Composite Microcapsules

Abstract

The present invention relates to microcapsules comprising a core and a composite shell comprising a plant-based coacervate and a polymeric material.

Description

[Technical Field]

[0001] The present invention relates to microcapsules comprising a core and a composite shell comprising a plant-based coacervate and a polymeric material.

[0002] Background technology One of the problems facing the cosmetics industry is that the olfactory benefits provided by odoriferous compounds are lost relatively quickly due to their volatility, especially that of "top notes." To control the release rate of volatile substances, delivery systems, such as microcapsules containing active ingredients, e.g., fragrances, are needed to protect the core payload and subsequently release it when triggered. A key requirement for these systems from the industry is that they must withstand suspension in difficult bases without physical dissociation or degradation. This is referred to as the chemical stability of the delivery system. For example, perfumed personal and household cleansers containing high levels of harsh surfactant detergents pose significant challenges to the stability of microcapsules. High levels of surfactants also increase the diffusion rate of active substances from microcapsules. This leads to leakage of active substances during storage and reduces the impact when the microcapsules are triggered to release. In addition, the mechanical stability of microcapsules can be compromised by physical forces, such as crushing, or other methods that compromise the integrity of the microcapsules.

[0003] Consumer demand for environmentally friendly delivery systems, along with performance in terms of stability and olfactory performance, is becoming increasingly important and is driving the development of new delivery systems.

[0004] Therefore, there remains a need to provide new microcapsules using more environmentally friendly materials without compromising the performance of the microcapsules, particularly with regard to stability in difficult media such as consumer product bases, and in providing good performance with regard to active ingredient delivery, e.g., olfactory performance in the case of perfumery ingredients.

[0005] Summary of the Invention It has now been found that microcapsules encapsulating hydrophobic materials such as fragrance oils can be obtained by forming a homogeneous composite shell comprising (or made from) a plant-based coacervate material and a polymeric material.

[0006] The first object of the present invention is to a core comprising a hydrophobic material, preferably a fragrance oil; and a polymer shell, wherein the polymer shell is polymer materials, · Core-shell microcapsules comprising a first polyelectrolyte and a coacervate comprising a second polyelectrolyte, wherein the first polyelectrolyte comprises a plant protein.

[0007] The second object of the present invention is to (i) providing a hydrophobic phase comprising a hydrophobic material and at least a multifunctional monomer; (ii) mixing the first polyelectrolyte and the second polyelectrolyte in the dispersed phase under conditions sufficient to avoid forming a suspension of complex coacervates; (iii) adding a hydrophobic phase to the dispersed phase to form a two-phase dispersion and applying conditions sufficient to form a coacervate; (iv) a process for preparing a core-shell microcapsule slurry, comprising providing conditions sufficient to induce interfacial polymerization to form a core-shell microcapsule slurry.

[0008] The third object is the core-shell microcapsule slurry obtained by the process defined above.

[0009] The present invention also relates to consumer products in the form of home care, fabric care or personal care products comprising said microcapsules or said microcapsule slurries.

[0010] Detailed Description of the Invention Unless otherwise indicated, percentages (%) are meant to indicate weight percent of a composition.

[0011] By "hydrophobic material" is meant any hydrophobic material (a single material or a mixture of materials) that forms a two-phase dispersion when mixed with water.

[0012] "Component" means a single compound or a combination of components.

[0013] By "fragrance or flavor oil" is meant a single flavoring or flavoring compound or a mixture of several flavoring or flavoring compounds.

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

[0015] By "microcapsules" and the like, in the present invention, is meant core-shell microcapsules having a particle size distribution in the micron range (e.g., an average diameter (Dv(50)) of about 1 to 3000 microns) and comprising an outer polymeric shell and an inner hydrophobic phase surrounded by the outer shell. According to one embodiment, the microcapsules have an average diameter of 1 to 500 microns, preferably 2 to 200 microns, more preferably 4 to 100 microns, and even more preferably 4 to 50 microns.

[0016] According to the present invention, the terms "average diameter" or "average size" are used interchangeably. According to one embodiment, the microcapsules are non-agglomerated. According to another embodiment, the microcapsules are partially agglomerated. According to yet another embodiment, the microcapsules are entirely agglomerated.

[0017] "Microcapsule slurry" means microcapsules dispersed in a liquid. According to one embodiment, the slurry is aqueous, i.e., the microcapsules are dispersed in an aqueous phase.

[0018] The microcapsules of the present invention are composite microcapsules. "Composite microcapsules" refers to core-shell microcapsules having a composite shell, i.e., a shell comprising at least two different materials (a first plant-based coacervate material and a second polymer material). According to the present invention, the terms "coacervate" and "hydrogel" can be used interchangeably. Hydrogel refers to a polymer network swollen with water.

[0019] According to one embodiment, by composite shell, a homogeneous shell is also to be understood, meaning that the plant-based coacervate and the polymeric material are homogeneously dispersed within the shell. In other words, the microcapsules do not contain two distinct layers, but a single composite shell. The microcapsules according to the present invention do not contain an inner shell of polymeric material and an outer shell of coacervate.

[0020] According to certain embodiments, the polymeric shell comprises the reaction product of a polymeric material and a coacervate. [Brief explanation of the drawings]

[0021] [Figure 1] 1A-1D represent optical microscopy and SEM images, respectively, of microcapsules of the present invention. [Figure 2] 1A-1D represent optical microscopy and SEM images, respectively, of microcapsules of the present invention. [Figure 3] 1A-1D represent optical microscopy and SEM images, respectively, of microcapsules of the present invention. [Figure 4] FIG. 1 shows the olfactory performance of Microcapsule A and Microcapsule B in fabric softener and liquid detergent, respectively. [Figure 5] FIG. 1 shows the olfactory performance of Microcapsule A and Microcapsule B in fabric softener and liquid detergent, respectively.

[0022] microcapsules The first object of the present invention is to a core comprising a hydrophobic material, preferably a fragrance oil; and a polymer shell, wherein the polymer shell is polymer materials, · Core-shell microcapsules comprising a first polyelectrolyte and a coacervate comprising a second polyelectrolyte, wherein the first polyelectrolyte comprises a plant protein.

[0023] Another object is a slurry comprising the microcapsules defined above.

[0024] Hydrophobic materials According to one embodiment, the core is an oily core.

[0025] Hydrophobic materials according to the present invention can be "inert" materials such as solvents, or can be active ingredients.

[0026] When the hydrophobic material is an active ingredient, the hydrophobic material is preferably selected from the group consisting of flavors, flavor ingredients, fragrances, fragrance ingredients, dietary supplements, cosmetics, pesticides, biocidal actives and mixtures thereof.

[0027] According to certain embodiments, the hydrophobic material comprises a mixture of a fragrance and another ingredient selected from the group consisting of a nutraceutical, a cosmetic, a pesticide, and a biocidal active.

[0028] According to one embodiment, the hydrophobic material comprises a phase change material (PCM).

[0029] 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 pesticides.

[0030] According to certain embodiments, the hydrophobic material comprises a mixture of a pesticide and another ingredient selected from the group consisting of fragrances, dietary supplements, cosmetics, and biocidal actives.

[0031] According to certain embodiments, the hydrophobic material comprises a fragrance.

[0032] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0033] According to a particular embodiment, the hydrophobic material consists of a biocidal active substance.

[0034] According to certain embodiments, the hydrophobic material comprises a pesticide.

[0035] By "perfume" (or equivalently "perfume oil") herein is meant an ingredient or composition that is liquid at about 20°C. According to any one of the above embodiments, the perfume oil can 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 modifying an odor. In other words, to be considered perfuming, such an ingredient must be recognized by those skilled in the art as not merely having an odor, but also being able to at least impart or modify the odor of the composition in a positive or pleasant way. For the purposes of the present invention, perfume oil also includes combinations of perfuming ingredients with substances that together improve, enhance or modify the delivery of the perfuming ingredient, such as perfume precursors, modifiers, emulsions or dispersions, as well as combinations that impart additional benefits beyond those that modify or impart odor, such as longevity, blooming, anti-malodor action, antimicrobial effect, microbial stability, pest control.

[0036] The nature and type of perfuming ingredients present in the oil phase do not warrant further detailed description herein, and are in any case not exhaustive; those skilled in the art can select them based on their general knowledge and according to the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming ingredients belong to various chemical classes, such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen or sulfite heterocycles, and essential oils (e.g., thyme oil), and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in each case listed in reference works such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent editions, or other works of a similar nature, as well as in the abundant patent literature in the field of perfumery.

[0037] 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 plant ingredients: eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0 2,7 ]undecane-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol, and / or alpha-pinene; 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 Ingredients: Methyl Dihydrojasmonate, Linalool, Citronellol, Phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, Hexylcinnamic Aldehyde, 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-indanemethanol, 2,6,6-trimethyl-3-cyclohexene-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, vergyl acetate, geraniol, p-mentha-1-en-8-ol, 4-(1,1-dimethylethyl)-1- Cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis-methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, vermicelli 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, amyl cinnamic aldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, vergyl isobutyrate, and / or a mixture of methyl ionone isomers; Fruit components: 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, allylheptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl [3-ethyl-2-oxiranyl]acetate, and / or diethyl 1,4-cyclohexanedicarboxylate; Green ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styrallyl acetate, allyl (2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol, and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; Musk components: 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-cyclohexyl lopentadecen-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; Wood components: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[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 isobornyl acetate; Other ingredients (e.g., in amber, powdered spice, or water): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane, and / or 3-(3-isopropyl-1-phenyl)butanal.

[0038] It is also understood that the ingredient may be a compound known to release various types of perfuming compounds in a controlled manner, also known as pro-perfumes or pro-fragrances. Non-limiting examples of suitable pro-perfumes include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan ...octanone, 3 Tan-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hex-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2-( (2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec-1-en-1-yl) 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.

[0039] The perfuming ingredients may be dissolved in a solvent currently used in the perfume industry. The solvent is preferably not alcohol. Examples of such solvents include diethyl phthalate, isopropyl myristate, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is highly hydrophobic and highly sterically hindered, such as Abalyn® or benzyl benzoate. Preferably, the perfume contains less than 30% solvent. More preferably, the perfume contains less than 20%, and even more preferably less than 10%, of solvent, all of which percentages are defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially solvent-free.

[0040] Preferred perfuming ingredients are those with high steric hindrance (bulky materials), in particular those from one of the following groups: Group 1: Perfuming ingredients containing a cyclohexane ring, a cyclohexene ring, a cyclohexanone ring or a cyclohexenone ring substituted with at least one linear or branched C1-C4 alkyl or alkenyl substituent; Group 2: Perfuming ingredients containing a cyclopentane ring, a cyclopentene ring, a cyclopentanone ring or a cyclopentenone ring substituted with at least one linear or branched C4-C8 alkyl or alkenyl substituent; Group 3: Perfuming ingredients comprising a phenyl ring substituted with at least one linear or branched C5-C8 alkyl or alkenyl substituent, or with at least one phenyl substituent and optionally with one or more linear or branched C1-C3 alkyl or alkenyl substituents, or perfuming ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched C5-C8 alkyl or alkenyl substituent, or with at least one phenyl substituent and optionally with 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: Perfuming ingredients containing camphor-like ring structures; Group 6: At least one of C7 to C 20 Perfuming ingredients containing ring structures; Group 7: Perfuming ingredients having a logP value of more than 3.5 and containing at least one tert-butyl substituent or at least one trichloromethyl substituent;

