Composite microcapsules

Abstract

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

[0002] One of the challenges facing the fragrance industry is that the olfactory benefits provided by odoriferous compounds, particularly top notes, are lost relatively quickly due to their volatility. To regulate the release rate of volatiles, delivery systems (e.g., fragrance-containing microcapsules) are required to protect and release the core payload upon triggering. A key requirement for these systems is the ability to remain suspended in challenging bases without physical decomposition or degradation. This is known as the chemical stability of the delivery system. For example, fragrances, personal and household cleansers containing high levels of aggressive surfactant detergents pose significant challenges to microcapsule stability. High levels of surfactant also increase the rate at which the active substance diffuses out of the delivery system, such as the microcapsule. This can lead to leakage of the active substance during storage and a reduction in the initial impact (effectiveness) of the microcapsule upon triggering release. Furthermore, the mechanical stability of the microcapsules can be compromised by physical forces (e.g., crushing) or other methods that compromise the integrity of the microcapsules.

[0003] In addition to performance in terms of stability and olfactory performance, consumer demand for eco-friendly delivery systems is becoming increasingly important and is driving the development of new delivery systems.

[0004] Therefore, there is still a need to provide new microcapsules using more eco-friendly materials without compromising the performance of the microcapsules, in particular with regard to stability in challenging media such as consumer product bases, and with regard to providing good olfactory performance in active ingredient delivery, for example in the case of perfuming ingredients. Summary of the Invention

[0005] It has now been discovered that high performance microcapsules encapsulating hydrophobic materials (such as flavor oils) can be obtained by forming a homogeneous composite shell comprising (or made from) a plant-based coacervate material and a polymeric material.

[0006] A first object of the present invention is a core-shell microcapsule comprising:

[0007] - a core comprising a hydrophobic material, preferably a fragrance oil, and

[0008] - a polymer shell comprising:

[0009] - Polymeric materials, and

[0010] a coacervate comprising a first polyelectrolyte and a second polyelectrolyte,

[0011] The first polyelectrolyte comprises plant protein.

[0012] A second object of the present invention is a method for preparing a core-shell microcapsule slurry, comprising the following steps:

[0013] (i) providing a hydrophobic phase comprising a hydrophobic material and at least one multifunctional monomer;

[0014] (ii) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient not to form a complex coacervate suspension; wherein the first polyelectrolyte comprises a plant protein;

[0015] (iii) adding the hydrophobic phase to the dispersed phase to form a two-phase dispersion, and applying conditions sufficient to form a coacervate,

[0016] (iv) providing conditions sufficient to initiate interfacial polymerization to form a core-shell microcapsule slurry.

[0017] A third object is a slurry of core-shell microcapsules obtained by the process as defined above.

[0018] The present invention also relates to a consumer product in the form of a home care, fabric care or personal care product comprising the microcapsules or the microcapsule slurry.

[0019] Detailed description of the invention

[0020] Unless otherwise indicated, percentages (%) refer to weight percent of the composition.

[0021] By "hydrophobic material," it is meant any hydrophobic material - a single material or a mixture of materials - that forms a two-phase dispersion when mixed with water.

[0022] By "ingredient" is meant a single compound or a combination of ingredients.

[0023] By "spice oil or flavoring (flavor) oil" is meant a single flavoring or flavoring compound or a mixture of several flavoring or flavoring compounds.

[0024] By “consumer product” or “final product,” we mean a finished good that is ready for distribution, sale, and use by consumers.

[0025] In the present invention, "microcapsules" or similar expressions refer to core-shell microcapsules having a particle size distribution in the micrometer range (e.g., an average diameter (Dv(50) of about 1 to 3000 micrometers) and comprising an outer polymer-based shell and an inner hydrophobic phase surrounded by the outer shell. According to one embodiment, the average diameter of the microcapsules is 1 to 500 micrometers, preferably between 2 and 200 micrometers, more preferably 4 to 100 micrometers, and even more preferably 4 to 50 micrometers.

[0026] According to the invention, the expressions "average diameter" or "average size" are used indifferently. According to one embodiment, the microcapsules are not agglomerated. According to another embodiment, the microcapsules are partially agglomerated. According to another embodiment, all of the microcapsules are agglomerated.

[0027] By "microcapsule slurry" is meant microcapsules dispersed in a liquid. According to one embodiment, the slurry is an aqueous slurry, ie the microcapsules are dispersed in an aqueous phase.

[0028] The microcapsules of the present invention are composite microcapsules. By "composite microcapsules," we mean 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 polymeric material). According to the present invention, "coacervate" or "hydrogel" can be used interchangeably. By hydrogel, we mean a polymer network swollen with water.

[0029] According to one embodiment, the composite shell is also understood to be a homogeneous shell, meaning that the plant-based coacervate and the polymeric material are uniformly dispersed within the shell. In other words, the microcapsule does not comprise two distinct layers, but rather a single composite shell. The microcapsules according to the present invention do not comprise an inner shell of polymeric material and an outer shell of coacervate.

[0030] According to one specific embodiment, the polymeric shell comprises the reaction product of a polymeric material and a coacervate. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figures 1 to 3 Optical microscope and SEM images of the microcapsules of the present invention are shown respectively.

[0032] Figure 4 and Figure 5 Represents the olfactory performance of microcapsule A and microcapsule B in fabric softener and liquid detergent, respectively. DETAILED DESCRIPTION

[0033] microcapsules

[0034] A first object of the present invention is a core-shell microcapsule comprising:

[0035] - a core comprising a hydrophobic material, preferably a fragrance oil, and

[0036] - a polymer shell comprising:

[0037] - Polymeric materials, and

[0038] a coacervate comprising a first polyelectrolyte and a second polyelectrolyte,

[0039] The first polyelectrolyte comprises plant protein.

[0040] Another object is a slurry comprising the microcapsules as defined above.

[0041] hydrophobic materials

[0042] According to one embodiment, the core is an oil-based core.

[0043] The hydrophobic material according to the present invention may be an "inert" material, such as a solvent or an active ingredient.

[0044] When the hydrophobic materials are active ingredients, they are preferably selected from the group consisting of flavors, flavoring ingredients, fragrances (daily fragrances), fragrance ingredients, nutritional supplements, cosmetics, pest control agents, biocide active ingredients and mixtures thereof.

[0045] According to a particular embodiment, the hydrophobic material comprises a mixture of a fragrance and another ingredient selected from the group consisting of a nutraceutical, a cosmetic, a pest control agent, and a biocide active ingredient.

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

[0047] According to a specific embodiment, the hydrophobic material comprises a mixture of a biocide active ingredient and another ingredient selected from the group consisting of a fragrance, a nutraceutical, a cosmetic, a pest control agent.

[0048] According to a specific embodiment, the hydrophobic material comprises a mixture of a pest control agent and another ingredient selected from the group consisting of a fragrance, a nutraceutical, a cosmetic, a biocide active ingredient.

[0049] According to one particular embodiment, the hydrophobic material comprises a fragrance.

[0050] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0051] According to a particular embodiment, the hydrophobic material consists of a biocide active ingredient.

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

[0053] By "fragrance" (or also referred to as "fragrance oil") it is meant here an ingredient or composition that is liquid at about 20°C. According to any of the above embodiments, the fragrance oil may be a single fragrance ingredient or a mixture of ingredients in the form of a fragrance composition. As a "fragrance ingredient" it is meant here a compound whose primary purpose is to impart or modify an odor. In other words, to be considered a fragrance ingredient such an ingredient must be recognized by a person skilled in the art as being capable of imparting or modifying the odor of a composition in at least an active or pleasant manner, rather than merely having an odor. For the purposes of the present invention, fragrance oils also include combinations of fragrance ingredients with substances that together improve, enhance or modify the delivery of the fragrance ingredient, such as fragrance precursors, emulsions or dispersions, as well as combinations that impart other benefits in addition to changing or imparting odor, such as long-lastingness, burst, malodor counteracting, antimicrobial effects, microbial stability, pest control.

[0054] The character and type of the perfuming ingredients present in the oil phase do not guarantee to be described in more detail here, and it is all that cannot be exhaustive in any case, and the technical staff can select them based on its general knowledge and according to expected use or application and required organoleptic effect. Generally speaking, these perfuming ingredients belong to different chemical classes, as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulfur-containing heterocyclic compounds and essential oils, and the perfuming auxiliary component can be natural origin or synthetic origin. In any case, many in these auxiliary components are listed in references such as the work Perfume and Flavor Chemicals of S.Arctander, 1969, Montclair, New Jersey, USA or its updated version or other works of similar nature, and in the patent documentation enriched in the spices field.

[0055] In particular, one may cite the perfuming ingredients commonly used in perfume formulations, for example:

[0056] -Aldehyde aroma components: decanal, dodecanal, 2-methylundecanal, 10-undecanal, octanal, nonanal and / or nonenal;

[0057] - Aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0-2,7-]undec-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or α-pinene;

[0058] - balsamic ingredients: coumarin, ethyl vanillin and / or vanillin;

[0059] - Citrus aroma ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-menthenadiene;

[0060] - Floral fragrance ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethyl alcohol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone (β-violet ketone), 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, 2,5-dimethyl-2-indanemethanol, 2,6,6-trimethyl-3-cyclohexen-1-yl 1-Hexanecarboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-ylpropanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menthen-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, methyl homocis-dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol , tricyclodecenyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-menthol, (S)-2-(1,1-dimethylpropoxy)propyl propionate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amylcinnamaldehyde, 8-decene-5-lactone, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, tricyclodecenyl isobutyrate, and / or a mixture of methylionone isomers;

[0061] - Fruity aroma ingredients: γ-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanoic acid ethyl ester, hexyl acetate, 2-methylbutyric acid ethyl ester, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, 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;

[0062] - Green fragrance ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styryl 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;

[0063] Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecene-2-one, 1-oxa-13-cyclohexadecene-2-one, (9Z)-9-cycloheptadecene-1-one, 2-{1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3-methyl-5- Cyclopentadecen-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]isochromene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate, oxacyclohexadecane-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl propionate;

[0064] - Wood fragrance ingredients: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxirane-2,9'-tricyclo[6.2.1.0 2,7 ] Undec[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate;

[0065] - Other ingredients (e.g., ambery, powdery, spicy, or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any of its stereoisomers, piperonal, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane, and / or 3-(3-isopropyl-1-phenyl)butanal.

[0066] It will also be understood that the ingredients may also be compounds known to release various types of perfuming compounds in a controlled manner, also known as pro-fragrances or pro-fragrances. Non-limiting examples of suitable pro-fragrances may include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyl oxy(phenyl)acetate, 3,7-dimethylocta-2,6-diene-1-oxo(phenyl)acetate. 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-(oct-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 2-(1-phenylethoxyprop-1-en-2-yl)naphthalene, (2-phenylethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)benzene 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 a mixture thereof.

[0067] The perfuming ingredients can be dissolved in solvents currently used in the perfume industry. The solvent is preferably not an alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, (rosin resin, available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes or isoparaffins. Preferably, the solvent is very hydrophobic and highly sterically hindered, e.g. or benzyl benzoate. Preferably, the fragrance contains less than 30% solvent. More preferably, the fragrance contains less than 20%, and even more preferably, less than 10% solvent, all of these percentages being by weight relative to the total weight of the fragrance. Most preferably, the fragrance is substantially free of solvent.

[0068] Preferred perfuming ingredients are those with high steric hindrance (bulky materials), in particular ingredients from one of the following groups:

[0069] - Group 1: perfuming ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted by at least one linear or branched C1-C4 alkyl or alkenyl substituent;

[0070] - Group 2: perfuming ingredients comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted by at least one linear or branched C4-C8 alkyl or alkenyl substituent;

[0071] - Group 3: perfuming ingredients comprising a benzene ring, or perfuming ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted by at least one linear or branched C5-C8 alkyl or alkenyl substituent, or substituted by at least one phenyl substituent and optionally substituted by one or more linear or branched C1-C3 alkyl or alkenyl substituents;

[0072] - Group 4: perfuming ingredients comprising at least two fused or linked C5 and / or C6 rings;

[0073] - Group 5: Perfuming ingredients containing a camphor-like ring structure;

[0074] - Group 6: Contains at least one C7-C 20 Ring-structured flavoring ingredients;

[0075] - Group 7: perfuming ingredients having a logP value higher than 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent;

[0076] Examples of components from each of these groups include:

[0077] - Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (source: Firmenich SA, Geneva, Switzerland), isocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (source: Firmenich SA, Geneva, Switzerland), nerol, terpineol, dihydroterpineol, terpene acetate, dihydroterpene acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-menthadien-7-ol (source: Firmenich SA, Geneva, Switzerland) SA, Geneva, Switzerland), l-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-menthyl acetate, (1R,2S,4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (Source: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, trimethylcyclohexyl acetate (cyclanol), 1,4-cyclohexanediethyl dicarboxylate (Source: Firmenich SA, Geneva, Switzerland), (3ARS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (Source: Firmenich SA, Geneva, Switzerland), (6R)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (Source: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde;

[0078] - Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (Source: Givaudan SA, Vergne, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (Source: Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'yl)-4-penten-2-ol (Source: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentane acetate (Source: Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (Source: Firmenich SA, Geneva, Switzerland), SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (Source: Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (Source: Givaudan SA, Vergne, Switzerland);

[0079] - Group 3: damascenone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (source: Firmenich SA, Geneva, Switzerland), (1'R)-2-[2-(4'-methyl-3'-cyclohexen-1'-yl)propyl]cyclopentanone, α-ionone, β-ionone, damascenone, a mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (source: Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (source: Firmenich SA, Geneva, Switzerland) SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl propionate (Source: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (Source: International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (Source: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (Source: Firmenich SA, Geneva, Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpene isobutyrate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate (Source: Firmenich SA, Geneva, Switzerland), 8-methoxy-1-menthene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate (Source: Firmenich SA, Geneva, Switzerland), p-tert-butylcyclohexanone, menthyl mercaptan, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allyl cyclohexylpropionate, cyclohexyl salicylate, 2-methoxy-4-methylphenyl methyl carbonate, 2-methoxy-4-methylphenyl ethyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate;

