil composition 1 with vortexing at room temperature for 1 min. 0.85 g of polyvinyl alcohol (PVA, Mowiol 18-88) was added to 60 g of demineralized (DI) water and dissolved after stirring at 70°C for 1 h. The oil phase was then added to the PVA / DI water phase and mixed by homogenization at 8400 rpm for 2 min. Once the oil-in-water emulsion was obtained, 0.25 g of NaI dissolved in a minimum amount of DI water was added to the oil-in-water emulsion and 1.9 g of hydrogen peroxide (H2O2 (30 wt% aqueous solution)) was added in two portions at 30 min intervals. The slurry was heated at 40°C for 3 h and then stirred at room temperature overnight.

[0207] Example 1G: Oil phase I was prepared by dissolving 3.66 g of trithiol monomer in 12 g of perfume oil composition 1 and 6 g of tert-butyl-1-cyclohexyl acetate, and oil phase II was prepared by adding 0.36 g of NaI to 1.2 g of IPOH. Oil phase II was then added to oil phase I while swirling. The water phase contained 0.9 g of polyvinyl alcohol (PVA, Mowiol 18-88) in 60 g of DI water. 1.35 g of H2O2 (30 wt.% aqueous solution) was added to the water phase beforehand. The oil and water phases were then homogenized at 8400 rpm for 2 minutes to form an oil-in-water emulsion. Then, another 1.35 g of H2O2 (30 wt.% aqueous solution) was added to the oil-in-water emulsion. After overnight reaction at room temperature, microcapsules were obtained.

[0208] Example 1H: The oil phase was obtained by dissolving 3.6 g of trithiol monomer in 18 g of perfume oil composition 1 with vortexing at room temperature for 1 min. 1.7 g of whey protein isolate (WPI) was added to 60 g of demineralized (DI) water and dissolved after stirring at 50°C for 30 min. The oil phase was then added to the WPI / DI water phase and mixed by homogenization at 10000 rpm for 2 min. Once the oil-in-water emulsion was obtained, 0.3 g of NaI dissolved in a minimum amount of DI water was added to the oil-in-water emulsion with stirring and 2.3 g of hydrogen peroxide (H2O2 (30 wt% aqueous solution)) was added to the slurry in two portions at 30 min intervals. After overnight reaction at room temperature, microcapsules were obtained.

[0209] Example 1I: Oil phase I was prepared by dissolving 3.6g of trithiol monomer in 18g of perfume oil composition 1, and oil phase II was prepared by adding 0.3g of NaI to 1.7g of ethyl acetate. Oil phase II was then added to oil phase I while swirling. The water phase contained 1.7g of whey protein isolate (WPI) in 60g of DI water. The oil and water phases were then mixed and homogenized at 10000 rpm for 2 minutes to form an oil-in-water emulsion. Then, 2.3g of H2O2 (30 wt% aqueous solution) was added to the oil-in-water emulsion in two portions at 30 min intervals. After overnight reaction at room temperature, microcapsules were obtained.

[0210] Example 1K: Oil phase I was obtained by dissolving 1.8 g of hexathiol monomer in 18 g of perfume oil composition 1 with vortexing at room temperature for 1 min. Oil phase II contains 0.1 g of NaI in 0.4 g of ethanol. The two oil phases were mixed together. 0.85 g of PVA (Mowiol 18-88) was added to 60 g of demineralized (DI) water and dissolved after stirring at 70°C for 1 h. The oil phase was then added to the PVA / DI water phase and mixed by homogenization at 8400 rpm for 2 min. 1.6 g of hydrogen peroxide (H2O2 (30 wt% in water)) was added to the emulsion in two portions (half each time added at 30 min intervals). After stirring overnight at room temperature, the reaction was stopped.