[0041] Examples of components from each of these groups are as follows: Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (manufacturer: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (manufacturer: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-p-menthadien-7-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 1-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-menthanyl acetate, (1R,2S,4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (manufactured by: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanediethyl dicarboxylate (manufactured by: Firmenich SA, Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (manufactured by: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (manufacturer: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde; Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Givaudan SA, Vernier, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (manufacturer: Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentane acetate (manufacturer: Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (manufacturer: Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (manufacturer: Givaudan SA, Vernier, Switzerland); Group 3: damascone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), (1'R)-2-[2-(4'-methyl-3'-cyclohexen-1'-yl)propyl]cyclopentanone, alpha-ionone, beta-ionone, damascenone, a mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate (manufactured by Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (manufactured by International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (manufactured by Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (manufactured by Firmenich SA, Geneva, Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpenyl isobutyrate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate (manufactured by Firmenich SA, Geneva, Switzerland), 8-methoxy-1-p-menthene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate (manufactured by Firmenich SA, Geneva,Switzerland), para-tert-butylcyclohexanone, menthenethiol, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allyl cyclohexylpropionate, cyclohexyl salicylate, 2-methoxy-4-methylphenyl methyl carbonate, ethyl 2-methoxy-4-methylphenyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate; Group 4: Methyl cedryl ketone (manufacturer: International Flavors and Fragrances, USA), (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6 ]dec-3-en-8-yl 2-methylpropanoate and (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6] in a mixture with dec-4-en-8-yl 2-methylpropanoate, vetiverol, vetiverone, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone (manufactured by International Flavors and Fragrances, USA), (5RS,9RS,10SR)-2,6,9,10-tetramethyl-1-oxaspiro[4.5]deca-3,6-diene, and (5RS,9SR,10RS) isomers, 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]deca-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indenone (manufactured by International Flavors and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (manufacturer: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undec-4-ene-9-spiro-2'-oxirane (manufacturer: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (manufacturer: Firmenich SA, Geneva, Switzerland), octalinol, (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan, manufacturer: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl acetate, and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl acetate, and tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl propanoate, and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl propanoate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptane-3-spiro-2'-cyclohexen-4'-one; Group 5: camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedrane, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (manufacturer: Firmenich SA, Geneva, Switzerland), cedrene, cedrenol, cedrol, 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-4-one 2,7 ] undecan-4-one (manufacturer: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (manufacturer: Firmenich SA, Geneva, Switzerland); Group 6: (Trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (Manufacturer: Firmenich SA, Geneva, Switzerland), 9-hexadecen-16-olide (Manufacturer: Firmenich SA, Geneva, Switzerland), pentadecenolide (Manufacturer: Firmenich SA, Geneva, Switzerland), 3-methyl-(4 / 5)-cyclopentadecenone (Manufacturer: Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (Manufacturer: Firmenich SA, Geneva, Switzerland), pentadecanolide (Manufacturer: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (Manufacturer: Firmenich SA, Geneva, Switzerland), 1-ethoxyethoxy)cyclododecane (manufacturer: Firmenich SA, Geneva, Switzerland), 1,4-dioxacycloheptadecane-5,17-dione, 4,8-cyclododecadien-1-one; Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (manufacturer: Givaudan SA, Vernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0042] Preferably, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients selected from groups 1 to 7 as defined above. More preferably, the perfume comprises at least 30%, preferably at least 50% of ingredients from groups 3 to 7 as defined above. Most preferably, the perfume comprises at least 30%, preferably at least 50% of ingredients from groups 3, 4, 6 or 7 as defined above.

[0043] 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.

[0044] According to a particular embodiment, the perfume used in the present invention contains less than 10% by weight of primary alcohols, less than 15% by weight of secondary alcohols, and less than 20% by weight of tertiary alcohols. Advantageously, the perfume used in the present invention contains no primary alcohols and less than 15% of secondary and tertiary alcohols.

[0045] According to one embodiment, the oily phase (or oily core) comprises: 25-100% by weight, preferably 25-98% by weight, of a perfume oil containing at least 15% by weight of a high-impact perfume raw material having a Log T<-4, 1.07g / cm 3 and 0 to 75% by weight, preferably 2 to 75% by weight, of a density balancing material having a density greater than 100%.

[0046] A "high impact perfume raw material" should be understood as a perfume raw material having a LogT<-4. The odor threshold concentration of a chemical compound is determined in part by its shape, polarity, partial charge, and molecular weight. For convenience, the odor threshold concentration is expressed as the base 10 logarithm of the threshold concentration, i.e., Log[Threshold] ("LogT").

[0047] "Density balancing material" is 1.07g / cm 3 and preferably has little or no odor.

[0048] The odor threshold concentration of a fragrance compound is determined using a gas chromatograph ("GC"). Specifically, the gas chromatograph is calibrated to determine the exact volume, split ratio, and hydrocarbon response of a fragrance oil component injected by a syringe using hydrocarbon standards of known concentration and chain length distribution. The air flow rate is accurately measured, and the sampled volume is calculated assuming the duration of a human inhalation lasts 12 seconds. Since the exact concentration at the detector at any time is known, the mass per inhaled volume and, therefore, the concentration of the fragrance compound are known. To determine the threshold concentration, a solution is delivered to a sniff port at the back-calculated concentration. Panelists smell the GC effluent and identify the retention time at which an odor is detected. The average across all panelists determines the odor threshold concentration of the fragrance compound. Determining odor thresholds is described in further 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.

[0049] High impact fragrance raw materials with Log T<-4 and 1.07 g / cm 3The properties of density-balanced materials having densities greater than 1000 .mu.m are described in WO 2018115250, the contents of which are incorporated by reference.

[0050] According to one embodiment, the high impact perfume raw materials having a Log T<-4 are (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenylacetate, pyrazobutyl, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl)pyridine, 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 1-(5,5-dimethyl (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[b]furan-2-one, 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'-trimethylbis(2-methyl-1-methyl- ... chloro[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)-furanone, methyl 2,4 -Dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4alpha,8abeta-dimethyl-4a-naphthalenol, patchoulol, 2-methoxy-4-(1-propenyl)phenol, a mixture containing (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylene-2-phenyl-2H-pyran, 4-methylene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,A 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-methylphenylisobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, beta,2,2,3-tetramethyl-delta-methylene-3-cyclopentene-1-butanol, delta damascone ((2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one) , (+-)-3,6-Dihydro-4,6-dimethyl-2-phenyl-2h-pyran, Anisaldehyde, Para-cresol, 3-Ethoxy-4-hydroxybenzaldehyde, Methyl 2-aminobenzoate, Ethyl methylphenylglycidate, Octalactone gamma, Ethyl 3-phenyl-2-propenoate, (-)-(2E)-2-Ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, Para-cresyl acetate, Dodecalactone, Tricyclone, (+)-(3R,5Z)- 3-Methyl-5-cyclopentadecen-1-one, undecalactone, (1R,4R)-8-mercapto-3-p-menthanone, (3S,3AS,6R,7AR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, beta-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-Methyl-4-cyclopentadecen-1-one, (+-)-5E3-methyl-5-cyclopentadecen-1-one, cyclopropyl methyl 3-hexenoate, (4E)-4-methyl-5-(4-methylphenyl)-4-pentenal, (+-)-1-(5-propyl-1,3-benzodioxol-2-yl)ethanone, 4-methyl-2-pentylpyridine, (+-)-(E)-3-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, (2S,5R)-5-methyl-2-(2-propanyl)cyclohexanone oxime, 6-hexyltetrahydro-2H-pyran-2-one, (+-)-3-(3-isopropyl (1-phenyl)butanal, methyl 2-(3-oxo-2-pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohex-2-enyl)pent-1-en-3-one, indole, 7-propyl-2H,4H-1,5-benzodioxepin-3-one, ethylpraline, (4-methylphenoxy)acetaldehyde, ethyltricyclo[5.2.1.0., 2,6]decane-2-carboxylate, (+)-(1'S,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol, (4E)-3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-isopropyl-6-methyl -Bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, methylnonylacetaldehyde, 4-formyl-2-methoxyphenyl 2-methylpropanoate, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, (1R,5R)-4,7,7-trimethyl-6-thiabiphenyl Cyclo[3.2.1]oct-3-ene, (1R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1,6-octadien-3-ol, (E)-3-phenyl-2-propenenitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopentene)

[0023] The methyl cyclohexene-1-yl (2E)-1-penten-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.

[0051] According to one embodiment, the perfume raw materials having a Log T<-4 are selected in the group consisting of aldehydes, ketones, alcohols, phenols, ester lactones, ethers, epoxides, nitriles and mixtures thereof.

[0052] According to one embodiment, the perfume raw material having a Log T<-4 comprises at least one compound selected from the group consisting of alcohols, phenols, ester lactones, ethers, epoxides, nitriles and mixtures thereof, preferably in an amount of 20-70% by weight, based on the total weight of the perfume raw material having a Log T<-4.

[0053] According to one embodiment, the perfume raw materials having a Log T<-4 comprise 20-70% by weight of aldehydes, ketones and mixtures thereof, based on the total weight of the perfume raw materials having a Log T<-4.

[0054] Thus, the remaining perfume raw materials contained in the oily core may have a Log T > -4.

[0055] According to one embodiment, the perfume raw materials having a Log T>-4 are ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal, vergyl propionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate, (+-)-(E)-4-methyl-3-decen-5-ol, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa-12 / 13-cyclohexadecen-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, aldehyde C11, (+-)-2,6-dimethyl-7-octen-2-ol, allyl 3-cyclohexylpropanoate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, allyl heptanoate, 2-(2-methyl- 2-propanyl)cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl butyrate, geranyl acetate, neryl acetate, (+-)-1-phenylethyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, ethyl 3-oxobutanoate, (2Z)-ethyl 3-hydroxy-2-butenoate, 8-p-menthanol, 8-p-menthanyl acetate, 1-p-menthanyl acetate, (+-)-2-(4-methyl-3-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 -Buten-2-one, 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, ethyl hexanoate, undecanal, decanal, 2-phenylethyl acetate, (1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol), (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2-propanylidene)cyclohexene, (+)-(R)-4-(2-methoxypropan-2-yl)-1-methylcyclohex-1-ene, vergyl acetate, (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1-[( (1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3R)-1-[(1S,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (+)-(1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, and mixtures thereof.

[0056] According to one embodiment, the oily core (or perfume formulation) comprises: 0 to 60% by weight of a hydrophobic solvent (based on the total weight of the fragrance formulation), 40 to 100% by weight of fragrance oil (based on the total weight of the fragrance formulation) having the following characteristics: o at least 35%, preferably at least 40%, preferably at least 50%, even more preferably at least 60% of perfuming ingredients having a log P greater than 3, preferably greater than 3.5; o at least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40% of high loft materials of groups 1 to 6, preferably 3 to 6, as defined above, and o perfume oils comprising at least two, preferably all, of 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 Log T<-4 as defined above, Optionally, it comprises a further hydrophobic active ingredient.

[0057] According to a particular embodiment, the perfume comprises 0-60% by weight of hydrophobic solvents.

[0058] According to a particular embodiment, the hydrophobic solvent is a density balancing material preferably selected in the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylate, benzyl cinnamate and mixtures thereof.

[0059] In certain embodiments, the hydrophobic solvent has a Hansen solubility parameter that is compatible with the encapsulated fragrance oil.

[0060] The term "Hansen Solubility Parameter" is understood to refer to the solubility parameter approach proposed by Charles Hansen, used to predict polymer solubility, and developed on the basis that the total energy of vaporization of a liquid is composed of several individual parts. To calculate the "weighted Hansen Solubility Parameter", the effects of (atomic) dispersion forces, (molecular) permanent dipole-permanent dipole forces, and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen Solubility Parameter" is calculated by the following equation: (δD 2 +δP 2 +δΗ 2 ) 0.5 where δD is the Hansen dispersion value (hereinafter also referred to as the atomic dispersion force), δP is the Hansen polarizability value (hereinafter also referred to as the dipole moment), and δH is the Hansen hydrogen bond ("h-bond") value (hereinafter also referred to as the 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).

[0061] The Euclidean difference in solubility parameters between the fragrance and the solvent is (4*(δD solvent -δD fragrance ) 2 +(δPsolvent -δP fragrance ) 2 +(δH solvent -δH fragrance ) 2 ) 0.5 where δD solvent , δP solvent and δH solvent are the Hansen dispersion value, Hansen polarizability value and Hansen h-bond value of the solvent, respectively, and δD fragrance , δP fragrance and δH fragrance are the Hansen dispersion value, Hansen polarizability value and Hansen h-bonding value of the fragrance, respectively.

[0062] In certain embodiments, the fragrance 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.

[0063] 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.

[0064] In certain embodiments, at least 90% of the fragrance oils, preferably at least 95% of the fragrance oils, and most preferably at least 98% of the fragrance 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.

[0065] 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.

[0066] According to one embodiment, the perfumed formulation comprises a fragrance modifier, which may be used in addition to the hydrophobic solvent, if present, or as a replacement for the hydrophobic solvent, if not present.

[0067] Preferably, fragrance modifiers are defined as fragrance materials having: i. Vapor pressure less than 0.0008 Torr at 22°C; ii. a clogP of 3.5 or greater, preferably 4.0 or greater, and more preferably 4.5; iii. at least two Hansen solubility parameters selected from a first group consisting of atomic dispersion forces of 12 to 20, dipole moments of 1 to 7, and hydrogen bonds of 2.5 to 11; iv. At least two Hansen solubility parameters selected from a second group consisting of atomic dispersion forces of 14 to 20, dipole moments of 1 to 8, and hydrogen bonds of 4 to 11 when in a solution containing compounds having a vapor pressure range of 0.0008 to 0.08 Torr at 22°C.