[0080] - Group 4: Methyl cedryl ketone (source: International Flavors and Fragrances, USA), 2-methylpropionic acid (1RS, 2SR, 6RS, 7RS, 8SR)-tricyclic [5.2.1.0 2,6 ]dec-3-en-8-yl ester and 2-methylpropionic acid (1RS, 2SR, 6RS, 7RS, 8SR)-tricyclo[5.2.1.0 2,6] mixture of dec-4-en-8-yl esters, vetyverol, vetyverone, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone (source: International Flavors and Fragrances, USA), (5RS,9RS,10SR)-2,6,9,10-tetramethyl-1-oxaspiro[4.5]dec-3,6-diene and (5RS,9SR,10RS) isomers, 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]dec-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indanone (source: International Flavors and Fragrances, USA) and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (Source: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undec-4-ene-9-spiro-2'-oxirane (Source: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthyl acetate (Source: Firmenich SA, Geneva, Switzerland), 1-naphthol (octalynol), (dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan (Source: Firmenich SA, Geneva, Switzerland) 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 propionate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl propionate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptane-3-spiro-2′-cyclohexen-4′-one;

[0081] - Group 5: Camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedane, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (source: Firmenich SA, Geneva, Switzerland), cedrene, cedrene alcohol, cedrol, 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecan-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecan-4-one 2,7] a mixture of undec-4-one (source: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (source: Firmenich SA, Geneva, Switzerland);

[0082] - Group 6: (trimethyl-13-oxabicyclo-[10.1.0]-tridec-4,8-diene (source: Firmenich SA, Geneva, Switzerland), 9-hexadecene-16-lactone (source: Firmenich SA, Geneva, Switzerland), cyclopentadecenolactone (source: Firmenich SA, Geneva, Switzerland), 3-methyl(4 / 5)-cyclopentadecenone (source: Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (source: Firmenich SA, Geneva, Switzerland), pentadecanolide (source: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (source: Firmenich SA, Geneva, Switzerland), (1-ethoxyethoxy)cyclododecane (source: Firmenich SA, Geneva, Switzerland), 1,4-dioxaheptadecan-5,17-dione, 4,8-cyclododecadien-1-one;

[0083] - Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propyl)phenyl]propanal (source: Givaudan SA, Vergne, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0084] Preferably, the fragrance 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 fragrance comprises at least 30%, preferably at least 50% of ingredients selected from Groups 3 to 7 as defined above. Most preferably, the fragrance comprises at least 30%, preferably at least 50% of ingredients selected from Group 3, Group 4, Group 6 or Group 7 as defined above.

[0085] According to another preferred embodiment, the fragrance comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients having a logP higher than 3, preferably higher than 3.5, even more preferably higher than 3.75.

[0086] According to a specific embodiment, the fragrance used in the present invention contains less than 10% of its own weight of primary alcohols, less than 15% of its own weight of secondary alcohols and less than 20% of its own weight of tertiary alcohols. Advantageously, the fragrance used in the present invention does not contain any primary alcohols and contains less than 15% of secondary and tertiary alcohols.

[0087] According to one embodiment, the oil phase (or oil-based core) comprises:

[0088] - 25 to 100 wt%, preferably 25 to 98 wt% of a fragrance oil comprising at least 15 wt% of a high impact fragrance raw material having a Log T < -4, and

[0089] - 0 to 75% by weight, preferably 2 to 75% by weight, with a density greater than 1.07 g / cm 3 Density balanced material.

[0090] "High impact fragrance raw materials" are understood to be fragrance raw materials with a Log T < -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 common logarithm of the threshold concentration, i.e., Log[threshold] ("LogT").

[0091] "Density balanced material" should be understood as having a density greater than 1.07 g / cm 3 And preferably materials with low odor or no odor.

[0092] The odour threshold concentration of the flavouring compounds is determined by using a gas chromatograph ("GC"). Specifically, the gas chromatograph is calibrated to determine the exact volume of the flavouring oil component injected by the syringe, the exact split ratio and the hydrocarbon response using hydrocarbon standards of known concentration and chain length distribution. The air flow rate is accurately measured and the sample volume is calculated assuming that the duration of a human inhalation lasts 12 seconds. Since the exact concentration at the detector at any point in time is known, the mass per volume inhaled is known and so is the concentration of the flavouring compound. To determine the threshold concentration, a solution is delivered to a sniffing port with a back-calculated concentration. The panellist sniffs the GC effluent and determines the retention time at which the odour is perceived. The average of all panellists determines the odour threshold concentration of the flavouring compound. The determination of odor thresholds is described in more detail in C. Vuilleumier et al., Multidimensional Visualization of Physical and Perceptual Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, Vol. 33, September,, 2008, pages 54-61.

[0093] In WO2018115250, high impact fragrance raw materials with Log T < -4 and with a density greater than 1.07 g / cm 3 The density of the density balance material properties, the contents of which are incorporated by reference.

[0094] According to one embodiment, the high impact fragrance raw materials with Log T<-4 are selected from the group consisting of: (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenyl acetate, pyrazole butyl ether, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl)pyridine, 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, -1-one, a mixture comprising (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one and (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one, (+-)-1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one, (1'S,3'R)-1-methyl-2-[(1',2',2'-trimethylbicyclo[3.1.0]hex-3'-yl)methyl]cyclopropyl}methanol , (+-)-3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, H-methyl-2h-1,5-benzodioxepin-3(4H)-one, (2E,6Z)-2,6-nonadien-1-ol, (4Z)-4-dodecenal, (+-)-4-hydroxy-2,5-dimethyl-3(2H)-furanone, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4α,8Aβ-dimethyl -4a-naphthol, patchouli alcohol, 2-methoxy-4-(1-propenyl)phenol, a mixture comprising (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylidene-2-phenyl-2H-pyran, a mixture comprising 4-methylidene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,6-dihydro-2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonenal, 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-nonalactone, (3aR,5AS,9AS,9BR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 7-isopropyl-2H,4H-1,5-benzodioxepin-3-one, coumarin, 4-methylphenyl isobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, β,2,2,3-tetramethyl-δ-formylidene-3-one -cyclopentene-1-butanol, δ-damascenone ((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, p-cresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2-aminobenzoate, ethyl methylphenyl glycidate, γ-octalactone, ethyl 3-phenyl-2-acrylate, (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, p-cresol acetate, lauroyl lactone, dimethyl tricyclo[7.1.1.0. 2,7] Undec-2-en-4-one (tricyclone), (+)-(3R,5Z)-3-cyclopentadecen-1-one, undecyl lactone, (1R,4R)-8-mercapto-3-menthone, (3S,3AS,6R,7AR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, β-ionone, (+-)-6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1,3,5-undecatriene, 10-undecenal, (9E)-9-undecene Aldehyde, (9Z)-9-undecenal, (Z)-4-decenal, (+-)-ethyl 2-methylpentanoate, 1,2-diallyldisulfane, 2-tridecenenitrile, 3-tridecenenitrile, (+-)-2-ethyl-4,4-dimethyl-1,3-oxathiinane, (+)-(3R,5Z)-3-methyl-5-cyclopentadecen-1-one, 3-(4-tert-butylphenyl)propanal, allyl (cyclohexyloxy)acetate, methyl naphthyl ketone, (+-)-(4E)-3-methyl-4-cyclopentadecen-1-one ketone, (+-)-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-propyl)cyclohexanone oxime, 6-hexyltetrahydro-2H-pyran-2-one, (+-)-3-(3-isopropyl-1-phenyl)butanal, 2-(3-oxo-2-pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohex-2-enyl)pent-1-en-3-one, indole, 7-propyl-2H,4H-1,5-benzodioxepin-3-one, ethyl maltol (ethyl praline), (4-methylphenoxy)acetaldehyde, tricyclo[5.2.1.0.(2,6)]decane-2-carboxylic acid ethyl ester, (+)-(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, methylnonyl acetaldehyde, 4-formyl-2-methoxyphenyl 2-methylpropionate, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, (1R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]oct-3-ene, (1R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1 ,6-octadien-3-ol, (E)-3-phenyl-2-propenenitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, (2 / 3-methylbutoxy) allyl 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.

[0095] According to one embodiment, the fragrance raw material with Log T < -4 is selected from the group consisting of aldehydes, ketones, alcohols, phenols, esters, lactones, ethers, epoxides, nitriles and mixtures thereof.

[0096] According to one embodiment, the fragrance raw material with Log T < -4 comprises at least one compound selected from the group consisting of alcohols, phenols, esters, lactones, ethers, epoxides, nitriles and mixtures thereof, preferably in an amount of 20 to 70 wt % based on the total weight of the fragrance raw materials with Log T < -4.

[0097] According to one embodiment, the fragrance raw materials with Log T <-4 comprise 20 to 70 wt. % of aldehydes, ketones and mixtures thereof, based on the total weight of the fragrance raw materials with Log T <-4.

[0098] Therefore, the remaining fragrance raw materials contained in the oil-based core may have a Log T > -4.

[0099] According to one embodiment, the fragrance raw materials with Log T>-4 are selected from the group consisting of ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal, tricyclodecenyl propionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-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-oxadiazol-1-ol, Cyclo[2.2.2]octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa-12-cyclohexadecene-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, C11 aldehyde, (+-)-2,6-dimethyl-7-octen-2-ol, allyl 3-cyclohexylpropionate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-n-propyl)cyclohexanone, allyl heptanoate, 2-(2-methyl-2-n-propyl)cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl butyrate, geranyl acetate, neryl acetate, (+-)-1-phenylethyl acetate Ester, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, ethyl 3-oxobutanoate, (2Z)-ethyl 3-hydroxy-2-butenoate, 8-p-menthol, 8-p-menthyl acetate, 1-p-menthyl acetate, (+-)-2-(4-methyl-3-cyclohexen-1-yl)-2-propyl acetate, (+-)-2-methylbutyl butyrate, 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 Ester, octanal, ethyl butyrate, (+-)-(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] heptane-2-ol), (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2-propylidene)cyclohexene, (+)-(R)-4-(2-methoxyprop-2-yl)-1-methylcyclohex-1-ene, tricyclodecenyl 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-methylpropyl propionate, and mixtures thereof.

[0100] According to one embodiment, the oil-based core (or fragrance formulation) comprises:

[0101] - 0 to 60% by weight of a hydrophobic solvent (based on the total weight of the fragrance formulation),

[0102] - 40 to 100 wt. % of a fragrance oil (based on the total weight of the fragrance formulation), wherein the fragrance oil has at least two, preferably all, of the following properties:

[0103] o at least 35%, preferably 40%, preferably at least 50%, more preferably at least 60% of the perfuming ingredients have a log P greater than 3, preferably greater than 3.5,

[0104] o at least 20%, preferably 25%, preferably at least 30%, more preferably at least 40% of bulky materials of Groups 1 to 6, preferably Groups 3 to 6, as defined above, and

[0105] o at least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least 30% of the high impact fragrance material as defined above having a Log T < -4,

[0106] - Optionally, additional hydrophobic active ingredients.

[0107] According to a particular embodiment, the fragrance comprises from 0 to 60% by weight of a hydrophobic solvent.

[0108] According to a particular embodiment, the hydrophobic solvent is a density balancing material, preferably selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylates, benzyl cinnamate and mixtures thereof.

[0109] In a particular embodiment, the hydrophobic solvent has a Hansen Solubility Parameter that is compatible with the entrapped fragrance oil.

[0110] The term "Hansen solubility parameter" is understood to refer to the solubility parameter method proposed by Charles Hansen for predicting the solubility of polymers and is based on the fact that the total vaporization energy of a liquid consists of several individual components. 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 as (δD 2 +δP 2 +δH 2 ) 0.5 , where δD is the Hansen dispersion value (hereinafter also referred to as atomic dispersion force), δP is the Hansen polarizability value (hereinafter also referred to as dipole moment), and δH is the Hansen hydrogen bond ("h-bond") value (hereinafter also referred to as hydrogen bond). For a more detailed explanation of this parameter and this value, please refer to Charles Hansen's "The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient", Danish Technical Press (Copenhagen, 1967).

[0111] The Euclidean difference of the solubility parameters of the fragrance and the solvent was calculated as (4*(δD solvent -δD fragrance ) 2 +(δP solvent -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 hydrogen bond value of the solvent respectively; and δD fragrance , δ fragrance and δH fragrance They are the Hansen dispersion value, Hansen polarizability value and Hansen hydrogen bond value of the fragrance respectively.

[0112] In a particular embodiment, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the first group consisting of: atomic dispersion force (δD) of 12 to 20, dipole moment (δP) of 1 to 8, and hydrogen bonding (δH) of 2.5 to 11.

[0113] In a particular embodiment, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the second group consisting of: atomic dispersion forces (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δP) of 1 to 8, preferably 1 to 7, and hydrogen bonds (δH) of 2.5 to 11, preferably 4 to 11.

[0114] In a particular embodiment, 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 the first group consisting of: atomic dispersion forces (δD) of 12 to 20, dipole moments (δP) of 1 to 8, and hydrogen bonding (δH) of 2.5 to 11.

[0115] In a particular embodiment, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the second group consisting of: atomic dispersion forces (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δP) of 1 to 8, preferably 1 to 7, and hydrogen bonds (δH) of 2.5 to 11, preferably 4 to 11.

[0116] According to one embodiment, the perfuming formulation comprises a fragrance modulator (which may be used together with the hydrophobic solvent when present, or as a substitute for the hydrophobic solvent when not present).

[0117] Preferably, a fragrance modulator is defined as a fragrance material having:

[0118] i. Vapor pressure less than 0.0008 Torr at 22°C;

[0119] ii. clogP of 3.5 or more, preferably 4.0 or more, more preferably 4.5;

[0120] iii. at least two Hansen solubility parameters selected from the first group consisting of: atomic dispersion forces of 12 to 20, dipole moments of 1 to 7, and hydrogen bonding of 2.5 to 11,

[0121] iv. at least two Hansen solubility parameters selected from the second group consisting of: atomic dispersion forces of 14 to 20, dipole moments of 1 to 8, hydrogen bonds of 4 to 11, when in solution with a compound having a vapor pressure in the range of 0.0008 to 0.08 Torr at 22°C.

[0122] Preferably, as examples, the following ingredients can be listed as regulators, but the list is not limited to the following substances: alcohol C12, oxahedral, 3-[(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecen-1-one, cyclopentadecanone, (8Z)-oxahedral, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, lilyral, 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-hexa Hydrocyclopenta[g]isochromene, (+)-(1S,2S,3S,5R)-2,6,6-trimethylspiro[bicyclo[3.1.1]heptane-3,1'-cyclohexane]-2'-en-4'-one, oxahedralidone, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, (+)-(4 R,4aS,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amylcinnamaldehyde, hexylcinnamaldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadien-3-one, (9Z)-9-cycloheptadecene-1-one.