[0211] Example 1L: Oil phase I was prepared by dissolving 1.44 g of hexathiol monomer and 0.36 g of trimethylolpropane adduct of xylylene diisocyanate (Takenate D-110N; Supplier: Mitsui Chemicals, 75% polyisocyanate / 25% ethyl acetate) in 18 g of perfume oil composition 2, and oil phase II was prepared by adding 0.016 g of NaI to 1.3 g of ethyl acetate. Oil phase II was then added to oil phase I while swirling. The water phase contained 0.85 g of polyvinyl alcohol (PVA, Mowiol 18-88) in 60 g of DI water. The oil and water phases were then mixed and homogenized at 8400 rpm for 2 minutes to form an oil-in-water emulsion. Then, 1.3 g of H2O2 (30 wt% aqueous solution) was added to the oil-in-water emulsion. After overnight reaction at room temperature, microcapsules were obtained.

[0212] Example 1P: 0.5 g of sodium caseinate and 1.5 g of whey protein isolate (WPI) were dissolved in 65.23 g of DI water. 0.4 g of CaCl2·2H2O (previously dissolved in 2 g of DI water) was added to the sodium caseinate / WPI solution and stirred for 10-15 minutes to form the emulsifier solution. 3.0 g of trithiol monomer was added to 20 g of perfume oil composition 1. 0.13 g of NaI was dissolved in 0.5 mL of ethanol and subsequently added to the perfume mixture to form the oil phase. The oil phase was added to the emulsifier solution and homogenized with a T25 Ultra Turrax at 7,000 rpm for 2 minutes to form an emulsion. This emulsion was added to a 100 mL reactor equipped with an anchor stirrer and stirred at 400 rpm. 1.94 g of H2O2 (30%) was added to the emulsion and stirred at room temperature for 16 hours. The reactor was heated to 45°C and the pH was adjusted to 6.5-7. 0.8 g of transglutaminase (Activa TI pre-dissolved in 4 g of DI water) was added and stirred for 3 hours. The pH was adjusted to 5.4 and the reactor was heated to 80°C and stirred for 30 minutes before being cooled to room temperature.

[0213] Example 1Q: 0.5g of sodium caseinate and 1.5g of whey protein isolate (WPI) were dissolved in 67.69g of DI water. 0.4g of CaCl2·2H2O (previously dissolved in 2g of DI water) was added to the sodium caseinate / WPI solution and stirred for 10-15 minutes to form the emulsifier solution. 1.6g of hexathiol monomer was added to 19.0g of perfume oil composition 2 and 1.0g of Uvinul A Plus (UV tracer). 0.019g of NaI was dissolved in 100uL of ethanol and subsequently added to the perfume mixture to form the oil phase. The oil phase was added to the emulsifier solution and homogenized with a T25 Ultra Turrax at 7,000 rpm for 2 minutes to form an emulsion. This emulsion was added to a 100mL reactor equipped with an anchor stirrer and stirred at 400 rpm. 1.39 g H2O2 (30%) was added to the emulsion and stirred at room temperature for 16 h. The reactor was heated to 45°C and the pH was adjusted to 6.5-7. 0.8 g transglutaminase (Activa TI pre-dissolved in 4 g DI water) was added and stirred for 3 h. The pH was adjusted to 5.4 and the reactor was heated to 80°C and stirred for 30 min before cooling to room temperature.

[0214] Example 2: Morphological and stability analysis Optical microscopy and scanning electron microscopy (SEM) revealed that the polydisulfide microcapsules prepared according to each of the methods described in Example 1 exhibited spherical structures with diameters in the micrometer range, as shown in the figures referred to within this example.

[0215] FIG. 1 is an SEM image of the hexathiol-based polydisulfide microcapsule slurry prepared in Example 1B.

[0216] FIG. 2 shows an SEM image of the hexathiol polydisulfide microcapsule slurry prepared in Example 1B diluted 20 times with fabric softener (Stepantex VL 90A (8.8%), calcium chloride solution 10% (0.36%), Proxel GXL (0.04%), fragrance (1%), water (89.72%)) and collected after 20 days, which is the basis for the good stability of the microcapsules of the present invention.