[0068] Preferably, by way of example, the following components may be listed as adjusters, but the list is not limited to the following materials: alcohol C12, oxacyclohexadec-12 / 13-en-2-one, 3-[(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecen-1-one, cyclopentadecanone, (8Z)- Oxacycloheptadec-8-en-2-one, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, 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,4a S,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amyl cinnamic aldehyde, hexyl cinnamic aldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadiene-3-one, (9Z)-9-cycloheptadecen-1-one.

[0069] According to a particular embodiment, the hydrophobic material does not include an active ingredient (such as a fragrance). According to this particular embodiment, the hydrophobic material comprises, and preferably consists of, a hydrophobic solvent preferably selected from the group consisting of isopropyl myristate, triglycerides (e.g., Neobee® MCT oil, vegetable oil), D-limonene, silicone oil, mineral oil, and mixtures thereof, and optionally, a hydrophilic solvent preferably selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol, glycol ethers, and mixtures thereof.

[0070] The term "biocide" refers to a chemical substance that can kill living organisms (e.g., microorganisms) or reduce or prevent their growth and / or accumulation. Biocides are commonly used in medicine, agriculture, forestry, and industries to prevent contamination of, for example, water, agricultural products including seeds, and oil pipelines. Biocides can be pesticides, including fungicides, herbicides, insecticides, algicides, molluscicides, acaricides, and rodenticides; and / or antimicrobial agents, such as bactericides, antibiotics, antibacterial agents, antivirals, antifungals, antiprotozoals, and / or antiparasitics.

[0071] As used herein, "pesticide" refers to a substance that repels or attracts pests, and serves to reduce, inhibit, or promote their growth, development, or activity. A pest refers to any organism, whether animal, plant, or fungus, that is invasive or bothersome to plants or animals, and includes insects, particularly arthropods, mites, spiders, fungi, weeds, bacteria, and other microorganisms.

[0072] By "flavor oil" is meant herein a flavor ingredient or a mixture of flavor ingredients, solvents or adjuvants currently used in the preparation of flavor formulations, i.e. a specific mixture of ingredients intended to be added to an edible composition or a chewable product in order to impart, improve or modify its organoleptic properties, in particular its flavor and / or taste. Flavor ingredients are well known to those skilled in the art and their nature does not warrant a detailed description herein, which is in any case not exhaustive, and a flavorist of ordinary skill can select them on the basis of his general knowledge according to the intended use or application and the organoleptic effect desired to be achieved. Many of these flavor ingredients are listed in reference works such as books by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, NJ, USA, or more recent editions thereof, or other works of a similar nature such as Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press or Synthetic Food Adjuncts, 1947, by M.B. Jacobs, van Nostrand Co., Inc. Solvents and adjuvants currently used in the preparation of flavor formulations are also well known in the art.

[0073] In particular embodiments, the flavor is a mint flavor. In even more particular embodiments, the mint is selected from the group consisting of peppermint and spearmint.

[0074] In a further embodiment, the flavor is a cooling agent or mixtures thereof.

[0075] In another embodiment, the flavor is a menthol flavor.

[0076] Flavors derived from or based on fruits in which citric acid is the predominant naturally occurring acid include, but are not limited to, citrus fruits (e.g., lemon, lime), limonene, strawberry, orange, and pineapple. In one embodiment, the flavored food product is lemon juice, lime juice, or orange juice extracted directly from the fruit. Further flavor embodiments include juices or liquids extracted from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, and any other citrus fruits, or varieties or hybrids thereof. In certain embodiments, the flavors include liquids extracted or distilled from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, any other citrus fruits, or varieties or hybrids thereof, pomegranates, kiwifruits, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruit, mangoes, pears, tomatoes, and strawberries.

[0077] In certain embodiments, the flavor comprises a composition comprising limonene, and in certain embodiments, the composition is a citrus fruit further comprising limonene.

[0078] In another particular embodiment, the flavor comprises a flavor selected from the group including strawberry, orange, lime, tropical, berry mix, and pineapple.

[0079] The term flavor includes not only flavors that impart or modify the smell of a food product, but also ingredients that impart or modify tastes, which do not necessarily have a taste or smell themselves, but can modify the taste provided by other ingredients, such as salt-enhancing ingredients, sweet-enhancing ingredients, umami-enhancing ingredients, bitter-blocking ingredients, etc.

[0080] In further embodiments, a suitable sweetener may be included in the particles described herein. In certain embodiments, the sweetener is selected from the group consisting of sugars (such as, but not limited to, sucrose), stevia components (such as, but not limited to, stevioside or rebaudioside A), sodium cyclamate, aspartame, sucralose, sodium saccharin, and acesulfame K, or mixtures thereof.

[0081] polymer materials According to the present invention, the polymeric shell comprises a polymeric material.

[0082] According to one embodiment, the polymeric material is selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, poly(beta amino ester), polylactic acid, poly(thiol-acrylate), polymers of urea and formaldehyde, polymers of melamine and formaldehyde, polymers of melamine and urea, or polymers of melamine and glyoxal, and mixtures thereof.

[0083] According to a particular embodiment, the polymeric material is a polyurea and / or a polyurethane.

[0084] According to one embodiment, the polymeric material is a polyurea-based material and comprises the reaction product of a polyisocyanate and, optionally, an amine. According to this particular embodiment, interfacial polymerization can be induced by the addition of a polyamine reactant. Preferably, the reactant is selected from the group consisting of water-soluble guanidine salts and guanazole to form the polyurea material with the polyisocyanate. According to another embodiment, the polyurea-based polymeric material is formed in the absence of added polyamine reactants, preferably resulting solely from the autopolymerization of at least one polyisocyanate in the presence of a catalyst.

[0085] According to another embodiment, the polymeric material is a polyurethane-based material and comprises the reaction product of a polyisocyanate and a polyol. According to this particular embodiment, the interfacial polymerization is induced by the addition of a polyol reactant. Preferably, the reactant is selected from the group consisting of monomeric and polymeric polyols having multiple hydroxyl groups available for reaction, and mixtures thereof.

[0086] According to another embodiment, the polymeric material is a polyurea / polyurethane-based material, comprising the reaction product of a polyisocyanate with a polyol and an amine. In this case, interfacial polymerization is induced by the addition of a mixture of reactants, as described in the first and second embodiments. In addition, a crosslinker having both amino and hydroxyl groups can be used to produce the polyurea / polyurethane material. Furthermore, a polyisocyanate having both urea and urethane functional groups can be used to produce the polyurea / polyurethane material.

[0087] According to another embodiment, the polymeric material is a polyamide-based material and comprises the reaction product of an acyl chloride and at least one amine, preferably at least two amines. According to certain embodiments, the second polymeric material is a polyamide-based material as disclosed in WO2020127743 or WO2020127749, the contents of which are incorporated herein by reference with respect to components and preparation methods.

[0088] According to one embodiment, the polymeric material is a copolymer such as poly(urea-urethane), poly(ester amide) and mixtures thereof.

[0089] According to one embodiment, the polymeric material is present in an amount of less than 10% by weight, preferably less than 8% by weight, preferably less than 6% by weight, preferably less than 4% by weight, more preferably less than 3% by weight, and even more preferably less than 2% by weight, based on the total weight of the microcapsule. According to particular embodiments, the polymeric material is present in an amount of less than 1-10% by weight, preferably less than 1-8% by weight, preferably less than 1-6% by weight, preferably less than 1-4% by weight, more preferably less than 1-3% by weight, and even more preferably less than 1-2% by weight, based on the total weight of the microcapsule. In fact, it is emphasized that in consumer products, even if the amount of polymeric material forming the wall is reduced, the microcapsules still exhibit good stability.

[0090] Plant-based coacervate According to the present invention, a coacervate is made from (including) a first and second polyelectrolyte, where the first polyelectrolyte comprises a plant protein.

[0091] According to one embodiment, the plant protein (first polyelectrolyte) is selected in the group consisting of potato protein, chickpea protein, pea protein, faba bean protein, barley protein, oat protein, soy protein, algae protein, wheat gluten protein, lupin protein, canola protein, hemp protein, rice protein, sunflower seed protein and mixtures thereof.

[0092] The first polyelectrolyte can include plant proteins and non-plant proteins, such as fungal proteins, mycoproteins, and mixtures thereof.

[0093] According to another embodiment, the first polyelectrolyte consists of a plant protein.

[0094] According to one embodiment, the first polyelectrolyte has a net positive charge when the pH is less than 8, and the second polyelectrolyte has a net negative charge when the pH is greater than 2.

[0095] According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 10%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 20%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 30%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 40%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 50%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 60%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 70%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 80%. According to one embodiment, the solubility of the protein, preferably a plant protein, is greater than 90%. The above solubilities are given in water at room temperature (typically 20°C) and preferably at natural pH.

[0096] The protein used in the present invention, preferably plant protein, can be native or partially or completely denatured by any suitable method.Denaturation is the process of modifying the three-dimensional structure of protein by unfolding, that is, involving the destruction and possible collapse of both the secondary and tertiary structure of protein.In fact, denaturation implies the destruction of many of the weak links or bonds (e.g., hydrogen bonds) within protein molecules that are responsible for the highly ordered structure of the protein in its native state.Denaturation can be reversible (proteins can restore their native state when the effect of denaturation is removed) or irreversible.

[0097] Denaturation can be brought about in a variety of ways. Proteins can be denatured by exposure to temperature, radiation, or mechanical stress, including shear, changes in pH (treatment with base or acid), treatment with oxidizing or reducing agents, inorganic salts, certain organic solvents, chaotropic agents (i.e., those with a positive chaotropic value (kJ / kg on the Hallsworth scale)). -1The compound may be modified with a compound having a carboxyl group (mol), such as a guanidine salt (e.g., guanidine carbonate, guanidine hydrochloride), urea, calcium chloride, n-butanol, ethanol, lithium perchlorate, lithium acetate, magnesium chloride, phenol, 2-propanol, sodium dodecyl sulfate, or thiourea.

[0098] Proteins used in the present invention can also be derivatized or modified (e.g., derivatized or chemically modified). For example, proteins can be modified by the covalent attachment of sugars, lipids, peptides, or chemical groups such as phosphate or methyl.

[0099] According to one embodiment, the first polyelectrolyte comprises at least one polypeptide.

[0100] According to a particular embodiment, the plant protein is potato protein.

[0101] Potato proteins are typically extracted from potato tubers (Solanum tuberosum). According to one embodiment, the potato proteins are native potato proteins and preferably comprise or consist of patatin.

[0102] A second polyelectrolyte, preferably selected from among polysaccharides or another polymer, having a charge of the opposite sign to that of the first polyelectrolyte. Generally, the second polyelectrolyte is negatively charged at pH>2.

[0103] According to one embodiment, the second polyelectrolyte is selected in the group consisting of gum arabic, alginates, cellulose derivatives, guar gum, pectinate salts, pectin, carrageenan, polyacrylic and methacrylic acids, cellulose derivatives, xanthan gum, microbial exopolysaccharides and mixtures thereof.

[0104] Among the cellulose derivatives, mention may be made, for example, of carboxymethylcellulose (preferably having a molecular weight of 35,000 to 50,000 Da), hydroxypropylmethylcellulose (HPMC) or mixtures thereof.

[0105] According to a particular embodiment, the second polyelectrolyte is gum arabic.

[0106] The weight ratio of the first polymer electrolyte to the second polymer electrolyte is preferably 0.2-5, more preferably 0.5-2, and even more preferably 1-2.

[0107] According to a particular embodiment, the weight ratio of the first polyelectrolyte to the second polyelectrolyte is 1.

[0108] According to a particular embodiment, the weight ratio of the first polyelectrolyte to the second polyelectrolyte is 1.5.

[0109] According to one embodiment, the microcapsules are a core containing a fragrance oil, as well as A shell comprising a polyurea and a coacervate comprising potato protein and gum arabic.

[0110] According to one embodiment, the microcapsules are a core containing a fragrance oil, as well as A shell comprising polyurea and a coacervate comprising canola protein and gum arabic.

[0111] According to a preferred embodiment, the coacervate is chemically hardened using a suitable crosslinker such as glutaraldehyde, glyoxal, formaldehyde, polyphenols (such as tannic acid), polyanhydrides or genipin, preferably used in an amount of 2% to 60% by weight, preferably 2% to 30% by weight, based on the first polyelectrolyte.

[0112] The polyanhydride crosslinker can be poly(ethylene-maleic anhydride), or poly(methyl vinyl ether-maleic anhydride).

[0113] According to certain embodiments, the coacervate is chemically hardened using glutaraldehyde as a cross-linking agent.

[0114] According to another particular embodiment, the coacervate is enzymatically hardened using an enzyme such as transglutaminase.

[0115] According to another embodiment, the coacervate is not crosslinked.