[0123] According to a particular embodiment, the hydrophobic material does not contain any active ingredient (e.g. fragrance). According to this particular embodiment, it comprises, preferably consists of, a hydrophobic solvent, preferably selected from isopropyl myristate, triglycerides (e.g. 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-butylene glycol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propylene glycol), 1,3-propylene glycol, dipropylene glycol, glycerol, glycol ethers and mixtures thereof.

[0124] The term "biocide" refers to a chemical substance that kills living organisms (e.g., microorganisms) or reduces or prevents their growth and / or accumulation. Biocides are commonly used in medicine, agriculture, forestry, and industry to prevent scaling of, for example, water, agricultural products (including seeds), and oil pipelines. Biocides can be pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides, and rodenticides; and / or antimicrobials, such as bactericides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals, and / or antiparasitics.

[0125] As used herein, "pest control agent" refers to a substance used to repel or attract pests to reduce, inhibit or promote their growth, development or activity. Pests are any organisms, whether animals, plants or fungi, that are invasive or troublesome to plants or animals, including insects, especially arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0126] By "flavor oil" is meant a flavoring ingredient, or a mixture of flavoring ingredients, solvents, or adjuvants currently used to prepare flavoring formulations, i.e., a specific mixture of ingredients intended to be added to an edible composition or chewable product to impart, improve, or modify its sensory properties, particularly its flavor and / or taste. Flavoring ingredients are well known to those skilled in the art, and their properties do not warrant a more detailed description here, which is in no way exhaustive, and a skilled flavorist can select them based on their general knowledge and the intended use or application and the desired sensory effect. Many of these flavoring ingredients are listed in the literature, such as S. Arctander's book Perfume and Flavor Chemicals, 1969, Montclair, NJ, USA, or its most recent editions, or other works of similar nature, such as Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press, or M.B. Jacobs' Synthetic Food Adjuncts, 1947, van Nostrand Co., Inc. The solvents and adjuvants currently used to prepare flavoring formulations are also well known in the art.

[0127] In a specific embodiment, the flavoring agent is a mint flavoring agent. In a more specific embodiment, the mint is selected from the group consisting of peppermint and spearmint.

[0128] In a further embodiment, the flavoring agent is a cooling agent or a mixture thereof.

[0129] In another embodiment, the flavor is a menthol flavor.

[0130] Flavorings derived from or based on fruits in which citric acid is the primary naturally occurring acid include, but are not limited to, citrus fruits (e.g., lemons, limes), limonene, strawberries, oranges, and pineapples. In one embodiment, the flavored food is lemon juice, lime juice, or orange juice extracted directly from the fruit. Other embodiments of flavorings include juices or liquids extracted from oranges, lemons, grapefruits, limes, citrons, clementines, mandarins, tangerines, and any other citrus fruits or their variants or hybrids. In a specific embodiment, flavorings include liquids extracted or distilled from oranges, lemons, grapefruits, limes, citrons, clementines, tangerines, any other citrus fruits or their variants or hybrids, pomegranates, kiwis, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruit, mangoes, pears, tomatoes, and strawberries.

[0131] In a specific embodiment, the flavor comprises a limonene-containing composition. In a specific embodiment, the composition is citrus further comprising limonene.

[0132] In another specific embodiment, the flavor comprises a flavor selected from the group consisting of strawberry, orange, lime, tropical fruit, berry mix, and pineapple.

[0133] The phrase flavoring agent includes not only flavoring agents that impart or modify the smell of food, but also ingredients that impart or modify taste. The latter do not necessarily have a taste or smell themselves, but can improve the taste provided by other ingredients such as salt-enhancing ingredients, sweet-enhancing ingredients, umami-enhancing ingredients, bitter-blocking ingredients, etc.

[0134] In further embodiments, suitable sweetening components may be included in the particles described herein. In a specific embodiment, the sweetening component 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 (cyclamate), aspartame, sucralose, saccharin sodium, and acesulfame potassium, or mixtures thereof.

[0135] Polymeric materials

[0136] According to the present invention, the polymeric shell comprises a polymeric material.

[0137] According to one embodiment, the polymeric material is selected from the group consisting of polyurea, polyester, polyurethane, polyamide, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, poly(β-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.

[0138] According to a particular embodiment, the polymeric material is polyurea and / or polyurethane.

[0139] 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 initiated by the addition of a polyamine reactant. Preferably, the reactant is selected from the group consisting of a water-soluble guanidine salt and a guanazole to form a polyurea material with the polyisocyanate. According to another embodiment, the polyurea-based polymeric material is formed without the addition of a polyamine reactant and is produced solely by the self-polymerization of at least one polyisocyanate, preferably in the presence of a catalyst.

[0140] 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, interfacial polymerization is initiated by adding a polyol reactant. Preferably, the reactant is selected from monomers and polymeric polyols having a plurality of hydroxyl groups available for reaction, and mixtures thereof.

[0141] According to another embodiment, the polymeric material is a polyurea / polyurethane based material, and comprises the reaction product of polyisocyanates and polyvalent alcohol and amine.In this case, interfacial polymerization is caused by adding the mixture of the reactant mentioned in the above first and second embodiments.In addition, the cross-linking agent with amino group and hydroxyl group can be used to generate the polyurea / polyurethane material.In addition, the polyisocyanates with urea and carbamate functional group can be used to generate the polyurea / polyurethane material.

[0142] According to another embodiment, the polymeric material is a polyamide-based material and comprises the reaction product of an acid chloride and at least one amine, preferably at least two amines. According to a specific embodiment, the second polymeric material is a polyamide-based material as disclosed in WO2020127743A1 or WO2020127749A1, the contents of which are incorporated herein by reference with respect to components and preparation methods.

[0143] According to one embodiment, the polymeric material is a copolymer, such as poly(urea-urethane), poly(esteramide), and mixtures thereof.

[0144] According to one embodiment, the polymeric material is present in an amount of less than 10%, preferably less than 8%, preferably less than 6%, preferably less than 4%, more preferably less than 3%, even more preferably less than 2%, based on the total weight of the microcapsule. According to a specific embodiment, the polymeric material is present in an amount of 1 to less than 10%, preferably 1 to less than 8%, preferably 1 to less than 6%, preferably 1 to less than 4%, more preferably 1 to less than 3%, even more preferably 1 to less than 2%. In fact, it has been emphasized that even if the amount of polymeric material forming the wall is reduced, the microcapsules still show good stability in consumer products.

[0145] Plant-based coacervates

[0146] According to the present invention, a coacervate is made from (comprising) first and second polyelectrolytes, wherein the first polyelectrolyte comprises a plant protein.

[0147] According to one embodiment, the plant protein (first polyelectrolyte) 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 protein and mixtures thereof.

[0148] The first polyelectrolyte may comprise plant protein and non-plant protein, such as fungal protein, mycoprotein, and mixtures thereof.

[0149] According to another embodiment, the first polyelectrolyte consists of a plant protein.

[0150] According to one embodiment, when the pH is less than 8, the first polyelectrolyte has a net positive charge, and when the pH is greater than 2, the second polyelectrolyte has a net negative charge.

[0151] According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 10%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 20%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 30%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 40%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 50%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 60%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 70%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 80%. According to one embodiment, the solubility of the protein (preferably plant protein) is greater than 90%. The above solubilities are given in water at room temperature (typically 20° C.) and preferably at natural pH.

[0152] The protein (preferably plant protein) used in the present invention can be natural, or partially or completely denatured by any suitable method. Denaturation is a process that changes the conformational structure of a protein by unfolding, that is, it involves the rupture and possible destruction of the secondary and tertiary structures of the protein. In fact, denaturation means the rupture of many weak connections or bonds (such as hydrogen bonds) within the protein molecule that are responsible for the highly ordered structure of the protein in its native state. Denaturation is reversible (when the denaturing effect is eliminated, the protein can return to its native state) or irreversible.

[0153] Denaturation can be achieved in a variety of ways. Proteins may be denatured by exposure to temperature, radiation or mechanical stress (including shear), changes in pH (treatment with bases or acids), treatment with oxidizing or reducing agents, inorganic salts, certain organic solvents, chaotropic agents (i.e., agents with a positive chaotropic value - kJ Kg on the Hallsworth scale), or by exposure to water. -1 The hydroxybenzoic acid ester can be denatured by treating with a molar compound 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, thiourea).

[0154] The proteins used in the present invention may also be derivatized or modified (eg, derivatized or chemically modified). For example, proteins may be modified by covalently attaching sugars, lipids, peptides, or chemical groups such as phosphates or methyl groups.

[0155] According to one embodiment, the first polyelectrolyte comprises at least one polypeptide.

[0156] According to a particular embodiment, the vegetable protein is potato protein.

[0157] Potato protein is typically extracted from potato tubers (Solanum tuberosum). According to one embodiment, the potato protein is a natural potato protein and is preferably patatin (potato tuber-specific protein).

[0158] The second polyelectrolyte is preferably selected from a polysaccharide or another polymer with a charge of the opposite sign compared to the first polyelectrolyte. Typically, when pH>2, the second polyelectrolyte is negatively charged.

[0159] According to one embodiment, the second polyelectrolyte is selected from the group consisting of gum arabic, alginates, cellulose derivatives, guar gum, pectinates, pectin, carrageenan, polyacrylic and methacrylic acids, cellulose derivatives, xanthan gum, microbial exopolysaccharides and mixtures thereof.

[0160] Among the cellulose derivatives, one may cite, for example, carboxymethylcellulose (preferably with a molecular weight of 35,000 to 50,000 Da), hydroxypropylmethylcellulose (HPMC) or mixtures thereof.

[0161] According to a particular embodiment, the second polyelectrolyte is gum arabic.

[0162] The weight ratio between the first polyelectrolyte and the second polyelectrolyte is preferably from 0.2 to 5, preferably from 0.5 to 2, more preferably from 1 to 2.

[0163] According to a particular embodiment, the weight ratio between the first polyelectrolyte and the second polyelectrolyte is 1.

[0164] According to a particular embodiment, the weight ratio between the first polyelectrolyte and the second polyelectrolyte is 1.5.

[0165] According to one embodiment, the microcapsules comprise:

[0166] - a kernel containing a fragrance oil, and

[0167] - a shell comprising polyurea and a coacervate comprising potato protein and gum arabic.

[0168] According to one embodiment, the microcapsules comprise:

[0169] - a kernel containing a fragrance oil, and

[0170] - a shell comprising polyurea and a coacervate comprising canola protein and gum arabic.

[0171] According to a preferred embodiment, the coacervate is chemically hardened using a suitable cross-linking agent such as glutaraldehyde, glyoxal, formaldehyde, polyphenols (e.g. tannic acid), polyanhydrides or genipin, preferably in an amount of 2% to 60%, preferably 2% to 30%, based on the weight of the first polyelectrolyte.

[0172] The polyanhydride crosslinking agent can be poly(ethylene-maleic anhydride) or poly(methyl vinyl ether-maleic anhydride).

[0173] According to one specific embodiment, the coacervate is chemically hardened using glutaraldehyde as a cross-linking agent.

[0174] According to another specific embodiment, the coacervate is enzymatically hardened using an enzyme such as transglutaminase.

[0175] According to another embodiment, the coacervate is not cross-linked.

[0176] Optional Ingredients

[0177] According to one embodiment, the microcapsule slurry comprises auxiliary ingredients selected from the group consisting of thickeners / rheology modifiers, preservatives, antimicrobial agents, opacity enhancers, mica particles, salts, pH stabilizers / buffering components, preferably in an amount of 0 to 15%, more preferably 0.1 to 10%, even more preferably 0.05 to 5%, based on the total weight of the slurry.

[0178] Among the different thickeners, one may cite, for example, anionic, cationic, nonionic or zwitterionic copolymers such as, but not limited to, polyacrylamide, polyacrylate, polyacryloyldimethyltaurate, polyquaternium-37, or carbomer and mixtures thereof. According to a particular embodiment, the thickener is xanthan gum, guar gum, diutan gum or mixtures thereof.

[0179] Among the different preservatives, there may be mentioned, for example, sodium benzoate, benzoic acid, benzisothiazolinone, methylchloroisothiazolinone, methylisothiazolinone, chlorhexidine digluconate, sodium hydroxymethylglycinate, parabens, triclosan, phenoxyethanol, caprylhydroxamic acid, potassium sorbate, lactic acid, ε-polylysine, caprylyl glycol, caprylhydroxamic acid, glycerol, glyceryl caprylate, ethylhexylglycerin and mixtures thereof.

[0180] According to another embodiment, the microcapsule slurry of the present invention comprises additional free (ie unencapsulated) fragrance, preferably in an amount of 5 to 50 wt. % based on the total weight of the slurry.

[0181] Outer coating layer

[0182] According to a specific 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 (such as those described in WO2021185724) and mixtures thereof to form the outer coating layer (coating) of the microcapsules.

[0183] 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 gum, hydroxypropyl cellulose and hydroxypropyl methylcellulose, pectin and mixtures thereof.

[0184] According to a particular embodiment, the coating consists of a cationic coating.

[0185] Cationic polymers are also well known to those skilled in the art. The cationic charge density of the preferred cationic polymer is at least 0.5 meq / g, more preferably at least about 1.5 meq / g, but also preferably less than about 7 meq / g, more preferably less than about 6.2 meq / g. The cationic charge density of the cationic polymer can be determined by the Kjeldahl method, as described in the chemical test for nitrogen determination in the United States Pharmacopoeia. Preferred cationic polymers are selected from units containing primary amine, secondary amine, tertiary amine and / or quaternary amine groups, which units can form part of the main polymer chain or can be carried by side substituents directly connected thereto. The weight average molecular weight (Mw) of the cationic polymer is preferably 10,000 to 3.5 M Daltons, more preferably 50,000 to 2 M Daltons.

[0186] According to a particular embodiment, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylaminomethacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-imidazol-3-ium ammonium chloride), vinylpyrrolidone, acrylamidopropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride are used. Preferably, the copolymer should be selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia gum hydroxypropyltrimonium chloride, guar gum hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride.

[0187] Specific examples of commercially available products include SC60 (cationic copolymer of acrylamidopropyltrimethylammonium chloride and acrylamide, source: BASF) or For example PQ 11N, FC 550 or Style (polyquaternium-11 to 68 or vinylpyrrolidone quaternized copolymers, source: BASF), or (C13S or C17, source: Rhodia).