[0217] Since SEM is performed under high vacuum, the mechanical stability of the microcapsules can be examined. Polydisulfide microcapsules that are stable under high vacuum usually exhibit good mechanical stability.

[0218] Figure 3 is an SEM image of the trithiol-based polydisulfide microcapsule slurry prepared in Example 1I. From Figure 3, it can be concluded that the trithiol-based polydisulfide microcapsules are also stable under high vacuum.

[0219] Example 3: Biomineralization of Adhesion Test Example Q The hexathiol-based disulfide microcapsules prepared in Example 1Q were coated with an additional calcium phosphate biomineral layer.

[0220] 15 g of the microcapsule slurry prepared in Example 1Q is diluted with 135 g of an alkaline buffer at pH 9, 4.5 mL. Then, 0.3 M calcium nitrate solution is added. The mixture is stirred at 250 rpm with an anchor stirrer in a closed reactor until the calcium ions have had enough time to interact with the anionic surface of the microcapsules.

[0221] (i) 4.5 mL of 0.18 M disodium phosphate solution is added slowly via syringe pump over 60 minutes (75 μL / min) to initiate nucleation of mineral on the capsule surface by precipitating calcium cations with phosphate anions, followed by stirring for an additional 60 minutes.

[0222] (ii) Then, equal volumes of 7.5 mL of 0.3 M calcium nitrate solution and 0.18 M sodium phosphate solution are added slowly simultaneously (125 μL / min each) via syringe pump over a period of 60 min, followed by stirring for 1 h to allow further precipitation of the minerals.

[0223] (iii) Equal volumes of 30 mL of 0.3 M calcium nitrate solution and 0.18 M sodium phosphate solution are then added slowly (500 μL / min) simultaneously over 60 minutes, followed by stirring for 60 minutes to allow further precipitation of the mineral material. In this example, this process is repeated once more to produce a robust mineral shell. The additions can also be systematically repeated to obtain the desired mineral shell thickness and properties.

[0224] Figure 4 shows the adhesion efficiency of the hexathiol-based disulfide microcapsule slurry prepared in Example 1Q to hair with and without a calcium phosphate biomineral layer, demonstrating that the adhesion of the microcapsules of the present invention can be improved by coating with a mineral layer.

[0225] Example 4: Dynamic Headspace Analysis FIG. 5 shows the dynamic headspace (DHS) analysis of polydisulfide core-shell microcapsules of Example 1B before rubbing and Example 1P before rubbing diluted 1:100 with demineralized water and dried on blotter paper for 24 hours, and compares it with the dynamic headspace analysis of Example 1B after rubbing with friction and Example 1P after rubbing.

[0226] Dynamic headspace (DHS) analysis revealed that the polydisulfide core-shell microcapsules exhibited a significant increase in area counts upon rubbing compared to the same microcapsules before rubbing, proving that the polydisulfide core-shell microcapsules could adequately protect the fragrance oil and burst upon friction, having a burst release behavior of the fragrance oil.

[0227] Example 5 Liquid fabric softener composition A sufficient amount of the exemplary microcapsules is weighed and mixed into a liquid fabric softener composition to add the equivalent of 0.2% perfume.

[0228] [Table 3]

[0229] Example 6 Powder detergent composition A sufficient amount of the exemplary microcapsules is weighed out and mixed into a powder detergent composition to add the equivalent of 0.2% perfume.

[0230] [Table 4]

[0231] Example 7 Liquid detergent composition The microcapsules of the present invention are dispersed in a liquid detergent base, as described below, to give a concentration of 0.22% encapsulated perfume oil.

[0232] [Table 5]

[0233] Example 8 Rinse-off conditioner The microcapsules of the present invention are dispersed in a rinse-off conditioner base, described below, such that the concentration of encapsulated perfume oil is 0.5%.

[0234] [Table 6]

[0235] Example 9 Shampoo Composition The microcapsules of the present invention are weighed and mixed into a shampoo composition, and 0.2% equivalent of a fragrance is added.