[0116] Optional ingredients According to one embodiment, the microcapsule slurry comprises auxiliary ingredients selected from the group of thickeners / rheology modifiers, preservatives, antimicrobial agents, opacifying agents, mica particles, salts, pH stabilizers / buffering ingredients, preferably in an amount of 0-15 wt %, more preferably 0.1-10 wt %, and even more preferably 0.05-5 wt %, based on the total weight of the slurry.

[0117] Among the various thickening agents, mention may be made, for example, of anionic, cationic, nonionic or zwitterionic copolymers, such as, but not limited to, polyacrylamide, polyacrylate, polyacryloyldimethyltaurate, polyquaternium-37, or carbomer, and mixtures thereof. According to certain embodiments, the thickening agent is xanthan gum, guar gum, diutan gum, or mixtures thereof.

[0118] Among the various preservatives, mention may be made, for example, of sodium benzoate, benzoic acid, benzisothiazolinone, methylchloroisothiazolinone, methylisothiazolinone, chlorhexidine digluconate, sodium hydroxymethylglycinate, parabens, triclosan, phenoxyethanol, caprylhydroxamic acid, potassium sorbate, lactic acid, E-polylysine, caprylyl glycol, caprylhydroxamic acid, glycerin, glyceryl caprylate, ethylhexylglycerin, and mixtures thereof.

[0119] According to another embodiment, the microcapsule slurry of the present invention comprises additional free (ie, non-encapsulated) perfume, preferably in an amount of 5 to 50% by weight based on the total weight of the slurry.

[0120] outer coating According to a particular embodiment of the present invention, the microcapsules according to the present invention comprise an outer coating material selected from the group consisting of polysaccharides, cationic polymers, polysuccinimide derivatives (e.g., as described in WO2021185724) and mixtures thereof to form an outer coating on the microcapsules.

[0121] Polysaccharide polymers are well known to those skilled in the art. Preferred nonionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose and hydroxypropyl methylcellulose, pectin and mixtures thereof.

[0122] According to a particular embodiment, the coating consists of a cationic coating.

[0123] Cationic polymers are also well known to those skilled in the art. Preferred cationic polymers have a cationic charge density of at least 0.5 meq / g, more preferably at least about 1.5 meq / g, but preferably less than about 7 meq / g, more preferably less than about 6.2 meq / g. The cationic charge density of the cationic polymer may be determined by the Kjeldahl method described in the United States Pharmacopeia under the chemical test for nitrogen determination. Preferred cationic polymers are selected from those containing units containing primary, secondary, tertiary, and / or quaternary amine groups, which may form part of the main polymer chain or may be borne by side substituents directly attached thereto. The weight-average (Mw) molecular weight of the cationic polymer is preferably 10,000 to 3.5 Mdaltons, more preferably 50,000 to 2 Mdaltons.

[0124] According to particular embodiments, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylamino methacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-imidazol-3-ium chloride), vinylpyrrolidone, acrylamidopropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride, or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride, and cellulose hydroxypropyltrimonium chloride are used. Preferably, the copolymer is selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride, or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride, and cellulose hydroxypropyltrimonium chloride.

[0125] Specific examples of commercially available products include Salcare® SC60 (cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, manufacturer: BASF) or Luviquat®, e.g. PQ 11N, FC 550 or Style (polyquaternium-11-68, or quaternized copolymer of vinylpyrrolidone, manufacturer: BASF), or Jaguar® (C13S or C17, manufacturer: Rhodia).

[0126] According to any one of the above embodiments of the present invention, the amount of said polymer is added in an amount of about 0%-5% w / w, or even about 0.1%-2% w / w, the percentage being expressed on a w / w basis relative to the total weight of the slurry. It will be clearly understood by those skilled in the art that only a portion of said added polymer will be incorporated into / deposited on the microcapsule shell.

[0127] In certain embodiments, the shell material is a biodegradable material.

[0128] In certain embodiments, the shell is at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradable within 60 days according to OECD 301F.

[0129] 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.

[0130] Thereby it is understood that the core-shell microcapsules, including all components such as the core, shell and optionally the coating, may 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.

[0131] In certain embodiments, the oil core, preferably a fragrance oil, is at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradable within 60 days according to OECD 301F.

[0132] OECD301F is the standard test method for biodegradability established by the Organization for Economic Cooperation and Development.

[0133] Exemplary methods for extracting shells to measure biodegradability are disclosed in Gasparini and all in Molecules 2020, 25, 718.

[0134] Multiple microcapsule systems According to one embodiment, the microcapsules of the present invention (first microcapsule slurry) may be used in combination with a second microcapsule slurry.

[0135] Another object of the present invention is to provide the microcapsule slurry of the present invention as a first microcapsule slurry; and a second microcapsule slurry, wherein the microcapsules contained in the first microcapsule slurry and the second microcapsule slurry differ in their hydrophobic material and / or their wall material, and / or the content of the wall material, and / or the curing conditions for forming the wall material, and / or their coating material.

[0136] According to certain embodiments, the microcapsule delivery system is in the form of a slurry.

[0137] The walls of the second type of microcapsules can vary. By way of non-limiting example, the polymer shell of the second type of microcapsules comprises a material selected from the group consisting of polyurea, polyurethane, polyamide, polyhydroxyalkanoate, polyacrylate, polyester, polyaminoester, polyepoxide, polysiloxane, polycarbonate, polysulfonamide, urea formaldehyde, melamine formaldehyde resin, melamine formaldehyde resin crosslinked with polyisocyanate or aromatic polyol, melamine urea resin, melamine glioxal resin, gelatin / gum arabic shell wall, and mixtures thereof.

[0138] The second type of microcapsules can comprise an oily core containing a hydrophobic active substance, preferably a fragrance, and a composite shell containing a first material and a second material, where the first material and the second material are different, and the first material is a coacervate and the second material is a polymeric material. In certain embodiments, the weight ratio of the first material to the second material is 50:50 to 99.9:0.1. In certain embodiments, the coacervate comprises a first polyelectrolyte, preferably selected from proteins (e.g., gelatin), polypeptides, or polysaccharides (e.g., chitosan), most preferably gelatin, and a second polyelectrolyte, preferably alginate, cellulose derivatives, guar gum, pectinate, carrageenan, polyacrylic and methacrylic acid, or xanthan gum, or even a plant gum such as acacia gum (gum arabic), most preferably gum arabic. The first material, which is a coacervate, can be chemically cured using a suitable crosslinker such as glutaraldehyde, glyoxal, formaldehyde, tannic acid, or genipin, or enzymatically cured using an enzyme such as transglutaminase. The second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, polymers of melamine and formaldehyde, polymers of melamine and urea, or polymers of melamine and glyoxal, and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount of less than 3 wt. %, preferably less than 1 wt. %, based on the total weight of the second type of microcapsule slurry.

[0139] By way of non-limiting example, the shell of the second type of microcapsules can be aminoplast-based, polyurea-based, or polyurethane-based. The shell of the second type of microcapsules can also be hybrid, i.e., organic-inorganic, e.g., a hybrid shell composed of at least two types of crosslinked inorganic particles, or even a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0140] According to one embodiment, the shell of the second type of microcapsules comprises an aminoplast copolymer, such as melamine-formaldehyde, or urea-formaldehyde, or crosslinked melamine formaldehyde or melamine glioxal.

[0141] According to another embodiment, the shell of the second type of microcapsules is a polyurea-based system made from, for example, but not limited to, an isocyanate-based monomer and an amine-containing crosslinker, such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules comprise a polyurea wall that is the reaction product of polymerization between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (e.g., a water-soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of the amine can be omitted. According to a particular embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol and 0.6% to 1% cationic copolymer of vinylpyrrolidone and quaternized vinylimidazole (all percentages defined by weight relative to the total weight of the colloidal stabilizer). According to another aspect, the emulsifier is an anionic or amphiphilic biopolymer which in one aspect may be selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate and mixtures thereof.

[0142] According to another embodiment, the microcapsule wall material of the second type of microcapsules may comprise any suitable resin, including, among others, melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include reaction products of aldehydes and amines, and suitable aldehydes include formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include methylolmelamine, methylated methylolmelamine, iminomelamine, and mixtures thereof. Suitable ureas include dimethylolurea, methylated dimethylolurea, urea-resorcinol, and mixtures thereof. Suitable materials for fabrication may be obtained from one or more of the following companies: Solutia Inc. (St. Louis, Missouri, USA), Cytec Industries (West Paterson, New Jersey, USA), and Sigma-Aldrich (St. Louis, Missouri, USA).

[0143] According to another embodiment, the second type of microcapsules are one-shell aminoplast core-shell microcapsules obtained by a process comprising the following steps: 1) mixing a perfume oil with at least a polyisocyanate having at least two isocyanate functional groups to form an oil phase; 2) dispersing or dissolving an aminoplast resin and optionally a stabilizer in water to form an aqueous phase; 3) preparing an oil-in-water dispersion having an average droplet size of 1 to 100 microns by mixing an oil phase and an aqueous phase; 4) carrying out a curing step to form the walls of the microcapsules; and 5) Optionally, drying the final dispersion to obtain dried core-shell microcapsules.

[0144] According to one embodiment, the second type of microcapsules are formaldehyde-free capsules. A typical process for preparing an aminoplast formaldehyde-free microcapsule slurry includes the following steps: 1) preparing an oligomeric composition comprising the reaction product of or obtainable by reacting together: a. a polyamine component in the form of melamine or in the form of a mixture of melamine with at least one C1-C4 compound containing two NH2 functional groups; b. Glyoxal and C 4-6 an aldehyde component in the form of a mixture of 2,2-dialkoxy-ethanal and optionally glyoxalate, said mixture comprising glyoxal / C 4-6 an aldehyde component having a molar ratio of 2,2-dialkoxy-ethanal of 1 / 1 to 10 / 1; and c. Protonic acid catalyst; 2) preparing an oil-in-water dispersion having a droplet size of 1 to 600 microns, comprising: a. Oil; b.Aqueous medium: c. at least the oligomeric composition obtained in step 1; d. At least a cross-linking agent selected from the following: i.C4-C 12 Aromatic or aliphatic di- or tri-isocyanates and their biuret, triuret, trimer, trimethylolpropane adducts and mixtures thereof; and / or ii. Di- or tri-oxirane compounds of the formula: A-(oxiran-2-ylmethyl) n (In the formula, n represents 2 or 3, and 1 represents a C2-C6 group optionally containing 2 to 6 nitrogen and / or oxygen atoms); e. Optionally, a C1-C4 compound containing two NH2 functional groups; 3) heating the dispersion; and 4) Cooling the dispersion.

[0145] In another particular embodiment, the second type of microcapsules comprises: an oily core containing a hydrophobic active substance, preferably a fragrance; optionally an inner shell made from polymerized multifunctional monomers; A biopolymer shell comprising proteins, wherein at least one protein is cross-linked.

[0146] According to a particular embodiment, the protein is selected in the group consisting of milk proteins, caseinates such as sodium or calcium caseinate, casein, whey protein, hydrolyzed proteins, gelatin, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate, most preferably sodium caseinate.

[0147] According to a particular embodiment, the protein comprises sodium caseinate and a globular protein preferably selected in the group consisting of whey protein, beta-lactoglobulin, ovalbumine, bovine serum albumin, vegetable proteins and mixtures thereof.

[0148] The protein is preferably a mixture of sodium caseinate and whey protein.

[0149] According to certain embodiments, the biopolymer shell comprises a cross-linked protein selected in the group consisting of sodium caseinate and / or whey protein.

[0150] According to certain embodiments, the second type of microcapsule slurry comprises at least one microcapsule made from: an oily core containing a hydrophobic active substance, preferably a fragrance; an inner shell made from polymerized multifunctional monomers, preferably polyisocyanates having at least two isocyanate functional groups; A biopolymer shell comprising proteins, wherein at least one protein is cross-linked, and the protein preferably comprises a mixture comprising sodium caseinate and a globular protein, preferably whey protein. Optionally, at least an outer mineral layer.

[0151] According to one embodiment, the sodium caseinate and / or whey protein are cross-linked proteins.

[0152] The weight ratio of sodium caseinate to whey protein is preferably 0.01-100, more preferably 0.1-10, and even more preferably 0.2-5.

[0153] In another particular embodiment, the second type of microcapsules are polyamide core-shell polyamide microcapsules comprising: an oily core containing a hydrophobic active substance, preferably a fragrance, and A polyamide shell comprising or obtained from: Acyl chloride, a first amino compound, a second amino compound, Optionally, carbohydrates.