[0188] According to any of the above embodiments of the present invention, the amount of the above polymer added is about 0% to 5% w / w, or even about 0.1% to 2% w / w, with the percentages being expressed on a w / w basis relative to the total weight of the slurry. It will be understood by those skilled in the art that only a portion of the added polymer will be incorporated into / deposited on the microcapsule shell.

[0189] In a particular embodiment, the shell material is a biodegradable material.

[0190] In a particular embodiment, the shell has a biodegradability according to OECD 30 IF within 60 days of at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%.

[0191] In a particular embodiment, the core-shell microcapsules have a biodegradability within 60 days according to OECD 30 IF of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%.

[0192] It will thus be appreciated that the core-shell microcapsules including all components, e.g. core, shell and optional coating, may have a biodegradability within 60 days according to OECD 301F of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%.

[0193] In a particular embodiment, the oil core, preferably a fragrance oil, has a biodegradability within 60 days of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% according to OECD 301F.

[0194] OECD301F is the Organization for Economic Co-operation and Development's standard test method for biodegradability.

[0195] A typical method for extracting shells to measure biodegradability is disclosed in Gasparini et al. in Molecules 2020, 25, 718.

[0196] Multiple microcapsule systems

[0197] According to one embodiment, the microcapsules of the present invention (microcapsules of the first type) can be used in combination with microcapsules of the second type.

[0198] Another object of the present invention is a microcapsule delivery system comprising:

[0199] - the microcapsule slurry of the present invention as the first microcapsule slurry, and

[0200] - 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 wall material content and / or curing conditions for forming the wall material and / or their coating layer material.

[0201] According to a particular embodiment, the microcapsule delivery system is in the form of a slurry.

[0202] The wall of the second type of microcapsules can vary. As non-limiting examples, the polymer shell of the second type of microcapsules comprises a material selected from the group consisting of polyureas, polyurethanes, polyamides, polyhydroxyalkanoates, polyacrylates, polyesters, polyurethanes, polyepoxides, polysiloxanes, polycarbonates, polysulfonamides, urea-formaldehydes, melamine-formaldehyde resins, melamine-formaldehyde resins crosslinked with polyisocyanates or aromatic polyols, melamine-urea resins, melamine-glyoxal resins, gelatin / gum arabic shell walls, and mixtures thereof.

[0203] The second type of microcapsules may comprise an oil-based core comprising a hydrophobic active substance, preferably a fragrance, and a composite shell comprising a first material and a second material, wherein the first material and the second material are different, the first material being a coacervate and the second material being a polymeric material. In a particular embodiment, the weight ratio between the first material and the second material is from 50:50 to 99.9:0.1. In a particular embodiment, the coacervate comprises a first polyelectrolyte, preferably selected from a protein (e.g., gelatin), a polypeptide or a polysaccharide (e.g., chitosan), most preferably gelatin, and a second polyelectrolyte, preferably an alginate, a cellulose derivative, guar gum, pectinate, carrageenan, polyacrylic acid and methacrylic acid or xanthan gum, or a plant gum such as acacia gum (gum arabic), most preferably gum arabic. The first material of the coacervate may be chemically hardened using a suitable crosslinking agent (e.g., glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin), or may be enzymatically hardened using an enzyme (e.g., transglutaminase). The second polymeric material may 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.

[0204] As non-limiting examples, 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 composite, i.e., organic-inorganic, such as a composite shell composed of at least two types of cross-linked inorganic particles, or a shell produced by the hydrolysis and condensation reaction of a polyalkoxysilane macromer composition.

[0205] According to one embodiment, the shell of the second type of microcapsules comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine-formaldehyde or melamine-glyoxal.

[0206] According to another embodiment, the shell of the second type of microcapsules is polyurea-based, made of, for example, but not limited to, isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules comprise a polyurea wall, which is the polymerization reaction product between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from amines (such as water-soluble guanidine salts and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of amines can be omitted. According to a specific embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol, 0.6% to 1% of a cationic copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (all percentages are defined by weight relative to the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is an anionic or amphiphilic biopolymer, which can be selected, for example, from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0207] According to another embodiment, the microcapsule wall material of the second type microcapsules may comprise any suitable resin, particularly including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, and the like. 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 methylol melamine, methylated methylol melamine, imino melamine, and mixtures thereof. Suitable ureas include dimethylol urea, methylated dimethylol urea, urea-resorcinol, and mixtures thereof. Suitable materials for manufacture may be obtained from one or more of the following companies: Solutia Inc. (St Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), Sigma-Aldrich (St. Louis, Missouri USA).

[0208] According to another embodiment, the second type of microcapsules are single-shell aminoplast core-shell microcapsules obtainable by a process comprising the following steps:

[0209] 1) mixing a fragrance oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase;

[0210] 2) dispersing or dissolving the aminoplast resin and optionally the stabilizer in water to form an aqueous phase;

[0211] 3) preparing an oil-in-water dispersion by mixing an oil phase and an aqueous phase, wherein the average droplet size is 1 to 100 microns;

[0212] 4) performing a curing step to form the wall of the microcapsules; and

[0213] 5) Optionally, the final dispersion is dried to obtain dry core-shell microcapsules.

[0214] According to one embodiment, the second type of microcapsules are formaldehyde-free capsules. A typical method for preparing a slurry of aminoplast formaldehyde-free microcapsules comprises the following steps:

[0215] 1) preparing an oligomeric composition comprising the reaction product of, or an oligomeric composition obtained by reacting together:

[0216] a. a polyamine component in the form of melamine or a mixture of melamine and at least one C1-C4 compound comprising two NH2 functional groups;

[0217] b. Glyoxal, C 4-6 The aldehyde component is in the form of a mixture of 2,2-dialkoxyacetaldehyde and optionally glyoxylate, the glyoxal / C 4-6 2,2-dialkoxyethanol in a molar ratio of 1 / 1 to 10 / 1; and

[0218] c. Protonic acid catalyst;

[0219] 2) preparing an oil-in-water dispersion wherein the droplet size is from 1 to 600 microns and comprising:

[0220] a.Oil;

[0221] b. Water medium

[0222] c. at least one oligomeric composition as obtained in step 1;

[0223] d. at least one cross-linking agent selected from the group consisting of:

[0224] i.C4-C 12 Aromatic or aliphatic di- or triisocyanates and their biuret, triuret, trimer, trimethylolpropane adducts and mixtures thereof; and / or

[0225] ii. Di- or tri-oxirane compounds of the formula

[0226] A-(Oxiran-2-ylmethyl) n

[0227] wherein n represents 2 or 3, A represents a C2-C6 group optionally containing 2 to 6 nitrogen and / or oxygen atoms;

[0228] e. Optionally, a C1-C4 compound comprising two NH2 functional groups;

[0229] 3) heating the dispersion;

[0230] 4) Cool the dispersion.

[0231] In another specific embodiment, the second type of microcapsules comprises:

[0232] - an oil-based core comprising a hydrophobic active substance, preferably a perfume,

[0233] - Optionally, an inner shell made from polymerized multifunctional monomers;

[0234] - A biopolymer shell comprising proteins, wherein at least one of the proteins is cross-linked.

[0235] According to a specific embodiment, the protein is selected from the group consisting of milk protein, caseinate (such as sodium caseinate or calcium caseinate), casein, whey protein, hydrolyzed protein, gelatin, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate, most preferably sodium caseinate.

[0236] According to a particular embodiment, the protein comprises sodium caseinate and globular proteins, preferably selected from the group consisting of whey protein, beta-lactoglobulin, ovalbumin, bovine serum albumin, vegetable proteins and mixtures thereof.

[0237] The protein is preferably a mixture of sodium caseinate and whey protein.

[0238] According to a specific embodiment, the biopolymer shell comprises cross-linked proteins selected from the group consisting of sodium caseinate and / or whey protein.

[0239] According to a particular embodiment, the second type of microcapsule slurry comprises at least one microcapsule made of:

[0240] - an oil-based core comprising a hydrophobic active substance, preferably a fragrance;

[0241] - an inner shell made from polymerized polyfunctional monomers; preferably a polyisocyanate having at least two isocyanate functional groups;

[0242] a biopolymer shell comprising proteins, wherein at least one of the proteins is cross-linked; wherein the proteins preferably comprise a mixture comprising sodium caseinate and globular proteins, preferably whey proteins;

[0243] - Optionally, at least one outer mineral layer.

[0244] According to one embodiment, the sodium caseinate and / or whey protein are cross-linked proteins.

[0245] The weight ratio between sodium caseinate and whey protein is preferably from 0.01 to 100, preferably from 0.1 to 10, more preferably from 0.2 to 5.

[0246] In another specific embodiment, the second type of microcapsules are polyamide core-shell polyamide microcapsules comprising:

[0247] - an oil-based core comprising a hydrophobic active substance, preferably a perfume, and

[0248] - a polyamide shell comprising or obtainable from:

[0249] acyl chloride,

[0250] The first amino compound,

[0251] · Second amino compound,

[0252] • Optionally, carbohydrates.

[0253] According to a particular embodiment, the second type of microcapsules comprises:

[0254] - an oil-based core comprising a hydrophobic active substance, preferably a perfume, and - a polyamide shell comprising or obtainable from:

[0255] Acid chloride, preferably in an amount of 5 to 98%, preferably 20 to 98%, more preferably 30 to 85% w / w;

[0256] a first amino compound, preferably in an amount of 1% to 50% w / w, preferably 7 to 40% w / w;

[0257] a second amino compound, preferably in an amount of 1% to 50% w / w, preferably 2 to 25% w / w;

[0258] Stabilizer, preferably a biopolymer, preferably in an amount of 0 to 90%, preferably 0.1 to 75%, more preferably 1 to 70%,

[0259] • Optionally, carbohydrates.

[0260] According to a particular embodiment, the second type of microcapsules comprises:

[0261] - an oil-based core comprising a hydrophobic active substance, preferably a perfume, and

[0262] - a polyamide shell comprising or obtainable from:

[0263] acyl chloride,

[0264] a first amino compound, which is an amino acid, preferably selected from the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and / or mixtures thereof,

[0265] a second amino compound selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine, and / or mixtures thereof, and

[0266] a biopolymer, preferably selected from the group consisting of potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten, lupin protein, soy protein, rice protein, whey protein, egg white protein, casein, sodium caseinate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin, and mixtures thereof,

[0267] Optionally, a carbohydrate, preferably selected from the group consisting of anionic alginic acid salts, preferably sodium alginate salts, pectin, lignin, anionic modified starches, carboxymethylcellulose, carrageenan, and mixtures thereof.

[0268] According to another embodiment, the shell of the second type of microcapsules is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea-based and polyurethane-based microcapsule slurries are described, for example, in International Patent Application Publication No. WO 2007 / 004166, European Patent Application Publication No. EP 2300146, and European Patent Application Publication No. EP 25799. Generally, the method for preparing a polyurea-based or polyurethane-based microcapsule slurry comprises the following steps:

[0269] a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase;

[0270] b) preparing an aqueous solution of an emulsifier or a colloidal stabilizer to form a dispersed phase;

[0271] c) adding the oil phase to the water phase to form an oil-in-water dispersion wherein the average droplet size is from 1 to 500 μm, preferably from 5 to 50 μm; and

[0272] d) applying conditions sufficient to initiate interfacial polymerization and form microcapsules in the form of a slurry.

[0273] Microcapsule powder

[0274] Another object of the present invention is to provide microcapsules in the form of powder by drying (e.g., spray drying) the microcapsule slurry. It should be understood that any standard method for carrying out this drying known to those skilled in the art is also applicable. In particular, the slurry can 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 gum, alginate, carrageenan or a cellulose derivative to provide microcapsules in powder form.

[0275] However, other drying methods may also be cited, such as extrusion, coating, spray granulation, fluidized bed, or even drying at room temperature using materials (carrier, desiccant) that meet specific criteria as disclosed in WO 2017 / 134179.

[0276] According to one particular embodiment, the carrier material comprises free fragrance oil, which may be the same as or different from the fragrance from the microcapsule core.

[0277] Another object of the present invention is a solid particle comprising:

[0278] - carrier material,

[0279] - microcapsules as defined above entrapped in said carrier material, and

[0280] - Optionally, free fragrance embedded in said carrier material.

[0281] In a particular embodiment, the support material comprises a monomeric, oligomeric or polymeric support material, or a mixture of two or more of these.

[0282] An oligomeric carrier is a carrier in which 2 to 10 monomer units are linked by covalent bonds. For example, if the oligomeric carrier is a carbohydrate, the oligomeric carrier may be sucrose, lactose, raffinose, maltose, trehalose, or fructo-oligosaccharides.

[0283] Examples of monomeric carrier materials are glucose, fructose, mannose, galactose, arabinose, fucose, sorbitol, mannitol and the like.

[0284] Polymeric carriers have more than 10 monomeric units linked by covalent bonds.

[0285] In a particular embodiment, the carrier may be a polymeric carrier material. Non-limiting examples of polymeric carrier materials include polyaspartic acid, modified polysuccinimides, lignin and its derivatives, polyoxazolines, polyhydroxyalcanoates, polyphenols, natural and synthetic clays, polyvinyl acetate, polyvinyl alcohol, dextrin, maltodextrin, glucose syrup, natural or modified starches, polysaccharides, carbohydrates, chitosan, gum arabic, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, acrylamide, acrylates, polyacrylic acid and related substances, maleic anhydride copolymers, amine-functional polymers, vinyl ethers, styrene, polystyrene sulfonates, ethylene acid, ethylene glycol-propylene glycol block copolymers, vegetable gums, acacia gum, pectin, xanthan gum, alginates, carrageenan, or cellulose derivatives such as carboxymethyl methylcellulose, methylcellulose or hydroxyethyl cellulose; chitin, proteins (animal and plant), polyaspartic acid, polysuccinimides and their derivatives, polyesters, polyurethanes, polyhydroxyalkanoates, polycarbonates, and mixtures thereof. Preferably, the polymeric carrier material comprises natural or modified starch, maltodextrin, carbohydrates, chitin, proteins (animal and plant), polyaspartic acid, polysuccinimide and its derivatives, polyesters, polyurethanes, polyhydroxyalkanoates, polycarbonates and mixtures thereof.