[0236] [Table 7]

[0237] Example 10 Antiperspirant roll-on emulsion composition The microcapsules of the present invention are weighed and mixed into an antiperspirant roll-on emulsion composition, and 0.2% equivalent of a fragrance is added.

[0238] [Table 8]

[0239] Parts A and 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. The mixture is then cooled to room temperature.

[0240] Example 11 Deodorant spray composition The microcapsules of the present invention are weighed and mixed into an antiperspirant roll-on emulsion composition, and 0.2% equivalent of a fragrance is added.

[0241] [Table 9]

[0242] All ingredients are mixed and dissolved according to the order in Table 11. Aerosol cans are then filled, crimped and propellant is added (aerosol fill: 40% active solution, 60% propane / butane 2.5 bar).

[0243] Example 12 Shower gel composition The microcapsules of the present invention are weighed and mixed in the following composition, and a fragrance equivalent to 0.2% is added.

[0244] [Table 10]

[0245] Example 13 Unit Dose Formulations A sufficient amount of the exemplary microcapsules is weighed out and mixed in a unit dose formulation and flavor equivalent to 0.2% is added.

[0246] The unit dose formulation can be contained in a PVOH (polyvinyl alcohol) film.

[0247] [Table 11]

[0248] Example 14 Cosmetic day cream A sufficient amount of the exemplified microcapsules is weighed out and mixed into a cosmetic skin cream (see composition below) at a concentration of 5% w / w.

[0249] [Table 12]

Claims

1. 1. A method for preparing a polydisulfide core-shell microcapsule slurry, the method comprising: a) dissolving at least one polythiol monomer in a hydrophobic material, preferably a perfume oil, to form an oil phase; b) dispersing the oil phase obtained in step a) in an aqueous phase to form an oil-in-water emulsion; c) applying conditions sufficient to induce thiol oxidation at the oil-water interface to form a polydisulfide core-shell microcapsule slurry; Including, an oxidation catalyst is added to the oil phase in step a) and / or to the oil-in-water emulsion obtained after step b), A stabilizer is added to the oil phase in step a) and / or to the aqueous phase in step b), A process wherein an oxidizing agent is added to the aqueous phase in step b) and / or to the oil-in-water emulsion obtained after step b).

2. The method further comprising: a) dissolving at least one polythiol monomer in a hydrophobic material, preferably a perfume oil, to form an oil phase; b) dispersing the oil phase obtained in step a) in an aqueous phase to form an oil-in-water emulsion; c) adding an oxidizing agent to the oil-in-water emulsion under stirring to induce thiol oxidation at the oil-water interface to form a polydisulfide core-shell microcapsule slurry; Including, an oxidation catalyst is added to the oil phase in step a) and / or to the oil-in-water emulsion obtained after step b), 2. The method of claim 1, wherein a stabilizer is added to the oil phase in step a) and / or to the aqueous phase in step b).

3. 3. The process according to claim 1 or 2, wherein the oxidation catalyst is added to the oil phase in step a).

4. 4. The method of claim 1, wherein the polythiol monomer is selected from the group consisting of difunctional thiol monomers, trifunctional thiol monomers, tetrafunctional thiol monomers, pentafunctional thiol monomers, hexafunctional thiol monomers, heptafunctional thiol monomers, octafunctional thiol monomers, thiolated polysaccharides, thiolated chitosan, thiolated proteins, thiolated pectins, thiolated polyols, hydrolyzed / reduced keratin, proteins having two or more thiol groups, and mixtures thereof.