[0154] According to certain embodiments, the second type of microcapsules comprises: an oily core containing a hydrophobic active material, preferably a fragrance; and A polyamide shell comprising or obtained from: Acyl chloride in an amount of preferably 5 to 98%, preferably 20 to 98%, more preferably 30 to 85% w / w a first amino compound in an amount preferably between 1% and 50% w / w, preferably between 7 and 40% w / w, a second amino compound in an amount preferably between 1% and 50% w / w, preferably between 2 and 25% w / w; a stabilizer, preferably a biopolymer, in an amount of preferably 0-90%, preferably 0.1-75%, more preferably 1-70%, Optionally, carbohydrates.

[0155] According to certain embodiments, the second type of microcapsules comprises: an oily core containing a hydrophobic active substance, preferably a fragrance, and A polyamide shell comprising or obtained from: Acyl chlorides, a first amino compound which is an amino acid preferably selected in the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and / or mixtures thereof; a second amino compound preferably selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine and / or mixtures thereof, and biopolymers preferably selected from the group consisting of potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, soy protein, rice protein, whey protein, egg albumin, casein, sodium caseinate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudo-collagen, silk protein, sericin powder, gelatin and mixtures thereof, Optionally, a carbohydrate preferably selected from the group consisting of an anionic salt of alginic acid, preferably sodium alginate, pectin, lignin, anionic modified starch, carboxymethylcellulose, carrageenan and mixtures thereof.

[0156] According to another embodiment, the shell of the second type of microcapsules is polyurea-based or polyurethane-based. Examples of processes for preparing polyurea-based and polyurethane-based microcapsule slurries are described, for example, in International Patent Application Publication No. WO2007 / 004166, European Patent Application Publication No. EP2300146 and European Patent Application Publication No. EP25799. Typically, the process for preparing polyurea-based or polyurethane-based microcapsule slurries includes the following steps: a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase; b) preparing an aqueous solution of an emulsifier or colloidal stabilizer to form an aqueous phase; c) adding an oil phase to an aqueous phase to form an oil-in-water dispersion having an average droplet size of 1 to 500 μm, preferably 5 to 50 μm; and d) applying conditions sufficient to induce interfacial polymerization and form microcapsules in the form of a slurry.

[0157] Microcapsule Powder Another object of the present invention is a microcapsule powder obtained by subjecting the microcapsule slurry to drying, such as spray drying, to provide the microcapsules as such, i.e., in powder form. It is understood that any standard method known to those skilled in the art for carrying out such drying can be applied. In particular, the slurry may be spray-dried, preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, gum arabic, vegetable gum, pectin, xanthan, alginate, carrageenan, or a cellulose derivative, to provide the microcapsules in powder form.

[0158] However, other drying methods may also be mentioned, such as extrusion, plating, spray granulation, fluidized bed or even drying at room temperature, using materials (carriers, desiccants) that meet certain criteria, as disclosed in WO 2017 / 134179.

[0159] According to a particular embodiment, the carrier material contains free perfume oil, which may be the same as or different from the perfume from the core of the microcapsules.

[0160] Another object of the present invention is a solid particle comprising: carrier materials, microcapsules as defined above encapsulated in said carrier material, and Optionally, free flavorings encapsulated in said carrier material.

[0161] In certain embodiments, the support material comprises a monomeric support material, an oligomeric support material, or a polymeric support material, or a mixture of two or more thereof.

[0162] An oligomeric carrier is a carrier in which 2 to 10 monomer units are covalently linked together. For example, when the oligomeric carrier is a carbohydrate, the oligomeric carrier can be sucrose, lactose, raffinose, maltose, trehalose, or a fructooligosaccharide.

[0163] Examples of monomeric carrier materials include, for example, glucose, fructose, mannose, galactose, arabinose, fucose, sorbitol, and mannitol.

[0164] The polymeric carrier has more than 10 monomer units covalently linked together.

[0165] In certain embodiments, the carrier may be a polymeric carrier material. Non-limiting examples of polymeric carrier materials include polyaspartates, modified polysuccinimides, lignin and its derivatives, polyoxazolines, polyhydroxyalkanoates, polyphenols, natural and synthetic clays, polyvinyl acetate, polyvinyl alcohol, dextrin, maltodextrin, glucose syrup, natural or modified starch, polysaccharides, carbohydrates, chitosan, gum arabic, polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, acrylamide, acrylates, polyacrylic acid and related maleic anhydride copolymers, amine functional polymers, vinyl ethers, styrene, polystyrene sulfonate, vinyl acid, ethylene glycol-propylene glycol block copolymers, vegetable gums, acacia gum, pectin, xanthan, alginates, carrageenan or cellulose derivatives such as carboxymethylmethylcellulose, methylcellulose or hydroxyethylcellulose; chitin, proteins (animal and vegetable), polyaspartates, polysuccinimides and its derivatives, polyesters, polyaminoesters, polyhydroxyalkanoates, polycarbonates and mixtures thereof. Preferably, the polymeric carrier material includes natural or modified starch, maltodextrin, carbohydrates, chitin, proteins (animal and vegetable), polyaspartate, polysuccinimide and its derivatives, polyesters, polyaminoesters, polyhydroxyalkanoates, polycarbonates and mixtures thereof.

[0166] According to one embodiment, the carrier material is selected in the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gum, pectin, xanthan, alginate, carrageenan, cellulose derivatives and mixtures thereof.

[0167] The solid particles and microcapsule powders defined above can be used interchangeably in the present invention.

[0168] Process for preparing microcapsules The microcapsules of the present invention may be prepared by a variety of processes.

[0169] Embodiment 1 The present invention also provides a process for preparing core-shell microcapsules, comprising: (i) providing a hydrophobic phase comprising a hydrophobic material and at least a multifunctional monomer; (ii) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient to avoid the formation of a suspension of complex coacervates, wherein the first polyelectrolyte comprises a plant protein; (iii) adding a hydrophobic phase to the dispersed phase to form a two-phase dispersion and applying conditions sufficient to form a coacervate; (iv) providing conditions sufficient to induce interfacial polymerization to form a core-shell microcapsule slurry.

[0170] Embodiment 2 The present invention also provides a process for preparing core-shell microcapsules, comprising: (i) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient to avoid forming a suspension of complex coacervates, wherein the first polyelectrolyte comprises a plant protein; (ii) providing a hydrophobic phase comprising a hydrophobic material and at least a multifunctional monomer; (iii) adding a hydrophobic phase to the dispersed phase to form a two-phase dispersion and applying conditions sufficient to form a coacervate; (iv) providing conditions sufficient to induce interfacial polymerization to form a core-shell microcapsule slurry.

[0171] Embodiment 3 The present invention also provides a process for preparing core-shell microcapsules, comprising: (i) adding a hydrophobic phase comprising a hydrophobic material and at least a multifunctional monomer to a dispersed phase comprising a first polyelectrolyte to form a two-phase dispersion, wherein the first polyelectrolyte comprises a plant protein; (ii) adding a second polyelectrolyte to the two-phase dispersion (iii) applying conditions sufficient to form a coacervate; (iv) providing conditions sufficient to induce interfacial polymerization to form a core-shell microcapsule slurry.

[0172] According to one embodiment, the pH of the solution containing both polyelectrolytes (step ii of embodiment 1; step i of embodiment 2; step ii of embodiment 3) is 1 to less than 2.5, preferably 1.5 to 2.2, so that the polyelectrolytes cannot interact to form coacervates.

[0173] According to one embodiment, the pH of the solution containing both polyelectrolytes (step ii of embodiment 1; step i of embodiment 2; step ii of embodiment 3) is 5 to 8, preferably 5.5 to 7, so that the polyelectrolytes cannot interact with each other to form coacervates.

[0174] Coacervation is carried out in step iii) and the pH of the solution is typically 2.5-4.2, preferably 2.8-4.

[0175] The interfacial polymerization may typically be carried out at a temperature of 50°C to 80°C with stirring for 2 to 40 hours to complete the reaction and form microcapsules in the form of a slurry, although the interfacial polymerization may also be carried out at room temperature, typically 20 to 30°C.

[0176] According to one embodiment, the dispersed phase comprises, and preferably consists of, water.

[0177] According to one embodiment, the dispersed phase is an aqueous phase.

[0178] According to one embodiment, the two-phase dispersion is an oil-in-water emulsion.

[0179] According to one embodiment, the dispersed phase comprises water and an alcohol such as glycerol, 1,4-butanediol, ethylene glycol, and mixtures thereof.

[0180] According to one embodiment, the hydrophobic phase is an oil phase.

[0181] According to one embodiment, the hydrophobic phase and / or the dispersed phase comprises an emulsifier, a surfactant or a mixture thereof. The surfactant may be nonionic, anionic, cationic or zwitterionic.

[0182] Emulsifiers and / or surfactants may be polyvinyl alcohol, sodium stearoyl lactylate, esters of mono- and diglycerides, lecithin, saponin, ascorbyl palmitate, sugar esters, sucrose esters, sucroglycerides, polyglycerol polyricinoleate, propylene glycol esters of fatty acids, sorbitan esters such as sorbitan tristearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monopalmitate, polysorbates such as polyoxyethylene(20) sorbitan monolaurate (polysorbate 20), polysorbate 40, polysorbate 60, polysorbate 80, Brij 35 (polyoxyethylene lauryl ether) or Brij 93 (polyethylene glycol oleyl ether), sodium dodecyl sulfate, tauride, sulfoacetate, alkyl ether sulfate, fatty alcohol sulfate, secondary alkyl sulfonate, alkyl benzene sulfonate, alkyl carboxylate and mixtures thereof.

[0183] Emulsifiers and / or surfactants are typically used in amounts of 0.001 to 5% based on the hydrophobic phase and / or dispersed phase.

[0184] According to one embodiment, the process steps are carried out in such a way that foam formation is suppressed or reduced. Such embodiments include, for example, the use of suitable mixing equipment and containers, adapting the agitation speed and container shape to minimize foam formation, the use of filling and mixing processes, or the use of suitable dosing equipment or methods, including membrane or microcapillary devices. The suppression or reduction of foam formation may also be achieved by the addition of antifoam (defoaming) agents, which may be introduced at any of the process steps.

[0185] Non-limiting examples of anti-foaming agents include mineral oils, oils, aliphatic esters, alcohols, amides, phosphates, metal soaps, organosilicon compounds, and mixtures thereof.

[0186] It should be understood that the antifoaming agent is not part of the shell.

[0187] When used, antifoaming agents are preferably used in an amount of 0.05 to 1% by weight based on the dispersed phase.

[0188] According to certain embodiments, no amines or polyamines susceptible to polymerization with the multifunctional monomers are added at any stage of the process.

[0189] Dispersion of the oil phase into the aqueous phase can be carried out by various well-known techniques, including but not limited to static mixers (SMX, Sulzer, Switzerland), vibratory mixers, stirred tank reactors, ultrasonic homogenizers, membrane emulsifiers (Micropure, UK), high-pressure homogenizers (APV, SPX Flow, USA) or microfluidic emulsifiers (Micronit, Netherlands).

[0190] According to one embodiment, the multifunctional monomer is selected in the group consisting of at least one isocyanate, anhydride or maleic anhydride, acyl chloride, epoxide, (meth)acrylate monomer, alkoxysilane and mixtures thereof.

[0191] According to a particular embodiment, the monomer added in step i) or ii) is at least one polyisocyanate having at least two isocyanate functional groups.

[0192] Suitable polyisocyanates for use in accordance with 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 (three isocyanate functional groups) are used.

[0193] According to one embodiment, the polyisocyanate is an aromatic polyisocyanate.

[0194] The term "aromatic polyisocyanate," as used herein, is intended to encompass any polyisocyanate containing an aromatic moiety. Preferably, the aromatic moiety contains a phenyl, toluyl, xylyl, naphthyl, or diphenyl moiety, more preferably a toluyl or xylyl moiety. Preferred aromatic polyisocyanates are biurets, polyisocyanurates, and trimethylolpropane adducts of diisocyanates, more preferably containing one of the specific aromatic moieties listed above. More preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® RC), a trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® L75), or a trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name Takenate® D-110N). In a most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

[0195] According to another embodiment, the polyisocyanate is an aliphatic polyisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain an aromatic moiety. Preferred aliphatic polyisocyanates are the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, the trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals), or the biuret of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N 100), of which the biuret of hexamethylene diisocyanate is even more preferred.

[0196] According to another embodiment, the polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both containing at least two or three isocyanate functional groups, such as a mixture of hexamethylene diisocyanate biuret and xylylene diisocyanate trimethylolpropane adduct, a mixture of hexamethylene diisocyanate biuret and toluene diisocyanate polyisocyanurate, or a mixture of hexamethylene diisocyanate biuret and toluene diisocyanate trimethylolpropane adduct. A mixture of hexamethylene diisocyanate biuret and xylylene diisocyanate trimethylolpropane adduct is most preferred. 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.

[0197] According to one embodiment, the multifunctional monomer is an acyl chloride.