[0286] According to one embodiment, the carrier material is selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gums, pectin, xanthan gum, alginates, carrageenan, cellulose derivatives and mixtures thereof.

[0287] Solid particles and microcapsule powders as defined above can be used without distinction in the present invention.

[0288] Method for preparing microcapsules

[0289] The microcapsules of the present invention can be prepared by different processes.

[0290] Implementation Plan 1

[0291] The present invention also relates to a method for preparing core-shell microcapsules, comprising the following steps:

[0292] (i) providing a hydrophobic phase comprising a hydrophobic material and at least one multifunctional monomer;

[0293] (ii) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient not to form a complex coacervate suspension; wherein the first polyelectrolyte comprises a plant protein,

[0294] (iii) adding the hydrophobic phase to the dispersed phase to form a two-phase dispersion, and applying conditions sufficient to form a coacervate,

[0295] (iv) providing conditions sufficient to initiate interfacial polymerization to form a core-shell microcapsule slurry.

[0296] Implementation Plan 2

[0297] The present invention also relates to a method for preparing core-shell microcapsules, comprising the following steps:

[0298] (i) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient not to form a complex coacervate suspension; wherein the first polyelectrolyte comprises a plant protein,

[0299] (ii) providing a hydrophobic phase comprising a hydrophobic material and at least one multifunctional monomer;

[0300] (iii) adding the hydrophobic phase to the dispersed phase to form a two-phase dispersion, and applying conditions sufficient to form a coacervate,

[0301] (iv) providing conditions sufficient to initiate interfacial polymerization to form a core-shell microcapsule slurry.

[0302] Implementation Plan 3

[0303] The present invention also relates to a method for preparing core-shell microcapsules, comprising the following steps:

[0304] (i) adding a hydrophobic phase comprising a hydrophobic material and at least one multifunctional monomer to a dispersed phase comprising a first polyelectrolyte; wherein the first polyelectrolyte comprises a plant protein, to form a two-phase dispersion;

[0305] (ii) adding a second polyelectrolyte to the two-phase dispersion,

[0306] (iii) applying conditions sufficient to form a coacervate,

[0307] (iv) providing conditions sufficient to initiate interfacial polymerization to form a core-shell microcapsule slurry.

[0308] According to one embodiment, (step ii) of embodiment 1; step i) of embodiment 2; step ii) of embodiment 3)) the pH of the solution containing two polyelectrolytes is 1 to less than 2.5, preferably 1.5 to 2.2, so that the polyelectrolytes cannot interact with each other to form a coacervate.

[0309] According to one embodiment, the pH of the solution containing the two 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 a coacervate.

[0310] Coagulation occurs in step iii) wherein the pH of the solution is typically between 2.5 and 4.2, preferably between 2.8 and 4.

[0311] The interfacial polymerization reaction is typically 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. However, the interfacial polymerization reaction can also be carried out at room temperature, typically at a temperature of 20 to 30°C.

[0312] According to one embodiment, the dispersed phase comprises water, preferably consists of water.

[0313] According to one embodiment, the dispersed phase is an aqueous phase.

[0314] According to one embodiment, the two-phase dispersion is an oil-in-water emulsion.

[0315] According to one embodiment, the dispersed phase comprises water and an alcohol, such as glycerol, 1,4-butanediol, ethylene glycol, and mixtures thereof.

[0316] According to one embodiment, the hydrophobic phase is an oil phase.

[0317] 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.

[0318] Emulsifiers and / or surfactants may be selected from the list consisting of polyvinyl alcohol, sodium stearoyl lactylate, mono- and diglycerides, lecithin, saponins, ascorbyl palmitate, sugar esters, sucrose esters, sucrose glycerides, 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 lauryl sulfate, taurates, sulfoacetates, alkyl ether sulfates, fatty alcohol sulfates, secondary alkyl sulfonates, alkylbenzol sulfonates, alkyl carboxylates and mixtures thereof.

[0319] Emulsifiers and / or surfactants are typically used in amounts of 0.001 to 5%, based on the hydrophobic phase and / or dispersed phase.

[0320] According to one embodiment, process steps are performed to suppress or reduce foam formation. This includes, for example, using appropriate mixing devices and containers, adjusting stirring speed and container geometry to minimize bubble formation, filling and mixing steps, or using appropriate metering devices or metering methods, including membrane or microcapillary devices. Foam formation can also be suppressed or reduced by adding defoaming agents, which can be introduced into any process step.

[0321] Non-limiting examples of defoaming agents include mineral oils, oils, fatty esters, alcohols, amides, phosphates, metallic soaps, silicones, and mixtures thereof.

[0322] It should be understood that the antifoaming agent is not part of the shell.

[0323] When used, the defoaming agent is preferably used in an amount of 0.05 to 1% by weight based on the dispersed phase.

[0324] According to a particular embodiment, no amines or polyamines susceptible to polymerizing with the polyfunctional monomers are added at any stage of the process.

[0325] The dispersion of the oil phase into the aqueous phase can be carried out by various known techniques. Non-limiting examples include static mixers (SMX, Sulzer, Switzerland), vibrating mixers, stirred tank reactors, ultrasonic homogenizers, membrane emulsifiers (Micropure, UK), high pressure homogenizers (APV, SPX Flow, USA) or microfluidic emulsifiers (Micronit, Netherlands).

[0326] According to one embodiment, the multifunctional monomer is selected from the group consisting of at least one isocyanate, anhydride or maleic anhydride, acid chloride, epoxide, (meth)acrylate monomer, alkoxysilane, and mixtures thereof.

[0327] According to one particular embodiment, the monomer added in step i) or ii) is at least one polyisocyanate having at least two isocyanate functional groups.

[0328] Suitable polyisocyanates for use according to the present invention include aromatic polyisocyanates, aliphatic polyisocyanates and mixtures thereof. The polyisocyanates contain at least 2, preferably at least 3, but may contain up to 6, or even only 4 isocyanate functional groups. According to a specific embodiment, triisocyanates (3 isocyanate functional groups) are used.

[0329] According to one embodiment, the polyisocyanate is an aromatic polyisocyanate.

[0330] The term "aromatic polyisocyanate" is intended herein to encompass any polyisocyanate containing an aromatic moiety. Preferably, it contains a phenyl, toluoyl, xylyl, naphthyl or diphenyl moiety. More preferably, a toluoyl or xylyl moiety. Preferred aromatic polyisocyanates are biuret, polyisocyanurate and trimethylolpropane adducts of diisocyanates, more preferably containing one of the above-mentioned specific aromatic moieties. More preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (available from Bayer under the trade name RC), trimethylolpropane adduct of toluene diisocyanate (available from Bayer under the trade name L75), trimethylolpropane adduct of xylylenediisocyanate (available from Mitsui Chemicals under the trade name In a most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylenediisocyanate.

[0331] According to another embodiment, the polyisocyanate is an aliphatic polyisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain any aromatic moieties. Preferred aliphatic polyisocyanates are trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate (available from Mitsui Chemicals) or biuret of hexamethylene diisocyanate (available from Bayer under the trade name N 100 is commercially available), among which the biuret of hexamethylene diisocyanate is more preferred.

[0332] According to another embodiment, the at least one polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both of which contain at least two or three isocyanate functional groups, such as a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylenediisocyanate, a mixture of a biuret of hexamethylene diisocyanate and a polyisocyanurate of toluene diisocyanate, and a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of toluene diisocyanate. Most preferably, it is a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylenediisocyanate. Preferably, when used as a mixture, the molar ratio between the aliphatic polyisocyanate and the aromatic polyisocyanate is 80:20 to 10:90.

[0333] According to one embodiment, the multifunctional monomer is an acid chloride.

[0334] According to a particular embodiment, the acid chloride conforms to the following formula (I):

[0335]

[0336] wherein n is an integer from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4, and

[0337] Where X is a C2 to C 45 a hydrocarbon group, optionally comprising at least one group selected from (i) to (xi), in particular a group selected from (i) to (vi):

[0338]

[0339] wherein R is a hydrogen atom or an alkyl group, such as a methyl group or an ethyl group, preferably a hydrogen atom.

[0340] It is understood that by "hydrocarbyl..." it is meant that the group is composed of hydrogen and carbon atoms and can be in the form of an aliphatic hydrocarbon, i.e. a straight-chain or branched saturated hydrocarbon (e.g. an alkyl), a straight-chain or branched unsaturated hydrocarbon (e.g. an alkenyl or alkynyl), a saturated cyclic hydrocarbon (e.g. a cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g. a cycloalkenyl or cycloalkynyl), or can be in the form of an aromatic hydrocarbon, i.e. an aryl, or can also be in the form of a mixture of the types of groups mentioned, for example, unless specifically limited to only one type mentioned, a particular group may contain straight-chain alkyl, branched alkenyl (e.g. having one or more carbon-carbon double bonds), (poly)cycloalkyl and aryl moieties. Similarly, in all embodiments of the present invention, when a group is mentioned in the form of more than one type of topology (e.g. straight-chain, cyclic or branched) and / or saturation or unsaturation (e.g. alkyl, aromatic or alkenyl), it is also meant that the group may contain moieties having any of the said topologies or saturation or unsaturation as explained above. Similarly, in all embodiments of the present invention, when a group is referred to as being in one form (e.g., alkyl) that is saturated or unsaturated, it is meant that the group can be of any type of topology (e.g., linear, cyclic, or branched) or have several moieties with various topologies.

[0341] It is understood that the term "...hydrocarbyl, optionally containing..." means that the hydrocarbyl group optionally contains heteroatoms to form ether, thioether, amine, nitrile or carboxylic acid groups and derivatives (including, for example, esters, acids, amides). These groups can replace hydrogen atoms of the hydrocarbyl group and thus be pendant to the hydrocarbon, or replace carbon atoms of the hydrocarbyl group (if chemically possible) and thus be inserted into the hydrocarbon chain or ring.

[0342] According to a specific embodiment, the acyl chloride is selected from the group consisting of benzene-1,3,5-triacyl trichloride (triformyl trichloride), benzene-1,2,4-triacyl trichloride, benzene-1,2,4,5-tetraacyl tetrachloride, cyclohexane-1,3,5-triacyl trichloride, isophthaloyl dichloride, diglycolyl dichloride dichloride), terephthaloyl chloride, fumaryl dichloride, adipoyl chloride, succinyl dichloride, propane-1,2,3-trichloride, cyclohexane-1,2,4,5-tetrachloride, 2,2'-disulfanediyl disuccinyl dichloride, 2-(2-chloro-2-oxoethyl)thiobutanedichloride, (4-chloro-4-oxobutanoyl)-L-glutamyl dichloride, (S)-4-((1,5-dichloro-1,5-dioxopentan-2-yl)amino)-4-oxobutanoic acid, 4-chloro-4-oxo-butyric acid 2,2-bis[(4-chloro-4-oxo-butyryl)oxymethyl]butyl ester, 4-chloro-4-oxo-butyric acid [2-[2,2-bis[(4-chloro-4-oxo 1,2,3-triyl tris(4-chloro-4-oxobutyric acid)propane-1,2,3-triyl tris(4-chloro-4-oxobutyric acid)propane-1,2-diyl tris(4-chloro-4-oxobutyric acid)propane-1,2-diyl tris(4-chloro-4-oxobutyric acid)propane-2,2-diyl tris(4-chloro-4-oxobutyric acid)propane-2,2-diyl tris(4-chloro-4-oxobutyric acid)propane-1,2-diyl tris(4-chloro-4-oxobutyric acid)propane-2,2-diyl tris(4-chloro-4-oxobutyric acid)benzoate, and mixtures thereof.

[0343] According to one embodiment, the content of the multifunctional monomer used in the process of the present invention is 0.1 to 15 wt %, preferably 0.5 to 3 wt %, based on the total amount of the oil phase.

[0344] According to any of the preceding embodiments, the aqueous phase may further comprise an amino resin in addition to the multifunctional monomer present in the oil phase.

[0345] Another object of the present invention is a core-shell microcapsule slurry obtained by the method disclosed above.

[0346] Perfuming compositions and consumer products

[0347] The microcapsules of the present invention can be used in combination with active ingredients. Therefore, one object of the present invention is a composition comprising:

[0348] (i) microcapsules or microcapsule slurries as defined above;

[0349] (ii) an active ingredient, preferably selected from the group consisting of a cosmetic ingredient, a skin care ingredient, a perfume ingredient, a flavoring ingredient, a malodor counteracting ingredient, a bactericide ingredient, a fungicide ingredient, a pharmaceutical or agrochemical ingredient, a disinfectant ingredient, an insect repellent or attractant, and mixtures thereof.

[0350] The capsules of the present invention show good performance in terms of stability in challenging media.

[0351] Another object of the present invention is a perfuming composition comprising:

[0352] (i) microcapsules or microcapsule slurries as defined above, wherein the oil comprises fragrance;

[0353] (ii) at least one ingredient selected from the group consisting of a fragrance carrier, a fragrance co-ingredient, and mixtures thereof;

[0354] (iii) optionally, at least one flavor adjuvant.

[0355] As liquid fragrance carriers there may be mentioned, as non-limiting examples, emulsifying systems, i.e. solvent and surfactant systems, or solvents commonly used in the perfumery industry. A detailed description of the properties and types of solvents commonly used in the perfumery industry is not exhaustive. However, there may be mentioned, as non-limiting examples, solvents such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate, which are the most commonly used. For compositions comprising both fragrance carriers and fragrance co-ingredients, in addition to those previously specified, other suitable fragrance carriers may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, for example those sold under the trademark Benzol. (Source: Exxon Chemical) Those known as glycol ethers and glycol ether esters, such as those sold under the trademark (Source: Dow Chemical Company) are known to those skilled in the art. By "fragrance co-ingredient" is meant a compound used in a perfuming preparation or composition to impart a hedonic effect and which is not a microcapsule as defined above. In other words, to be considered a perfuming co-ingredient, it must be recognized by those skilled in the art as being capable of imparting or modifying the odor of a composition in an active or pleasant manner, rather than merely possessing an odor.