5. The polythiol monomer may be a bifunctional thiol monomer, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, dithioerythritol, 1,4-butanediol bis(thioglycolate), 4,4'-biphenyldithiol, ethylene bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), 1,10-decanedithiol, 1,11-undecanedithiol, 1,16-hexadecanedithiol, 1,4-benzenedithiol, 3,7-dithia-1,9-nonanedithiol, 4,4'-thiobisbenzenethiol, hexa(ethylene glycol)dithiol, bis(2-mercaptoethyl)sulfide, 3,6 5. The process according to claim 1, wherein the thiol monomer is selected from the group consisting of: dioxa-1,8-octanedithiol, 1,5-dimercaptonaphthalene, 1,3-benzenedithiol, 2,3-butanedithiol, dithiothreitol, 2,3-dimercapto-1-propanol, 2,2'-(ethylenedioxy)diethanethiol, hexa(ethylene glycol)dithiol, tetra(ethylene glycol)dithiol, polyethylene glycol dithiol, most preferably ethylene glycol bis(3-mercaptopropionate), a trifunctional thiol monomer, preferably tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, or a hexafunctional thiol monomer, preferably dipentaerythritol hexakis(3-mercaptopropionate), or a mixture thereof.

6. 6. The method according to any one of claims 1 to 5, wherein the stabilizer is a colloidal stabilizer, preferably selected from the group of polyvinyl alcohol, whey protein isolate, sodium caseinate, gum arabic, sugar beet pectin, gelatine, proteins, preferably soy proteins, potato proteins and / or hydrolyzed silk proteins, more preferably selected from the group of polyvinyl alcohol, whey protein isolate and / or sodium caseinate.

7. 7. The method according to any one of claims 1 to 6, wherein the oxidizing agent is iodine, iodide salts, iron(II) sulfate, hydrogen peroxide, iodobenzene diacetate, ammonium persulfate, potassium ferricyanide, ammonium perborate, ferric chloride, potassium dichromate, potassium bromide, bromine, triiodide salts, copper(II) sulfate, N-bromosuccinimide, or mixtures thereof, preferably hydrogen peroxide.

8. The process according to any one of claims 1 to 7, wherein the oxidizing agent is used in a molar ratio of thiol functional groups to oxidizing agent of from 1:10 to 1:0.01, preferably from 1:6 to 1:0.5, more preferably from 1:2 to 1:

1.

9. 9. The process according to any one of claims 1 to 8, wherein the oxidation catalyst is iodine, iodobenzene diacetate, a bromide salt, or an iodide salt, or a mixture thereof, preferably an iodide salt selected from the group of sodium iodide, potassium iodide or tetrabutylammonium iodide, most preferably sodium iodide.

10. 10. The process according to any one of claims 1 to 9, wherein at least one further multifunctional monomer, preferably a polyisocyanate, is added to the process, preferably to the oil phase in step a).

11. 11. The method of claim 1, further comprising an additional drying step d) of drying the polydisulfide core-shell microcapsule slurry to form a polydisulfide core-shell microcapsule powder.

12. a) an oily core comprising a hydrophobic material, preferably a perfume oil; b) a polymer shell comprising disulfide bonds formed by oxidizing at least one polythiol monomer with an oxidizing agent in the presence of an oxidation catalyst; 12. A polydisulfide core-shell microcapsule prepared by the method of claim 1 , comprising:

13. a) the polydisulfide core-shell microcapsule according to claim 12; b) at least one component selected from the group consisting of a perfume carrier and a perfume base; c) optionally at least one active ingredient; d) optionally at least one perfuming co-ingredient; e) optionally at least one flavor adjuvant; A fragrance composition comprising:

14. a) a personal care or fabric care active base; b) the polydisulfide core-shell microcapsule according to claim 12 or the fragrance composition according to claim 13; Including, consumer products.

15. 15. The consumer product of claim 14, wherein the consumer product is in the form of a personal care composition, a home care composition or a fabric care composition, preferably a hair care product, such as a shampoo or a hair conditioner, a shower gel, a soap bar, a lotion, an antiperspirant, such as an antiperspirant roll-on stick or an antiperspirant deodorant, an oral care product, a laundry care product, such as a rinse-off conditioner, a leave-on conditioner, a fabric softener, a liquid or solid detergent, preferably a fabric liquid detergent or a fabric powder detergent, most preferably a shower gel or a fabric softener.

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