[0198] According to a particular embodiment, the acyl chloride has the following formula (I): [ka] In the formula, n is an integer of 1 to 8, preferably 1 to 6, and more preferably 1 to 4. X is an (n+1)-valent C2 to C6 alkyl group optionally containing at least one group selected from (i) to (xi), particularly (i) to (vi). 45 is a hydrocarbon group, [ka] R is a hydrogen atom or an alkyl group such as a methyl group or an ethyl group, preferably a hydrogen atom.

[0199] By "...hydrocarbon group..." is meant that the group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i.e., a linear or branched saturated hydrocarbon (e.g., an alkyl group), a linear or branched unsaturated hydrocarbon (e.g., an alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g., a cycloalkyl), or an unsaturated cyclic hydrocarbon (e.g., a cycloalkenyl or cycloalkynyl), or an aromatic hydrocarbon, i.e., an aryl group, or may be in the form of a mixture of the above types of groups; for example, a particular group may contain linear alkyl, branched alkenyl (e.g., having one or more carbon-carbon double bonds), (poly)cycloalkyl, and aryl moieties, unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of more than one type of topology (e.g., linear, cyclic, or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic, or alkenyl), it also means that the group may contain moieties having any one of the above topologies, or moieties that are saturated or unsaturated, as explained above. Similarly, in any embodiment of the present invention, when a group is referred to as being in one type of saturated or unsaturated form (e.g., alkyl), it means that the group can be of any type of topology (e.g., linear, cyclic, or branched) or can have some moieties with different topologies.

[0200] The term "hydrocarbon group optionally comprising" is understood to mean that said hydrocarbon group optionally comprises heteroatoms and forms ether, thioether, amine, nitrile or carboxylic acid groups and derivatives, including, for example, esters, acids, amides. These groups may replace hydrogen atoms of the hydrocarbon group and thus be laterally attached to said hydrocarbon, or may replace carbon atoms (where chemically possible) of the hydrocarbon group and thus be inserted into a hydrocarbon chain or ring.

[0201] According to certain embodiments, the acyl chloride is selected from the group consisting of benzene-1,3,5-tricarbonyl trichloride (trimesoyl trichloride), benzene-1,2,4-tricarbonyl trichloride, benzene-1,2,4,5-tetracarbonyl tetrachloride, cyclohexane-1,3,5-tricarbonyl trichloride, isophthaloyl dichloride, diglycolyl dichloride, terephthaloyl chloride, fumaryl dichloride, adipoyl chloride, succinic acid dichloride, propane-1, 2,3-Tricarbonyl trichloride, Cyclohexane-1,2,4,5-tetracarbonyl tetrachloride, 2,2'-disulfanediyldisuccinyl dichloride, 2-(2-chloro-2-oxo-ethyl)sulfanylbutanedioyl dichloride, (4-chloro-4-oxabutanoyl)-L-glutamoyl dichloride, (S)-4-((1,5-dichloro-1,5-dioxopentan-2-yl)amino)-4-oxobutanoic acid, 2,2-bis[(4-chloro-4-oxo so-butanoyl)oxymethyl]butyl 4-chloro-4-oxo-butanoate, [2-[2,2-bis[(4-chloro-4-oxo-butanoyl)oxymethyl]butoxymethyl]-2-[(4-chloro-4-oxo-butanoyl)oxymethyl]butyl]4-chloro-4-oxo-butanoate, 2,2-bis[(2-chlorocarbonylbenzoyl)oxymethyl]butyl 2-chlorocarbonyl-benzoate, [2-[2,2-bis[(2-chlorocarbonylbenzoyl )oxymethyl]butoxymethyl]-2-[(2-chlorocarbonylbenzoyl)oxymethyl]butyl] 2-chlorocarbonylbenzoate, 4-(2,4,5-trichlorocarbonylbenzoyl)oxybutyl 2,4,5-trichlorocarbonyl-benzoate, propane-1,2,3-triyltris(4-chloro-4-oxobutanoate), propane-1,2-diylbis(4-chloro-4-oxobutanoate), and mixtures thereof.

[0202] According to one embodiment, the polyfunctional monomer used in the process of the present invention is present in an amount corresponding to 0.1 to 15% by weight, preferably 0.5 to 3% by weight, based on the total amount of the oil phase.

[0203] According to any of the previous embodiments, in addition to the multifunctional monomer present in the oil phase, the aqueous phase may include an amino resin.

[0204] Another object of the present invention is the core-shell microcapsule slurry obtained by the process disclosed above.

[0205] Perfuming compositions and consumer products The microcapsules of the present invention can be used in combination with active ingredients. (i) microcapsules or microcapsule slurries as defined above, (ii) A composition comprising an active ingredient preferably selected from the group consisting of a cosmetic ingredient, a skin care ingredient, a fragrance ingredient, a flavoring ingredient, a malodor control ingredient, a bactericidal ingredient, a fungicidal ingredient, a pharmaceutical or pesticide ingredient, a disinfectant ingredient, an insect repellent or insect attractant, and mixtures thereof.

[0206] The capsules of the present invention exhibit good performance in terms of stability in difficult media.

[0207] Another object of the present invention is to provide (i) microcapsules or microcapsule slurries as defined above, wherein the oil contains a fragrance; (ii) at least one component selected from the group consisting of cosmetic carriers, cosmetic adjuncts, and mixtures thereof; (iii) Optionally, a perfuming composition comprising at least one cosmetic adjuvant.

[0208] Non-limiting examples of liquid cosmetic carriers include emulsifying systems, i.e., solvent and surfactant systems, or solvents commonly used in cosmetics. A detailed description of the nature and types of solvents commonly used in cosmetics cannot be exhaustive. However, non-limiting examples include the most commonly used solvents, such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol, or ethyl citrate. For compositions containing both a cosmetic carrier and a cosmetic auxiliary ingredient, other suitable cosmetic carriers besides those specified above may also include ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those known under the trademark Isopar® (manufactured by Exxon Chemical), or glycol ethers and glycol ether esters, such as those known under the trademark Dowanol® (manufactured by Dow Chemical Company). By "perfume adjunct" is meant herein a compound that is used in a perfume preparation or composition to impart a hedonic effect and is not a microcapsule as defined above. In other words, to be considered perfuming, such an adjunct must be recognized by those skilled in the art not only as having an odor, but also as being able to at least impart or modify the odor of the composition in a positive or pleasant way.

[0209] The nature and type of perfuming co-ingredients present in the perfuming composition do not warrant further detailed description herein, and are in any case not exhaustive; those skilled in the art can select them based on their general knowledge and in accordance with the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming co-ingredients belong to various chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen or sulfite heterocyclic compounds, and essential oils, and said perfuming co-ingredients may be of natural or synthetic origin. Many of these co-ingredients are listed in reference works such as S. Arctander, *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its more recent editions, or other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may be compounds known to release various types of perfuming compounds in a controlled manner. The auxiliary ingredients are 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-(1-phenethoxyprop-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 or mixtures thereof.

[0210] By "cosmetic adjuvant" is meant herein an ingredient capable of imparting additional benefits such as color, specific light resistance, chemical stability, etc. A detailed description of the nature and types of adjuvants commonly used in perfume bases is not exhaustive, but it should be mentioned that said ingredients are well known to those skilled in the art.

[0211] Preferably, the perfuming composition according to the invention comprises 0.01 to 30% by weight of microcapsules or microcapsule slurries as defined above.

[0212] The microcapsules of the present invention can be advantageously used in many fields of application and can be used in consumer products, in liquid form applicable to liquid consumer products, and in powder form applicable to powder consumer products.

[0213] According to a particular embodiment, the consumer product as defined above is liquid and comprises: a) 2 to 65% by weight of at least one surfactant, based on the total weight of the consumer product; b) water or a water-miscible hydrophilic organic solvent, and c) microcapsule slurries or microcapsules as defined above, d) Optionally, non-encapsulated flavorings.

[0214] According to a particular embodiment, the consumer product as defined above is in powder form and comprises: a) 2 to 65% by weight of at least one surfactant, based on the total weight of the consumer product; b) Microcapsule powder as defined above. c) Optionally, a flavoring powder different from the microcapsules defined above.

[0215] In the case of microcapsules containing a perfume oily core, the product of the present invention can be used in perfumed consumer products, such as those belonging to fine fragrance or "functional" cosmetics. Functional cosmetics include, in particular, personal care products, including hair care, body cleansing, skin care, and hygiene care, as well as home care products, including laundry care, surface care, and air care. Therefore, another object of the present invention consists in perfumed consumer products containing the microcapsules defined above or the perfume composition defined above as a perfume ingredient. The perfume element of said consumer product can be a combination of the perfume microcapsules defined above, free encapsulated or non-encapsulated perfume, and other types of perfume microcapsules other than those disclosed herein.

[0216] In particular, liquid consumer products, a) 2 to 65% by weight of at least one surfactant, based on the total weight of the consumer product; b) water or a water-miscible hydrophilic organic solvent, and c) A liquid consumer product comprising a perfuming composition as defined above is another object of the present invention.

[0217] Also, a powder consumer product comprising: (a) 2 to 65 wt. % of at least one surfactant, based on the total weight of the consumer product; and (b) Powdered consumer products comprising the perfuming composition defined above are part of the present invention.

[0218] Thus, the microcapsules of the present invention can be added to perfumed consumer products either as such or as part of the perfume composition of the present invention.

[0219] For the sake of clarity, it must be mentioned that by "perfumed consumer product" is meant a consumer product that is expected to provide, among other benefits, a perfume effect to the surface to which it is applied (e.g., skin, hair, fabric, paper or household surfaces) or in the air (air freshener, deodorant, etc.). In other words, a perfumed consumer product according to the invention is a manufactured product that comprises a functional formulation, also called a "base", together with an effective amount of a benefit agent, in particular the microcapsules according to the invention.

[0220] The nature and type of other components of perfumed consumer products do not warrant further detailed description herein, and in any case, this description is not exhaustive, and those skilled in the art can select them based on their general knowledge according to the nature and desired effect of the product.Base formulations of consumer products that can incorporate the microcapsules of the present invention can be found in the abundant literature on such products.These formulations do not warrant further detailed description herein, and in any case, this description is not exhaustive.Those skilled in the art of formulating such consumer products can completely select suitable ingredients based on their general knowledge and available literature.

[0221] Non-limiting examples of suitable perfumed consumer products include fragrances, such as fine fragrances, colognes, aftershaves, body splashes; fabric care products, such as liquid or solid detergents, tablets and unit doses (single or multi-chamber), fabric softeners, dryer sheets, fabric refreshers, ironing waters or bleaches; personal care products, such as hair care products (e.g., shampoos, hair conditioners, colorants or hairsprays), cosmetics (e.g., vanishing creams, body lotions or deodorants or antiperspirants) or skin care products (e.g., air care products, such as air fresheners or "ready to use" powdered air fresheners; or home care products, such as all-purpose cleaners, liquid or powder or tablet dishwashing products, toilet cleaners, or products for cleaning various surfaces, such as sprays and wipes intended to treat / refresh textile or hard surfaces (floors, tiles, stone floors, etc.); hygiene products, such as sanitary napkins, diapers, toilet paper.

[0222] Another object of the present invention is to provide Personal care active bases, and A consumer product comprising a microcapsule or a microcapsule slurry as defined above, or a perfuming composition as defined above, It is a consumer product in the form of a personal care composition.

[0223] The personal care active bases that can incorporate the microcapsules of the present invention can be found in the abundant literature on such products.These formulations do not warrant the detailed description herein, and are in any case not exhaustive.Those skilled in the art of formulating such consumer products can completely select suitable ingredients based on their general knowledge and available literature.

[0224] The personal care composition is preferably selected in the group consisting of hair care products (e.g. shampoos, hair conditioners, colorants or hair sprays), cosmetics (e.g. vanishing creams, body lotions or deodorants or antiperspirants) or skin care products (e.g. perfumed soaps, shower or bath mousses, body washes, oils or gels, bath salts or hygiene products);

[0225] Another object of the present invention is to provide Home care active bases or fabric care active bases, and A consumer product comprising a microcapsule or a microcapsule slurry as defined above, or a perfuming composition as defined above, Consumer products in the form of home care or fabric care compositions.

[0226] Home care active bases or fabric care active bases that can incorporate the microcapsules of the present invention can be found in the abundant literature on such products.These formulations do not warrant detailed description herein, and are in any case not exhaustive.Those skilled in the art of formulating such consumer products can fully select suitable ingredients based on their general knowledge and available literature.

[0227] Preferably, the consumer product contains 0.1 to 15% by weight, more preferably 0.2 to 5% by weight, of the microcapsules or microcapsule slurry of the present invention, these percentages being defined by weight relative to the total weight of the consumer product. Naturally, the above concentrations may be adapted according to the desired beneficial effect for each product.