[0356] The nature and type of the flavoring co-ingredients present in the perfuming compositions do not guarantee a more detailed description here, and they are all impossible to be exhaustive in any case, and the skilled person can select them according to their common sense and according to the intended use or application and the required organoleptic effect. Generally speaking, these flavoring co-ingredients belong to different chemical classifications, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds and essential oils, and the flavoring co-ingredients can be of natural or synthetic origin. In any case, many of these co-ingredients are listed in references such as the work Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA or its updated version or other works of similar nature, as well as in the patent literature rich in the field of spices. It is also understood that the co-ingredients can also be compounds known to release various types of flavoring compounds in a controlled manner.The auxiliary component can be selected from the group consisting of: 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-phenylethyl oxy(phenyl)acetate, 3,7-dimethylocta-2,6-diene-1-ol oxy(phenyl)acetate. -yl ester, (Z)-hex-3-en-1-yl oxy(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethyloct-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-en-1-yl , (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(oct-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 2-(1-phenylethoxyprop-1-en-2-yl)naphthalene, (2-phenylethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)benzene 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 a mixture thereof.

[0357] By "perfuming adjuvants" it is meant here ingredients capable of imparting additional added benefits such as colour, specific lightfastness, chemical stability, etc. A detailed description of the nature and types of adjuvants commonly used in perfuming bases is not exhaustive, but it must be mentioned that said ingredients are well known to those skilled in the art.

[0358] Preferably, the perfuming composition according to the invention comprises from 0.01 to 30% by weight of microcapsules or microcapsule slurry as defined above.

[0359] The microcapsules of the present invention can be advantageously used in many fields of application and in consumer products. The microcapsules can be used in liquid form for liquid consumer products or in powder form for powder consumer products.

[0360] According to a particular embodiment, the consumer product as defined above is a liquid and comprises:

[0361] a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product;

[0362] b) water or a water-miscible hydrophilic organic solvent; and

[0363] c) a microcapsule slurry or microcapsules as defined above,

[0364] d) Optionally, non-encapsulated flavors.

[0365] According to a particular embodiment, the consumer product as defined above is in powder form and comprises:

[0366] a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product;

[0367] b) Microcapsule powder as defined above.

[0368] c) Optionally, a spice powder, which is different from the microcapsules as defined above.

[0369] In the case of microcapsules comprising a perfume oil-based core, the products of the invention are particularly useful for perfumed consumer products, such as products belonging to the category of high-quality fine fragrances or "functional" fragrances. Functional fragrances include in particular personal care products, including hair care, body cleansing, skin care, hygiene care, and home care products, including clothing care, surface care and air care. Therefore, another object of the present invention is a perfumed consumer product comprising as a perfume ingredient a microcapsule as defined above or a perfume composition as defined above. The perfume ingredient of the consumer product may be a combination of perfume microcapsules as defined above and free or non-encapsulated perfumes, as well as other types of perfume microcapsules than those disclosed herein.

[0370] In particular, the following liquid consumer product is another object of the present invention, comprising:

[0371] a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product;

[0372] b) water or a water-miscible hydrophilic organic solvent; and

[0373] c) A perfuming composition as defined above.

[0374] Likewise, the following powdered consumer product is also part of the present invention, comprising:

[0375] (a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product; and

[0376] (b) A perfuming composition as defined above.

[0377] Thus, the microcapsules of the invention can be added as such or as part of a perfuming composition of the invention to already perfumed consumer products.

[0378] For the sake of clarity, it must be mentioned that a "perfumed consumer product" is a consumer product intended to deliver, among other benefits, a perfumed effect to the surface to which it is applied (e.g. skin, hair, fabrics, paper or household surfaces) or to the air (air fresheners, deodorants / deodorants, etc.). In other words, a perfumed consumer product according to the present invention is a processed product comprising a functional formulation (also called a "base") and a benefit agent, comprising an effective amount of microcapsules according to the present invention.

[0379] The nature and types of the other ingredients of the perfumed consumer product do not warrant a detailed description here, which is in no way exhaustive; the skilled person will be able to select them based on his general knowledge and the properties and desired effects of the product in question. The extensive literature on such products contains formulations of base materials for consumer products into which the microcapsules according to the invention can be incorporated. These formulations do not warrant a detailed description here, which is in no way exhaustive. A skilled person in the art of formulating such consumer products will be fully capable of selecting suitable components based on his general knowledge and the available literature.

[0380] Non-limiting examples of suitable perfumed consumer products may be perfumes, such as high-quality perfumes, colognes, aftershaves, body-splashes; fabric care products, such as liquid or solid detergents, tablets and capsules (single or multi-chamber), fabric softeners, dryer sheets, fabric refreshers, ironing water, or bleach; personal care products, such as hair care products (e.g., shampoo, hair conditioner, coloring preparations or hair spray), cosmetic preparations (e.g., vanishing creams, body lotions, or deodorants or antiperspirants), or skin care products (e.g., soaps, bath or shower mousses, body washes, wash), bath oil or shower gel, bath salts, or hygiene products); 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 powdered or tablet dishwashing products, toilet bowl cleaners or products for cleaning various surfaces, such as sprays and wipes for treating / refreshing textiles or hard surfaces (floors, tiles, stone floors, etc.); hygiene products, such as sanitary napkins, diapers, toilet paper.

[0381] Another object of the present invention is a consumer product comprising:

[0382] - personal care active bases, and

[0383] - microcapsules or microcapsule slurries as defined above or perfuming compositions as defined above,

[0384] Wherein the consumer product is in the form of a personal care composition.

[0385] The personal care active bases into which the microcapsules of the present invention can be incorporated can be found in a large amount of literature related to such products. These formulations do not warrant a detailed description here, which is by no means exhaustive. A person skilled in the art of formulating such consumer products is fully capable of selecting suitable components based on his general knowledge and the available literature.

[0386] The personal care composition is preferably selected from the group consisting of a hair care product (e.g. a shampoo, a hair conditioner, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream, a body lotion, or a deodorant or an antiperspirant), or a skin care product (e.g. a soap, a bath or shower mousse, a body wash, a bath oil or shower gel, bath salts or a hygiene product).

[0387] Another object of the present invention is a consumer product comprising:

[0388] - home care or fabric care active bases, and

[0389] - microcapsules or microcapsule slurries as defined above or perfuming compositions as defined above,

[0390] Wherein the consumer product is in the form of a home care or fabric care composition.

[0391] Home care or fabric care bases, into which the microcapsules of the present invention can be incorporated, can be found in the extensive literature relating to such products. These formulations do not warrant a detailed description here, which is by no means exhaustive. A person skilled in the art of formulating such consumer products will be well able to select suitable components based on his general knowledge and the available literature.

[0392] Preferably, the consumer product comprises 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. Of course, the above concentrations can be adjusted according to the desired beneficial effects of each product.

[0393] An object of the present invention is a consumer product, preferably a home care or fabric care consumer product, comprising the microcapsules or microcapsule slurry as defined above, wherein the pH of the consumer product is less than 7.

[0394] An object of the present invention is a consumer product, preferably a home care or fabric care consumer product, comprising the microcapsules or microcapsule slurry as defined above, wherein the pH of the consumer product is equal to or greater than 7.

[0395] For liquid consumer products referred to hereinafter, "active base" is to be understood as an active base comprising active materials (typically including surfactants) and water.

[0396] For solid consumer products referred to hereinafter, "active base" is to be understood as meaning the active base comprising active materials (typically including surfactants) and adjuvants (e.g. bleaches, buffers; builders; soil removers or soil suspension polymers; granular enzyme particles, corrosion inhibitors, defoamers, suds suppressors; dyes, fillers and mixtures thereof).

[0397] fabric softener

[0398] An object of the present invention is a consumer product in the form of a fabric softener composition comprising:

[0399] - 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 (esterquats), Hamburg ester quaternary ammonium salts (HEQ) (1,2-stearoyl-3-trimethylammonium-propane (chloride salt)), TEAQ (triethanolamine quaternary ammonium salt), silicones 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,

[0400] - microcapsule slurry or microcapsules as defined above, 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,

[0401] -Optionally, free fragrance oil.

[0402] liquid detergent

[0403] An object of the present invention is a consumer product in the form of a liquid detergent composition comprising:

[0404] - a liquid detergent active base; preferably comprising at least one active material selected from the group consisting of anionic surfactants, such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants, such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucamides, the active base preferably being used in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0405] - microcapsule slurry or microcapsules as defined above, 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,

[0406] -Optionally, free fragrance oil.

[0407] Solid detergent

[0408] An object of the present invention is a consumer product in the form of a solid detergent composition comprising:

[0409] a solid 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), copolymers of ethylene oxide (EO) and propylene oxide (PO), amine oxides, alkyl polyglucosides, alkyl polyglucamides, the active base preferably being used in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0410] - microcapsule powder or microcapsule slurry or microcapsules as defined above, 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,

[0411] -Optionally, free fragrance oil.

[0412] Shampoo / shower gel

[0413] An object of the present invention is a consumer product in the form of a shampoo or shower gel composition comprising:

[0414] - 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-based surfactants 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,

[0415] - microcapsule slurry or microcapsules as defined above, 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,

[0416] -Optionally, free fragrance oil.

[0417] Rinse-off conditioner

[0418] An object of the present invention is a consumer product in the form of a rinse-off conditioner composition comprising:

[0419] - 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,

[0420] - microcapsule slurry or microcapsules as defined above, 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,

[0421] -Optionally, free fragrance oil.

[0422] Solid flavor enhancer

[0423] An object of the present invention is a consumer product in the form of a solid scent booster comprising:

[0424] a solid carrier, preferably selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, sugars such as sucrose, mono-, disaccharides and polysaccharides and derivatives such as starch, cellulose, methylcellulose, ethylcellulose, propylcellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol and isomalt, PEG, PVP, citric acid or any water-soluble solid acid, fatty alcohols or fatty acids and mixtures thereof,

[0425] - microcapsule slurry or microcapsules as defined above, in powder form, 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.

[0426] -Optionally, free fragrance oil.

[0427] Liquid Fragrance Enhancer

[0428] An object of the present invention is a consumer product in the form of a liquid flavor enhancer comprising:

[0429] - aqueous phase,

[0430] - a surfactant system consisting essentially of one or more than one nonionic surfactant, wherein the surfactant system has an average HLB of 10 to 14, preferably selected from the group consisting of ethoxylated aliphatic alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono- and polyglycerol esters, sucrose ester compounds, polyoxyethylene hydroxy esters, alkyl polyglucosides, amine oxides and combinations thereof;

[0431] - a linker selected from the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxycarboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants with an HLB of less than 10, and mixtures thereof, and

[0432] - Microcapsule slurry or microcapsules as defined above, in the form of a slurry, 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.

[0433] -Optionally, free fragrance oil.

[0434] hair dye

[0435] An object of the present invention is a consumer product in the form of an oxidative hair dyeing composition comprising:

[0436] - an oxidizing phase comprising an oxidizing agent and a basic phase comprising an alkaline agent, a dye precursor and a coupling compound; wherein the dye precursor and the coupling compound form an oxidative hair dye in the presence of the oxidizing agent, preferably in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0437] - microcapsule slurry or microcapsules as defined above, 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,

[0438] -Optionally, free fragrance oil.

[0439] Perfuming composition

[0440] According to a particular embodiment, the consumer product is in the form of a perfuming composition comprising, based on the total weight of the perfuming composition:

[0441] - 0.1 to 30% by weight, preferably 0.1 to 20% by weight, of microcapsules or microcapsule slurry as defined above,

[0442] - 0 to 40% by weight, preferably 3 to 40% by weight, of fragrance, and

[0443] - 20 to 90% by weight, preferably 40 to 90% by weight, of ethanol.

[0444] The present invention will now be further described by way of examples. It should be understood that the invention as claimed is not intended to be limited in any way by these examples.

[0445] Example

[0446] Example 1

[0447] Potato protein-based composite microcapsules

[0448] Scheme for preparing microcapsules A

[0449] Prepare potato protein solution in deionized water (natural pH 6.8) 200, source: Avebe).

[0450] Prepare gum arabic solution in deionized water (Superstab TM , source: Nexira).

[0451] The pH of the potato protein and gum arabic solutions were adjusted to 2 using concentrated HCl (37%) and then mixed to obtain an aqueous phase.

[0452] Preparation of polyisocyanate ( —trimethylolpropane adduct of benzyl diisocyanate, source: Mitsui Chemicals, Inc., Japan, 75% polyisocyanate in ethyl acetate) and fragrance oil (see Table 1), which was then added to the aqueous phase (potato protein / gum arabic solution (pH ˜2)) using an Ultra-Turrax with shearing at 13,500 rpm for 1 minute to obtain an oil-in-water emulsion.

[0453] The pH was then raised to pH 3 by addition of NaOH 1 M (0.73 g) with stirring.

[0454] After checking for coagulation by light microscopy, glutaraldehyde was added and the suspension was stirred at room temperature for 4 hours.

[0455] Table 1: Composition of Fragrance Oil A

[0456] Element % in oil 2-Methylvalerate Ethyl ester 3.2％ Eucalyptol 7.8％ 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde 0.75％ Aldehyde C10 0.75％ Citronellyl nitrile 4.3％ Isobornyl acetate 3％ 2-tert-Butyl-1-cyclohexyl acetate 9.8％ Citronellyl acetate 1.3％ 2-Methylundecanal 3％ diphenyl ether 0.8％ Aldehyde C12 1.3％ Dicyclopentadienyl acetate 9.85％ β-ionone 3.3％ γ-Undecalactone 18.75％ Hexyl salicylate 15.9％ Benzyl salicylate 16.2％

[0457] Table 2: Composition of microcapsules

[0458]

[0459] 1) Solanic 200 2% solution, source: Avebe

[0460] 2) Superstab TM Source: Nexira

[0461] 3) D110N, Source: Mitsui Chemicals, Inc.

[0462] 4) Source: Merck-Sigma Aldrich

[0463] Figure 1 and Figure 2 Optical microscope and SEM microscope images of the microcapsules are shown, respectively.

[0464] Example 2

[0465] Potato protein-based composite microcapsules

[0466] Microcapsules B were prepared according to the protocol of Example 1, except that at the end of the process the suspension was heated at 85°C for 30 minutes.

[0467] Example 3

[0468] Rapeseed protein-based composite microcapsules

[0469] Preparation scheme of microcapsule C

[0470] 50 g of canola protein (CP) was prepared in deionized water (natural pH = 6.5) ( Source: DSM) as a 4% solution.

[0471] Prepare 50 g of gum arabic (GA) (Superstab TM , source: Nexira) as a 4% solution.

[0472] The two solutions were mixed together and concentrated HCl (37%) (0.36 g) was added to lower the pH to 2.4.

[0473] The mixture consists of 30g of spices and 0.75g of The oil solution made with 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.