[0228] An object of the present invention is a consumer product, preferably a home care consumer product or a fabric care consumer product, comprising microcapsules or a microcapsule slurry as defined above, wherein the consumer product has a pH of less than 7.

[0229] An object of the present invention is a consumer product, preferably a home care consumer product or a fabric care consumer product, comprising microcapsules or a microcapsule slurry as defined above, wherein the consumer product has a pH of 7 or greater.

[0230] In the case of liquid consumer products referred to below, by "active base" it should be understood that the active base comprises active ingredients (which typically include surfactants) and water.

[0231] In the case of solid consumer products referred to below, by "active base" it should be understood that the active base includes active materials (which typically include surfactants) and adjuvants (bleaches, buffers; builders; soil release or suspension polymers; granulating enzyme particles, corrosion inhibitors, antifoaming agents, foam suppressants; dyes, fillers and mixtures thereof, etc.).

[0232] Fabric softener The object of the present invention is to a fabric softener active base preferably comprising at least one active material selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (ester quats), Hamburg ester quats (HEQ) (1,2-stearoyl-3-trimethylammonium-propane (chloride salt)), TEAQ (triethanolamine quat), silicones and mixtures thereof, wherein the active base is preferably used in an amount of 85 to 99.95 wt. %, based on the total weight of the composition; microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, - A consumer product in the form of a fabric softener composition, optionally containing free perfume oil.

[0233] Liquid detergent The object of the present invention is to a liquid detergent active base preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkylbenzenesulfonates (ABS), secondary alkylsulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides, wherein the active base is preferably used in an amount of 85 to 99.95% by weight, based on the total weight of the composition; microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, - A consumer product in the form of a liquid detergent composition, optionally containing free perfume oil.

[0234] Solid detergent The object of the present invention is to a solid detergent active base preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkyl benzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkyl amines, alkanol amides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides, wherein the active base is preferably used in an amount of 85 to 99.95 wt. %, based on the total weight of the composition; a microcapsule powder or a microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, A consumer product in the form of a solid detergent composition, optionally containing free perfume oil.

[0235] Shampoo / Shower gel The object of the present invention is to a shampoo or shower gel active base preferably comprising at least one active material selected from the group consisting of sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside, and amino acid surfactants, and mixtures thereof, wherein the active material is preferably used in an amount of 85 to 99.95% by weight, based on the total weight of the composition; microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, a consumer product in the form of a shampoo or shower gel composition, optionally containing free perfume oil.

[0236] Rinse-off conditioner The object of the present invention is to 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, the active base preferably being used in an amount of 85 to 99.95% by weight, based on the total weight of the composition; microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, A consumer product in the form of a rinse-off conditioner composition, optionally containing free fragrance oil.

[0237] Solid Aroma Booster The object of the present invention is to solid carriers preferably selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolites, sodium carbonate, sodium bicarbonate, clays, 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, microcapsule slurries or microcapsules as defined above in powder form, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, A consumer product in the form of a solid fragrance booster composition, optionally containing free fragrance oil.

[0238] Liquid Aroma Booster The object of the present invention is to ·Aqueous phase, a surfactant system consisting essentially of a plurality of nonionic surfactants, the surfactant system having an average HLB of 10 to 14 and preferably selected from the group consisting of ethoxylated fatty alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono- and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxyl esters, alkyl polyglucosides, amine oxides and combinations thereof; a linker selected from the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxylcarboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants with an HLB of less than 10 and mixtures thereof, and microcapsule slurry or microcapsules as defined above in the form of a slurry, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, A consumer product in the form of a liquid fragrance booster composition, optionally containing free fragrance oil.

[0239] Hair coloring The object of the present invention is to an oxidation phase comprising an oxidizing agent, and an alkaline phase comprising an alkalizing agent, a dye precursor and a coupling compound, wherein said dye precursor and said coupling compound in the presence of the oxidizing agent form an oxidative hair dye, preferably in an amount of 85 to 99.95 wt. %, based on the total weight of the composition; microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, A consumer product in the form of an oxidative hair coloring composition, optionally containing free fragrance oil.

[0240] Perfuming composition According to certain embodiments, the consumer product comprises: 0.1 to 30%, preferably 0.1 to 20%, of the microcapsule slurry or microcapsules defined above, Fragrance 0-40%, preferably 3-40%, and The fragrance composition contains 20 to 90% by weight, preferably 40 to 90% by weight, of ethanol based on the total weight of the fragrance composition.

[0241] The present 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.

[0242] Example Example 1 Potato protein-based composite microcapsules Protocol for preparing microcapsules A A potato protein solution (Solanic® 200, manufactured by Avebe) was prepared in DI water (natural pH 6.8).

[0243] A gum arabic solution (Superstab™, manufacturer: Nexira) was prepared in DI water.

[0244] The potato protein solution and gum arabic solution were adjusted to pH 2 using concentrated HCl (37%) and then mixed to obtain the aqueous phase.

[0245] An oil phase containing polyisocyanate (Takenate® - trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc., Japan, a 75% solution of polyisocyanate in ethyl acetate) and fragrance oil (see Table 1) was prepared and then added to the aqueous phase (potato protein / gum arabic solution (pH approx. 2)) under Ultra-Turrax at 13,500 rpm for 1 minute to obtain an oil-in-water emulsion.

[0246] The pH was then raised to pH 3 by adding NaOH 1M (0.73 g) with stirring.

[0247] After coacervation was confirmed by optical microscopy, glutaraldehyde was added and the suspension was stirred at room temperature for 4 hours.

[0248] [Table 1]

[0249] [Table 2]

[0250] Figures 1 and 2 represent optical and SEM microscopy of the microcapsules, respectively.

[0251] Example 2 Potato protein-based composite microcapsules Microcapsules B were prepared according to the protocol of Example 1, except that the suspension was heated to 85°C for 30 minutes at the end of the process.

[0252] Example 3 Canola protein composite microcapsules Protocol for preparing microcapsules C A 50 g 4% solution of canola protein (CP) (CanolaPro®, manufacturer: DSM) was prepared in deionized water (natural pH=6.5). A 50 g 4% solution of gum arabic (GA) (Superstab™, manufacturer: Nexira) was prepared in deionized water (pH=6).

[0253] Both solutions were mixed together and concentrated HCl (37%) (0.36 g) was added to lower the pH to 2.4.

[0254] An oil solution made from 30g of perfume and 0.75g of Takenate® D110N was added to the biopolymer solution and sheared using an ultra turrax at 9500 rpm for 2 minutes to form an oil-in-water emulsion.

[0255] The pH of the emulsion was then adjusted to 4.09 by dropwise addition of NaOH 1 M solution (2.3 g) under mechanical stirring.

[0256] Coacervation of the CP / GA complex around the oil droplets was confirmed by optical microscopy.

[0257] Next, 0.22 g of a 50% solution of glutaraldehyde was added to the resulting suspension, and the slurry was stirred at room temperature at 800 rpm for 3.5 hours, and then heated at 75°C for 1 hour under the same stirring conditions.

[0258] [Table 3]

[0259] Figure 3 shows optical and SEM microscopy of the microcapsules, respectively.

[0260] Example 4 Stability of the microcapsules of the present invention The microcapsules of the present invention are dispersed in a fabric softener (FS) composition as set forth in Table 4 or a liquid detergent (LD) composition as set forth in Table 5 to obtain a concentration of 0.116% encapsulated perfume oil.

[0261] [Table 4]

[0262] [Table 5]

[0263] 2 g of sample (base containing capsules) is weighed into a 20 mL vial. 10 mL of extraction solvent isooctane containing an internal standard 1,4-dibromobenzene with a precisely known concentration of approximately 90 ng / uL is added to the vial. This is then shaken at 40 RPM for 45 minutes to extract the free flavor. The solvent phase is then removed.

[0264] To measure base leakage, an Agilent GCFID7890A is used, the injector is set to 250°C, helium is used as the carrier gas at a flow rate of 1 mL / min, and the oven temperature is programmed from 120°C, held for 5 minutes, ramped to 170°C at 10°C / min, ramped to 220°C at 25°C / min, and then ramped to 260°C at 25°C / min. A later run is applied at 260°C to complete the measurement.

[0265] Prepare calibration solutions at 100, 300, and 600 ng / uL fragrance oil in isooctane. It is important that the fragrance oil used to create the calibration curve comes from the same batch as that used to produce the microcapsules.

[0266] The stability of microcapsules A and B is shown in Figures 4 and 5, respectively.

[0267] It can be concluded that the microcapsules of the present invention exhibit good stability in fabric softeners and liquid detergents.

[0268] Example 5 Olfactory performance of the microcapsules of the present invention protocol The perfume oil dosage in the fabric softener was 0.1%. The perfume oil dosage in the liquid detergent was 0.2%.

[0269] Washing Protocol: Program: 40℃ - Short rotation - 900 rpm Towels: 36 Unscented detergent: 55g Fabric softener: 23g

[0270] Storage Protocol Drying: The towels were placed on a drying rack for 1 day to dry.

[0271] evaluation: One pair of towels per panelist: Panelists were asked to smell the dried towels and rate the fragrance intensity using a scale of 0 (no odor) to 10 (extremely strong odor). They then rubbed the towels back and forth three times and asked to rate the fragrance intensity after rubbing using the same scale.

[0272] [Table 6]

[0273] A noticeable perfume boost after scrubbing was observed in both fabric conditioner and liquid detergent applications.

[0274] Example 6 Microcapsules Biodegradable Shell extraction (following the method disclosed in Gasparini and all in Molecules 2020, 25, 718) The microcapsule slurry was freeze-dried. The collected solid was milled for 30 seconds using an IKA tube-mill control. The resulting paste (fragrance oil + polymer shell) was suspended in 300 mL of ethyl acetate, and the mixture was stirred at room temperature for 1 hour. The solid was collected by filtration under vacuum using a Gooch filter crucible (porosity 4). This extraction process was repeated five times to remove the maximum amount of fragrance oil from the shell. The powder was dried under vacuum (10 mBar) at 50°C until the polymer weight, monitored by gravimetry, was constant. The resulting powder was milled for 1 minute and 30 seconds using an IKA tube-mill control, suspended in Di water (0.5% w / w), and stirred at 300 RPM for 24 hours at room temperature. The water was removed by filtration under vacuum using a Gooch filter crucible (porosity 4), and the powder was dried at room temperature for 2.5 days, then under vacuum (10 mBar) at 50°C overnight. Finally, the resulting powder was ground for 1 minute 30 seconds using an IKA tube-mill control and extracted five more times with ethyl acetate as described above. The final powder was dried overnight under vacuum (10 mBar) at 50°C. To ensure complete removal of the fragrance, samples were analyzed by GC pyrolysis and sent for biodegradation analysis according to OECD method 301F.

[0275] The biodegradability of the shell of Microcapsule A was greater than 50% after 60 days of testing.

[0276] Example 7 Shell Composition of the Capsules of the Invention as Determined by Solid-State NMR NMR made it possible to determine the following shell composition of microcapsule A based on the carbon signals from the individual components: 52% potato protein 28% Gum Arabic 14% Polyisocyanate 6% balance (glutaraldehyde)

[0277] Furthermore, relaxation time measurements showed that all nuclei statistically had the same environment underlying the homogeneity of the shell.

[0278] Example 8 Spray-dried microcapsule preparation Emulsions A to E are prepared having the following components:

[0279] [Table 7]

[0280] [Table 8]

[0281] The ingredients of the polymer matrix (maltodextrin and capsul™, or capsul™, citric acid and tripotassium citrate) are added to water at 45-50°C until completely dissolved.

[0282] For emulsion D, free perfume C is added to the water phase.

[0283] The microcapsule slurry is added to the resulting mixture, which is then gently mixed at 25°C (room temperature).

[0284] Granulated powders A to E are prepared by spray drying emulsions A to E using a Sodeva Spray Dryer (manufacturer, France) with the air inlet temperature set at 215°C and a throughput of 500 ml / h. The air outlet temperature is 105°C. The emulsions before atomization are at ambient temperature.

[0285] Example 9 Liquid fragrance booster composition A sufficient amount of the exemplified microcapsules is weighed and mixed in a liquid fragrance booster to add the equivalent of 0.2% fragrance.

[0286] [Table 9]

[0287] Prepare different ringing gel compositions according to the following protocol (compositions 1-6).

[0288] In the first step, the aqueous phase (water), the solvent (propylene glycol), if present, and the surfactant are mixed together at room temperature with a magnetic stirrer at 300 rpm for 5 minutes.