[0474] The pH of the emulsion was then adjusted to 4.09 by adding NaOH 1 M solution (2.3 g) dropwise under mechanical stirring.

[0475] The aggregation of CP / GA complexes around the oil droplets was examined by optical microscopy.

[0476] Then, 0.22 g of a 50% solution of glutaraldehyde was added to the suspension thus obtained, and the slurry was stirred at 800 rpm at room temperature for 3.5 hours and then heated at 75° C. for 1 hour under the same stirring conditions.

[0477] Table 3: Composition of microcapsules

[0478]

[0479] 1) Source: DSM

[0480] 2) Superstab TM Source: Nexira

[0481] 3) D110N, Source: Mitsui Chemicals, Inc.

[0482] 4) Source: Merck-Sigma Aldrich

[0483] Figure 3 Optical microscope and SEM microscope images of the microcapsules are shown, respectively.

[0484] Example 4

[0485] Stability of the microcapsules of the present invention

[0486] The microcapsules of the present invention were dispersed in the fabric softener (FS) composition described in Table 4 or in the liquid detergent (LD) composition described in Table 5 to obtain a concentration of 0.116% encapsulated fragrance oil.

[0487] Table 4: Fabric Conditioner Composition

[0488] product weight% Stepantex VL 90A 8.88 Calcium chloride solution 10% 0.36 Proxel GXL 0.04 spices 1.00 water 89.72 total 100

[0489] Table 5: Liquid detergent composition

[0490] Element Concentration [wt%] <![CDATA[C 14-17 Sodium secondary alkyl sulfonate 1) ]]> 7 <![CDATA[C 12-18 and C 18 - Unsaturated fatty acids 2) ]]> 7.5 <![CDATA[C with 7 mol EO 12 / 14 Fatty alcohol polyglycol ether 3) > 17 triethanolamine 7.5 Propylene glycol 11 citric acid 6.5 potassium hydroxide 9.5 <![CDATA[Properase L 4) ]]> 0.2 <![CDATA[Puradax EG L 4) ]]> 0.2 <![CDATA[Purastar ST L 4) ]]> 0.2 <![CDATA[Acrylate / Steareth-20 Methacrylate Structured Crosslinked Polymer 5) > 6 Deionized water 27.4

[0491] 1) Hostapur SAS 60; Source: Clariant

[0492] 2) Edenor K 12-18; Source: Cognis

[0493] 3) Genapol LA 070; Source: Clariant

[0494] 4) Source: Genencor International

[0495] 5) Aculyn 88; Source: Dow Chemical

[0496] Weigh 2g of sample (base and capsule) into a 20mL vial. Add 10mL of the extraction solvent, isooctane, containing an internal standard, 1,4-dibromobenzene, at a precisely known concentration of approximately 90ng / μL. Shake at 40 RPM for 45 minutes to extract the free fragrance. Then remove the solvent phase.

[0497] To measure the leakage in the base material, an Agilent GCFID7890A was used with the injector set at 250°C, helium as the carrier gas at a flow rate of 1 mL / min, and the oven temperature was programmed to start at 120°C, hold for 5 minutes, increase to 170°C at 10°C / min, increase to 220°C at 25°C / min, and then increase to 260°C at 25°C / min. For subsequent runs, measurements were completed at 260°C.

[0498] Calibration solutions of 100, 300, and 600 ng / μL of the aromatic oil were prepared in isooctane. It is important that the aromatic oil used to prepare the calibration curves comes from the same batch used to produce the microcapsules.

[0499] The stability of microcapsules A and B are as follows Figure 4 and Figure 5 shown.

[0500] It can be concluded that the microcapsules of the present invention show good stability in fabric softeners and liquid detergents.

[0501] Example 5

[0502] Olfactory performance of the microcapsules of the present invention

[0503] plan

[0504] The dosage of fragrance oil in fabric softener is 0.1%.

[0505] The dosage of fragrance oil in liquid detergent is 0.2%.

[0506] Cleaning solution :

[0507] Program: 40°C - short spin - 900 rpm

[0508] Towels: 36

[0509] Unscented detergent: 55g

[0510] Softener: 23g

[0511] Storage Solutions

[0512] Drying: Place the towel on a drying rack to dry for 1 day

[0513] Evaluate:

[0514] Each panelist was given a set of towels: they were asked to smell the dry towels and rate the scent intensity on a scale of 0 (no scent) to 10 (very strong scent). They were then asked to rub the towels back and forth three times and rate the scent intensity after rubbing them using the same scale.

[0515] Table 6: Olfactory performance results

[0516]

[0517] A noticeable fragrance enhancement is perceived after rubbing in both fabric softener and liquid detergent applications.

[0518] Example 6

[0519] Biodegradability of microcapsules

[0520] Shell extraction (Following the method published in Gasparini et al. in Molecules 2020, 25, 718)

[0521] The microcapsule slurry is freeze-dried. Use a crusher IKA tube mill control to grind the recovered solid for 30 seconds. The resulting paste (aromatic oil+polymer shell) is suspended in 300mL ethyl acetate, and the mixture is stirred at room temperature for 1 hour. Solids are collected by vacuum filtration on a Gooch filter crucible (porosity 4). Repeat this extraction step 5 times to remove the maximum amount of aromatic oil from the shell. The powder is dried under vacuum (10mBar) at 50°C until the polymer weight monitored by gravimetric analysis is constant. Use a crusher IKA tube mill control to grind the resulting powder for 1 minute and 30 seconds, suspend in deionized water (0.5% w / w) and stir at room temperature for 24 hours with 300RPM. Remove water by vacuum filtration on a Gooch filter crucible (porosity 4), and the powder is dried at room temperature for 2.5 days, then dried overnight at 50°C under vacuum (10mBar). Finally, the resulting powder was ground using a crusher IKA tube mill control for 1 minute 30 seconds and extracted five more times with ethyl acetate as described above. The final powder was dried overnight at 50°C under vacuum (10 mBar). To ensure complete fragrance removal, samples were analyzed by GC pyrolysis and biodegradation measurements were performed according to the OECD 301F method.

[0522] After 60 days of testing, the biodegradability of the shell of microcapsule A was greater than 50%.

[0523] Example 7

[0524] Determination of the shell composition of the capsules of the present invention by solid-state NMR

[0525] Based on the carbon signals of the individual components, NMR was able to determine the following shell composition of microcapsule A:

[0526] -52% potato protein

[0527] -28% gum arabic

[0528] -14% polyisocyanate

[0529] -6% residual (glutaraldehyde)

[0530] Furthermore, relaxation time measurements have demonstrated that all nuclei have statistically identical environments, which is the basis for shell homogeneity.

[0531] Example 8

[0532] Preparation of spray-dried microcapsules

[0533] Emulsions A to E were prepared having the following compositions.

[0534] Table 7: Composition of emulsions A to E and composition of granular powders A to E after spray drying

[0535]

[0536] 1) Capsul™, Ingredion

[0537] 2) Maltodextrin 10DE Source: Roquette

[0538] 3) Maltose, Lehmann & Voss

[0539] 4) Silica, Evonik

[0540] 5) See Table 8

[0541] Table 8: Composition of Fragrance B

[0542]

[0543] 1) Firmenich SA, Switzerland

[0544] 2) 3-(4-tert-Butylphenyl)-2-methylpropanal, Givaudan SA, Vergne, Switzerland

[0545] 3) 1-(Octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone, International Flavors & Fragrances, USA

[0546] 4) Firmenich SA, Switzerland

[0547] 5) Methyl dihydrojasmonate, Firmenich SA, Switzerland

[0548] 6) Firmenich SA, Switzerland

[0549] The components of the polymer matrix (maltodextrin and capsules) were mixed at 45-50°C. TM or Capsul™, citric acid, and tripotassium citrate) are added to water until completely dissolved.

[0550] For Emulsion D, free fragrance C was added to the water phase.

[0551] The microcapsule slurry was added to the resulting mixture.Then, the resulting mixture was gently mixed at 25°C (room temperature).

[0552] Granular powders A-E were prepared by spray drying emulsions A-E using a Sodeva spray dryer (source: France) with an inlet temperature of 215°C and a throughput of 500 mL per hour. The outlet temperature was 105°C. The emulsions were at ambient temperature before atomization.

[0553] Example 9

[0554] Liquid flavor enhancer composition

[0555] Sufficient example microcapsules were weighed and mixed into the liquid flavor enhancer to add the equivalent of 0.2% flavor.

[0556] Table 9: Liquid Fragrance Enhancer Composition

[0557]

[0558] 1) Deceth-8; Trademark and source: KLK Oleo

[0559] 2) Laureth-9; Trademark and Source:

[0560] 3) Plantacare 2000UP; Trademark and source: BASF

[0561] Different ringing gel compositions (Compositions 1 to 6) were prepared according to the following protocol.

[0562] In the first step, the aqueous phase (water), solvent (propylene glycol) (if present) and surfactant were mixed together at room temperature using a magnetic stirrer at 300 rpm for 5 minutes.

[0563] In a second step, the linker was dissolved in the hydrophobic active ingredient (fragrance) at room temperature with stirring on a magnetic stirrer at 300 rpm. The resulting mixture was mixed for 5 minutes.

[0564] The water phase and the oil phase are then mixed together at room temperature for 5 minutes to form a clear or milky ringing gel.

[0565] Example 10

[0566] Liquid detergent compositions

[0567] Sufficient example microcapsules were weighed and mixed into liquid detergent to add the equivalent of 0.2% perfume.

[0568] Table 10: Liquid detergent composition

[0569] Element Concentration [wt%] <![CDATA[C 14-17 Sodium secondary alkyl sulfonate 1) ]]> 7 <![CDATA[C 12-18 and C 18 - Unsaturated fatty acids 2) ]]> 7.5 <![CDATA[C with 7 mol EO 12 / 14 Fatty alcohol polyethylene glycol ether 3) > 17 triethanolamine 7.5 Propylene glycol 11 citric acid 6.5 potassium hydroxide 9.5 <![CDATA[Properase L 4) ]]> 0.2 <![CDATA[Puradax EG L 4) ]]> 0.2 <![CDATA[Purastar ST L 4) ]]> 0.2 <![CDATA[Acrylate / Steareth-20 Methacrylate Structured Crosslinked Polymer 5) > 6 Deionized water 27.4

[0570] 6) Hostapur SAS 60; Source: Clariant

[0571] 7) Edenor K 12-18; Source: Cognis

[0572] 8) Genapol LA 070; Source: Clariant

[0573] 9) Source: Genencor International

[0574] 10) Aculyn 88; Source: Dow Chemical

[0575] Example 11

[0576] Unit dose formulations

[0577] Sufficient exemplary microcapsules were weighed and mixed into the unit dose formulation to add the equivalent of 0.2% flavor.

[0578] The unit dose may be contained in a PVOH (polyvinyl alcohol) film.

[0579] Table 11: Composition of unit dose

[0580] Element Concentration [wt%] C12-C14 alkyl polyethoxylate 15 C12-C14 alkyl polyethoxylate sulfate monoethanolamine salt 9.5 Linear alkylbenzene sulfonic acid 17 citric acid 0.5 C12-C18 fatty acids 17 enzymes 1.2 fluorescent brightener 0.3 1,2-Propanediol 12 glycerin 9 Sodium hydroxide 1 Monoethanolamine 6 PDMS 2.5 Potassium sulfite 0.2 water 8.8 total 100

[0581] Example 12

[0582] Powder detergent compositions

[0583] Sufficient exemplified microcapsules were weighed and mixed into a powder detergent composition to add the equivalent of 0.2% perfume.

[0584] Table 12: Powder detergent composition

[0585] Element Number of copies Anion (linear alkylbenzene sulfonate) 20％ Nonionic (alcohol ethoxylate (5-9 ethylene oxide)) 6％ Detergents (zeolite, sodium carbonate) 25％ silicates 6％ sodium sulfate 35％ Others (enzymes, polymers, bleaching agents) 7.5％ Spray-dried microparticle powders A to E 0.5％

[0586] Example 13

[0587] Concentrated all-purpose cleaning composition

[0588] Sufficient exemplary microcapsules were weighed and mixed into a concentrated all-purpose cleaner composition to add the equivalent of 0.2% fragrance.

[0589] Table 13: Concentrated All-Purpose Cleaner Compositions

[0590] Element Amount (weight %) Function <![CDATA[Ethoxylated alcohol (C9-C11, 8EO) (1) > 20 nonionic surfactants <![CDATA[Sodium dodecylbenzenesulfonate (2) > 16 Anionic surfactants <![CDATA[Sodium cumene sulfonate (3) > 8 Hydrotrope <![CDATA[Methylchloroisothiazolinone Methylisothiazolinone 3.3:1 (4) > 0.8％ preservative water 55.9 solvent

[0591] 1) Neodol Trademark and source: Shell Chemical

[0592] 2) Biosoft Trademark and source: Stepan Company

[0593] 3) Stepanate Trademark and source: Stepan Company

[0594] 4) Kathon Trademark and source: Dow Chemical Company

[0595] Mix all ingredients together and dilute the mixture to 100% with water.

[0596] Example 14

[0597] Solid flavor enhancer composition

[0598] The following compositions were prepared.

[0599] Table 14: Salt-based solid flavor enhancer composition

[0600] Element Number of copies Sodium chloride 95 Spray-dried microparticle powders A to E 5

[0601] Table 15: Urea-based solid flavor enhancer composition

[0602] Element Number of copies Urea (beads) 94 Spray-dried microparticle powders A to E 8 Bentonite 3 spices 3

[0603] Example 15

[0604] Shampoo composition

[0605] Sufficient exemplary microcapsules were weighed and mixed into a shampoo composition to add the equivalent of 0.2% fragrance.

[0606] Table 16: Shampoo composition

[0607]

[0608] 1)Ucare Polymer JR-400, Noveon

[0609] 2) Schweizerhall

[0610] 3) Glydant, Lonza

[0611] 4)Texapon NSO IS, Cognis

[0612] 5) Tego Betain F 50, Evonik

[0613] 6)Amphotensid GB 2009,Zschimmer&Schwarz

[0614] 7) Monomuls 90L-12, Gruenau

[0615] 8) Monosodium paraben, NIPA

[0616] Disperse Polyquaternium-10 in water. Mix the remaining ingredients of Phase A separately by adding them one by one, mixing thoroughly after each adjuvant is added. Add this premix to the Polyquaternium-10 dispersion and mix for an additional 5 minutes. Then, add the premixed Phase B and premixed Phase C (heat Monomuls 90L-12 to melt in Texapon NSO IS) while stirring. Add Phase D and Phase E while stirring. Adjust the pH to pH: 5.5-6.0 with citric acid solution.