[0289] In the second step, the linker is dissolved in the hydrophobic active ingredient (fragrance) at room temperature while stirring at 300 rpm using a magnetic stirrer. The resulting mixture is mixed for 5 minutes.

[0290] The water and oil phases are then mixed together at room temperature for 5 minutes to form a clear or milky ringing gel.

[0291] Example 10 Liquid detergent composition A sufficient amount of the exemplified microcapsules is weighed and mixed into a liquid detergent to add the equivalent of 0.2% perfume.

[0292] [Table 10]

[0293] Example 11 Unit Dose Formulations A sufficient amount of the exemplary microcapsules is weighed and mixed in a unit dose formulation to add the equivalent of 0.2% fragrance.

[0294] The unit dose formulation can be contained in a PVOH (polyvinyl alcohol) film.

[0295] [Table 11]

[0296] Example 12 Powder detergent composition A sufficient amount of the exemplified microcapsules is weighed and mixed into a powder detergent composition to add the equivalent of 0.2% perfume.

[0297] [Table 12]

[0298] Example 13 Concentrated multi-use cleaner composition A sufficient amount of the exemplary microcapsules is weighed and mixed into a concentrated all-purpose cleaner composition to add the equivalent of 0.2% perfume.

[0299] [Table 13]

[0300] All ingredients were mixed together and then the mixture was diluted to 100% with water.

[0301] Example 14 Solid fragrance booster composition The following compositions are prepared:

[0302] [Table 14]

[0303] [Table 15]

[0304] Example 15 Shampoo composition A sufficient amount of the exemplified microcapsules is weighed and mixed into a shampoo composition to add the equivalent of 0.2% perfume.

[0305] [Table 16]

[0306] Polyquaternium-10 is dispersed in water. The remaining ingredients of Phase A are mixed separately by sequential addition, mixing thoroughly after each adjustment. This premix is then added to the Polyquaternium-10 dispersion and mixed for 5 minutes. Phase B and premixed Phase C (heat to melt Monomuls 90L-12 in Texapon NSO IS) are then added. The mixture is mixed thoroughly. Phases D and E are then added with stirring. The pH is adjusted with citric acid solution until the pH is 5.5-6.0.

[0307] Example 16 Shampoo composition A sufficient amount of the exemplified microcapsules is weighed and mixed into a shampoo composition to add the equivalent of 0.2% perfume.

[0308] [Table 17]

[0309] The premix containing guar hydroxypropyltrimonium chloride and polyquaternium-10 is added to the water and tetrasodium EDTA while mixing. When the mixture is homogeneous, NaOH is added. Phase C ingredients are then added and the mixture is heated to 75°C. Phase D ingredients are added and mixed until homogeneous. Heating is stopped and the mixture is allowed to cool to room temperature. At 45°C, while mixing the ingredients of Phase E, the final viscosity is adjusted with 25% NaCl solution and the pH is adjusted to 5.5-6 with 10% NaOH solution.

[0310] Example 17 Rinse-off hair composition A sufficient amount of the exemplified microcapsules is weighed and mixed into a rinse-off composition to add the equivalent of 0.2% perfume.

[0311] [Table 18]

[0312] Mix the ingredients of Phase A until a homogeneous mixture is obtained. Completely dissolve the tylose. Then heat the mixture to 70-75°C. Combine the ingredients of Phase B and melt at 70-75°C. Then add the ingredients of Phase B to Phase A with thorough mixing and continue mixing until cooled to 60°C. Then add the ingredients of Phase C with stirring and continued mixing until the mixture cools to 40°C. Adjust the pH with citric acid solution until the pH is 3.5-4.0.

[0313] Example 18 Antiperspirant spray anhydrous composition A sufficient amount of the exemplary microcapsules is weighed and mixed into an antiperspirant spray anhydrous composition to add the equivalent of 0.2% perfume.

[0314] [Table 19]

[0315] Using a high-speed stirrer, add the silica and quaternium-18-hectorite to the mixture of isopropyl myristate and cyclomethicone. Once fully swollen, add the aluminum chlorohydrate in small increments with stirring until the mixture is homogeneous and free of lumps. Fill an aerosol can with 25% of the suspension and 75% of the propane / butane (2.5 bar).

[0316] Example 19 Antiperspirant spray emulsion composition A sufficient amount of the exemplary microcapsules is weighed and mixed into an antiperspirant spray emulsion composition to add the equivalent of 0.2% perfume.

[0317] [Table 20]

[0318] The ingredients of Part A and Part B are weighed separately. The ingredients of Part A are heated to 60°C and the ingredients of Part B are heated to 55°C. With continuous stirring, the ingredients of Part B are poured into A in small portions. The mixture is stirred thoroughly until it reaches room temperature. The ingredients of Part C are then added. The emulsion is mixed and introduced into an aerosol can. The propellant is compressed and added.

[0319] Aerosol filling: 30% emulsion: 70% propane / butane 2.5bar

[0320] Example 20 Deodorant spray composition A sufficient amount of the exemplary microcapsules is weighed and mixed into an antiperspirant deodorant spray composition to add the equivalent of 0.2% perfume.

[0321] [Table 21]

[0322] All ingredients are mixed and dissolved according to the order in Table 24. Aerosol cans are then filled, compressed and propellant added (aerosol fill: 40% active solution 60% propane / butane 2.5 bar).

[0323] Example 21 Antiperspirant roll-on emulsion composition A sufficient amount of the exemplary microcapsules is weighed and mixed into an antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.

[0324] [Table 22]

[0325] Parts A and B are heated separately to 75°C, part A is added to part B while stirring, and the mixture is homogenized for 10 minutes. The mixture is then cooled while stirring, and part C is added slowly while stirring when the mixture reaches 45°C, and part D when the mixture reaches 35°C. The mixture is then cooled to room temperature.

[0326] Example 22 Antiperspirant roll-on composition A sufficient amount of the exemplary microcapsules is weighed and mixed into an antiperspirant roll-on composition to add the equivalent of 0.2% perfume.

[0327] [Table 23]

[0328] The ingredients of Part B are mixed in a container, then the ingredients of Part A are added. Part C is then dissolved in Parts A and B. Along with the fragrance, 1 part Cremophor RH40 is added to 1 part fragrance while mixing thoroughly.

[0329] Example 23 Antiperspirant roll-on composition A sufficient amount of the exemplary microcapsules is weighed and mixed into an antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.

[0330] [Table 24]

[0331] Part A is prepared by gradually sprinkling hydroxyethyl cellulose into water while rapidly stirring with a turbine. Stirring is continued until the hydroxyethyl cellulose is completely swollen and a clear gel is obtained. Then, while continuing to stir until the whole is homogeneous, part B is poured into part A little at a time. Add part C.

[0332] Example 24 Alcohol-free deodorant pump A sufficient amount of the exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.

[0333] [Table 25]

[0334] Mix all ingredients in the order listed and heat the mixture slightly to dissolve the cetyl lactate.

[0335] Example 25 Deodorant pump containing alcohol formulation A sufficient amount of the exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.

[0336] [Table 26]

[0337] Mix together the ingredients from Part B. Dissolve the ingredients of Part A in the order listed and pour into Part B.

[0338] Example 26 Talc Compound A sufficient amount of granules A to E is weighed out and introduced into a standard talc base: 100% talc, very slight characteristic odor, white powder, manufacturer: LUZENAC, mixed, and 0.2% equivalent of flavoring is added.

[0339] Example 27 Shower gel reference A sufficient amount of the exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.

[0340] [Table 27]

[0341] Mix the ingredients and adjust the pH to 6-6.3 (viscosity: 4500 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0342] Example 28 Shower gel composition A sufficient amount of the exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.

[0343] [Table 28]

[0344] The ingredients are mixed and the pH is adjusted to 4.5 (viscosity: 3000 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0345] Example 29 Shower gel composition A sufficient amount of the exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.

[0346] [Table 29]

[0347] The ingredients are mixed and the pH adjusted to 4.5 (viscosity: 4000 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0348] Example 30 Hand-washing dish detergent A sufficient amount of the exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.

[0349] [Table 30]

[0350] Mix diethanolamide with water containing sodium hydroxide. Add LAS. After neutralizing the LAS, add the remaining ingredients. Check the pH (7-8) and adjust if necessary.

[0351] Example 31 Soap bar formulations A soap bar composition containing the exemplary microcapsules is prepared at a concentration of 7.5% w / w.

[0352] [Table 31]

[0353] Example 32 Toothpaste formulations A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor:

[0354] [Table 32]

[0355] Example 33 Dicalcium phosphate toothpaste formulations A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor:

[0356] [Table 33]

[0357] Example 34 Alcohol-free mouthwash formula A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor:

[0358] [Table 34]

[0359] Example 35 Mouthwash formulations A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor:

[0360] [Table 35]

Claims

1. 1. A core-shell microcapsule comprising a core comprising a hydrophobic material, preferably a perfume oil, and a polymeric shell, wherein the polymeric shell comprises: - a polymer material; a coacervate comprising a first polyelectrolyte and a second polyelectrolyte, wherein the first polyelectrolyte comprises a plant protein; Core-shell microcapsules.

2. 2. The microcapsule of claim 1, wherein the polymeric material and the coacervate are homogeneously distributed within the shell.

3. 3. The microcapsules of claim 1 or 2, wherein the plant protein is selected from the group consisting of potato protein, chickpea protein, pea protein, faba bean protein, barley protein, oat protein, soy protein, algae protein, wheat gluten protein, lupin protein, canola protein, hemp protein, rice protein, sunflower seed protein and mixtures thereof.

4. 4. The microcapsule of claim 3, wherein the plant protein is potato protein.

5. 5. The microcapsules of claim 1, wherein the second polyelectrolyte is selected from the group consisting of gum arabic, alginates, cellulose derivatives, guar gum, pectinates, pectin, carrageenan, polyacrylic and methacrylic acid, cellulose derivatives, xanthan gum, microbial exopolysaccharides, and mixtures thereof.

6. 6. The microcapsule of claim 5, wherein the second polyelectrolyte is gum arabic.

7. 7. The microcapsules of any one of claims 1 to 6, wherein the polymeric material is selected from the group consisting of polyurea, polyester, polyurethane, polyamide, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, poly(beta amino ester), polylactic acid, poly(thiol-acrylate), polymers of urea and formaldehyde, polymers of melamine and formaldehyde, polymers of melamine and urea, or polymers of melamine and glyoxal, and mixtures thereof.

8. The microcapsules according to any one of claims 1 to 7, a core containing a flavoring oil, and A shell comprising a polyurea and a coacervate comprising potato protein and gum arabic. A microcapsule comprising:

9. 9. The microcapsule of claim 1, wherein the polymeric material is present in an amount of less than 10% by weight based on the total weight of the microcapsule.

10. (i) providing a hydrophobic phase comprising a hydrophobic material and at least a multifunctional monomer; (ii) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient to avoid forming a suspension of complex coacervates, wherein the first polyelectrolyte comprises a plant protein; (iii) adding the hydrophobic phase to the dispersed phase to form a two-phase dispersion and applying conditions sufficient to form a coacervate; (iv) providing conditions sufficient to induce interfacial polymerization to form a core-shell microcapsule slurry.

1. A process for preparing core-shell microcapsules comprising:

11. A consumer product base and a microcapsule as defined in any one of claims 1 to 9. A consumer product comprising: Preferably, consumer products in the form of home or personal care products.

12. 12. The consumer product of claim 11, 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), 1,2-stearoyl-3-trimethylammonium-propane (chloride salt), TEAQ (triethanolamine quats), silicones and mixtures thereof, said active base preferably being used in an amount of 85 to 99.95 wt. %, based on the total weight of the composition; Microcapsules as defined in any one of claims 1 to 9, preferably in an amount of 0.05 to 15 wt. %, more preferably 0.1 to 5 wt. %, based on the total weight of the composition. Optionally, free fragrance oil 1. A consumer product in the form of a fabric softener composition comprising:

13. 12. The consumer product of claim 11, A liquid detergent active base preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkyl benzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkyl amines, 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, wherein said active base is preferably used in an amount of 85 to 99.95 wt. %, based on the total weight of the composition; Microcapsules as defined in any one of claims 1 to 9, preferably in an amount of 0.05 to 15 wt. %, more preferably 0.1 to 5 wt. %, based on the total weight of the composition. Optionally, free fragrance oil 1. A consumer product in the form of a liquid detergent composition comprising:

14. 12. The consumer product of claim 11, a solid detergent active base preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkyl benzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkyl amines, 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, said active base preferably being used in an amount of 85 to 99.95 wt. %, based on the total weight of the composition; microcapsules as defined in any one of claims 1 to 9, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition; Optionally, free fragrance oil 1. A consumer product in the form of a solid detergent composition comprising:

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