[0617] Example 16

[0618] Shampoo composition

[0619] Sufficient exemplary microcapsules were weighed and mixed into the shampoo composition to add the equivalent of 0.2% fragrance.

[0620] Table 17: Shampoo composition

[0621]

[0622]

[0623] 1) EDETA B powder, BASF

[0624] 2) Jaguar C14 S, Rhodia

[0625] 3)Ucare Polymer JR-400, Noveon

[0626] 4)Sulfetal LA BE,Zschimmer&Schwarz

[0627] 5)Zetesol LA,Zschimmer&Schwarz

[0628] 6) Tego Betain F 50, Evonik

[0629] 7)Xiameter MEM-1691,Dow Corning

[0630] 8) Lanette 16, BASF

[0631] 9) Comperlan 100, Cognis

[0632] 10) Cutina AGS, Cognis

[0633] 11) Kathon CG, Rohm & Haas

[0634] 12) D-Panthenol, Roche

[0635] Add the premix containing guar hydroxypropyltrimonium chloride and polyquaternium-10 to the water and tetrasodium EDTA while mixing. When the mixture is homogeneous, add the sodium hydroxide solution. Then, add the Phase C ingredients. Heat the mixture to 75°C. Add the Phase D ingredients and mix until homogeneous. Remove from heat and allow the mixture to cool to room temperature. At 45°C, add the Phase E ingredients while mixing. Adjust the final viscosity with a 25% sodium chloride solution and the pH to 5.5-6 with a 10% sodium hydroxide solution.

[0636] Example 17

[0637] Rinse-off hair composition

[0638] Sufficient exemplary microcapsules are weighed and mixed into a rinse-off composition to add the equivalent of 0.2% perfume.

[0639] Table 18: Rinse-off compositions

[0640]

[0641] 1)Genamin KDMP,Clariant

[0642] 2)Tylose H10 Y G4,Shin Etsu

[0643] 3) Lanette O, BASF

[0644] 4)Arlacel 165,Croda

[0645] 5)Incroquat Behenyl TMS-50-PA-(MH),Croda

[0646] 6) Brij S20, Croda

[0647] 7)Xiameter MEM-949,Dow Corning

[0648] 8) Alfa Aesar

[0649] Mix the ingredients of Phase A until a homogeneous mixture is obtained. Allow the Tylose to dissolve completely. 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 good stirring and continue mixing until the mixture reaches a temperature of 60°C. Then, add the ingredients of Phase C while stirring and continue mixing until the mixture cools to 40°C. Adjust the pH to 3.5-4.0 with citric acid solution.

[0650] Example 18

[0651] Antiperspirant spray anhydrous composition

[0652] Sufficient exemplary microcapsules were weighed and mixed into the antiperspirant spray anhydrous composition to add the equivalent of 0.2% fragrance.

[0653] Table 19: Antiperspirant Spray Anhydrous Composition

[0654] Element Amount (weight %) <![CDATA[Cyclic dimethylsiloxane 1) > 53.51 Isopropyl myristate 9.04 <![CDATA[Silicon dioxide 2) > 1.03 <![CDATA[Quaternary ammonium salt-18 hectorite 3) > 3.36 <![CDATA[Aluminum Chlorohydrate 4) > 33.06

[0655] 1) Dow 345Fluid; Trademark and source: Dow Corning

[0656] 2) 200; Trademark and source: Evonik

[0657] 3) 38; Trademark and source: Elementis Specialities

[0658] 4) Micro Dry Ultrafine; Source: Reheis

[0659] Using a high-speed blender, add silica and quaternium-18-hectorite to the mixture of isopropyl myristate and cyclomethicone. Once fully swollen, add aluminum chlorohydrate in portions while stirring until the mixture is homogeneous and free of lumps. Fill an aerosol can with 25% of the suspension and 75% of propane / butane (2.5 bar).

[0660] Example 19

[0661] Antiperspirant spray emulsion composition

[0662] Sufficient exemplary microcapsules were weighed and mixed into the antiperspirant spray emulsion composition to add the equivalent of 0.2% fragrance.

[0663] Table 20: Antiperspirant Spray Emulsion Composition

[0664] Element Amount (weight %) <![CDATA[Polysorbate 65 1) (Part A)]]> 0.95 <![CDATA[Polyglyceryl-2 Dimer Dihydroxystearate 2) (Part A)]]> 1.05 <![CDATA[Cetyl PEG / PPG-10 / 1 Dimethicone 3) (Part A)]]> 2.75 <![CDATA[Cyclic dimethylsiloxane 4) (Part A)]]> 16.4 <![CDATA[Isopropyl isostearate 5) (Part A)]]> 4.5 <![CDATA[Phenoxyethanol 6) (Part A)]]> 0.5 <![CDATA[Ethylhexyl glycerin 7) (Part A)]]> 0.2 <![CDATA[C12-15 alkyl benzoate 8) (Part A)]]> 5.65 <![CDATA[Silylated silica stone 9) (Part A)]]> 0.1 <![CDATA[Sodium methylparaben 10) (Part B)]]> 0.1 <![CDATA[Aluminum Chlorohydrate 11) (Part B)]]> 20 Water (Part B) 44.47 Fragrances (Section C) 3.33

[0665] 1) Tween 65; Trademark and source: CRODA

[0666] 2) Dehymuls PGPH; Trademark and source: BASF

[0667] 3) Abil EM-90; Trademark and source: BASF

[0668] 4) Dow Corning 345 fluid; Trademark and source: Dow Corning

[0669] 5) Crodamol ipis; Trademark and source: CRODA

[0670] 6) Phenoxyethanol; Trademark and source: LANXESS

[0671] 7) Sensiva sc 50; Trademark and source: KRAFT

[0672] 8) Tegosoft TN; Trademark and Source: Evonik

[0673] 9) Aerosil R 812; Trademark and source: Evonik

[0674] 10) Nipagin mna; Trademark and source: CLARIANT

[0675] 11) Locron L; Trademark and Source: CLARIANT

[0676] Weigh the ingredients of Parts A and B separately. Heat the ingredients of Part A to 60°C and the ingredients of Part B to 55°C. Pour the ingredients of Part B into Part A in a small portion while continuously stirring. Stir the mixture thoroughly until it reaches room temperature. Then, add the ingredients of Part C. Mix the emulsion and place it into an aerosol can. Compress the propellant and add it.

[0677] Aerosol filling: 30% emulsion: 70% propane / butane 2.5 bar

[0678] Example 20

[0679] Deodorant spray composition

[0680] Sufficient exemplary microcapsules were weighed and mixed into an antiperspirant deodorant spray composition to add the equivalent of 0.2% fragrance.

[0681] Table 21: Deodorant Spray Composition

[0682] Element Amount (weight %) Ethanol 95% 90.65 <![CDATA[Triclosan 1) > 0.26 Isopropyl myristate 9.09

[0683] 1) DP 300; Trademark and source: BASF

[0684] All ingredients were mixed and dissolved according to the order of Table 24. The aerosol can was then filled, compressed and the propellant added (aerosol fill: 40% active solution, 60% propane / butane 2.5 bar).

[0685] Example 21

[0686] Antiperspirant roll-on lotion composition

[0687] Sufficient exemplary microcapsules were weighed and mixed into an antiperspirant roll-on composition to add the equivalent of 0.2% fragrance.

[0688] Table 22: Antiperspirant Roll-On Composition

[0689] Element Amount (weight %) <![CDATA[Stearyl alcohol polyether-2 1) (Part A)]]> 3.25 <![CDATA[Stearyl alcohol polyether-21 2) (Part A)]]> 0.75 <![CDATA[PPG-15 Stearyl Ether 3) (Part A)]]> 4 Deionized water (Part B) 51 <![CDATA[50% Aqueous Solution of Aluminum Chlorohydrate 4) (Part C)]]> 40 Fragrances (Section D) 1

[0690] 1) BRIJ 72; Source: ICI

[0691] 2) BRIJ 721; Source: ICI

[0692] 3) ARLAMOL E; Source: UNIQEMA-CRODA

[0693] 4) LOCRON L; Source: CLARIAN

[0694] Heat Parts A and B separately to 75°C; add Part A to Part B while stirring, and homogenize the mixture for 10 minutes. Then, cool the mixture while stirring. When the mixture reaches 45°C, slowly add Part C. When the mixture reaches 35°C, slowly add Part D while stirring. Then, cool the mixture to room temperature.

[0695] Example 22

[0696] Antiperspirant roll-on composition

[0697] Sufficient exemplary microcapsules were weighed and mixed into an antiperspirant roll-on composition to add the equivalent of 0.2% fragrance.

[0698] Table 23: Antiperspirant Roll-On Composition

[0699] Element quantity Water (Part A) 45 <![CDATA[50% aqueous solution of aluminum chlorohydrate 1) (Part B)]]> 20 Denatured alcohol (96% ethanol) (Part B) 30 <![CDATA[Ceteth-12 2) (Part C)]]> 2 <![CDATA[Ceteareth-30 3) (Part C)]]> 2 Fragrances (Section D) 1

[0700] 1) LOCRON L; Source: CLARIANT

[0701] 2) EUMULGIN B-1; Source: BASF

[0702] 3) EUMULGIN B-3; Source: BASF

[0703] Combine the ingredients of Part B in a container and then add the ingredients of Part A. Then dissolve Part C into Parts A and B. For fragrance, add 1 part Cremophor RH40 to 1 part fragrance while mixing well.

[0704] Example 23

[0705] Antiperspirant roll-on composition

[0706] Sufficient exemplary microcapsules were weighed and mixed into an antiperspirant roll-on composition to add the equivalent of 0.2% fragrance.

[0707] Table 24: Antiperspirant Roll-On Composition

[0708] Element Amount (weight %) Water (Part A) 50.51 <![CDATA[Hydroxyethyl cellulose 1) (Part A)]]> 0.71 Ethanol 95% (Part B) 40.40 1,2-Propanediol (Part B) 5.05 <![CDATA[Triclosan 2) (Part B)]]> 0.30 <![CDATA[PEG-40 Hydrogenated Castor Oil 3) (Part C)]]> 3.03

[0709] 1) 250H; Trademark and source: Ashland

[0710] 2) DP 300; Trademark and source: BASF

[0711] 3) RH 40; Trademark and source: BASF

[0712] Prepare Part A by sprinkling hydroxyethylcellulose little by little into the water while stirring rapidly with a turbine. Continue stirring until the hydroxyethylcellulose is fully swollen and forms a clear gel. Then, pour Part B little by little into Part A while continuing to stir until the mixture is homogeneous. Add Part C.

[0713] Example 24

[0714] Deodorant pumps with alcohol-free formulations

[0715] Sufficient exemplary microcapsules were weighed and mixed into the following composition to add the equivalent of 0.2% fragrance.

[0716] Table 25: Deodorant Composition

[0717] Element Amount (weight %) <![CDATA[C12-15 alkyl lactate 1) > 5 <![CDATA[Polydimethylsiloxane 2) > 91.6 <![CDATA[Hexadecyl lactate 3) > 1 <![CDATA[Octyldodecanol 4) > 0.8 <![CDATA[Triclosan 5) > 0.1 spices 1.5

[0718] 1) Ceraphyl 41; Trademark and source: ASHLAND

[0719] 2) DOW CORNING 200FLUID 0.65cs; Trademark and source: DOW CORNING CORPORATION

[0720] 3) Ceraphyl 28; Trademark and source: ASHLAND

[0721] 4) Eutanol G; Trademark and source: BASF

[0722] 5) DP 300; Trademark and source: BASF

[0723] Combine all ingredients in the order listed and heat the mixture slightly to dissolve the cetyl lactate.

[0724] Example 25

[0725] Deodorant pump with alcohol-based formula

[0726] Sufficient exemplary microcapsules were weighed and mixed into the following composition to add the equivalent of 0.2% fragrance.

[0727] Table 26: Deodorant Composition

[0728] Element Amount (weight %) Ethanol (Part A) 60 <![CDATA[PEG-6 Caprylic / Capric Glycerides 1) (Part A)]]> 2 Water (Part A) 35.6 <![CDATA[PEG-40 Hydrogenated Castor Oil 2) (Part B)]]> 0.4 Spices (Part B) 2

[0729] 1) Softigen 767; Trademark and source: CRODA

[0730] 2) RH 40; Trademark and source: BASF

[0731] Combine the ingredients in Part B. Dissolve the ingredients in Part A in the order listed, then pour into Part B.

[0732] Example 26

[0733] Talc formulations

[0734] Weigh out sufficient amounts of microgranules A to E and mix into a standard talc base: 100% talc, very slight characteristic odor, white powder, source: LUZENAC, to add the equivalent of 0.2% of fragrance.

[0735] Example 27

[0736] Shower Gel Reference

[0737] Sufficient exemplary microcapsules were weighed and mixed into the following composition to add the equivalent of 0.2% fragrance.

[0738] Table 27: Body wash composition

[0739] Element Amount (weight %) Function Deionized water 49.350 solvent <![CDATA[Sodium EDTA 1) > 0.050 chelating agents <![CDATA[Acrylate copolymer 2) > 6.000 thickener <![CDATA[Sodium C12-C15 alcohol polyether sulfate 3) > 35.000 surfactants 20% sodium hydroxide aqueous solution 1.000 pH adjusters <![CDATA[Cocamidopropyl betaine 4) > 8.000 surfactants <![CDATA[Methylchloroisothiazolinone and Methylisothiazolinone 5) > 0.100 preservative Citric acid (40%) 0.500 pH adjusters

[0740] 1) EDETA B powder; Trademark and source: BASF

[0741] 2) CARBOPOL AQUA SF-1 polymer; Trademark and source: NOVEON

[0742] 3) ZETESOL AO 328U; Trademark and source: ZSCHIMMER & SCHWARZ

[0743] 4) TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0744] 5) KATHON CG; Trademark and source: ROHM & HASS

[0745] The ingredients were mixed and the pH was adjusted to 6-6.3 (viscosity: 4500 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0746] Example 28

[0747] Shower gel composition

[0748] Sufficient exemplary microcapsules were weighed and mixed into the following composition to add the equivalent of 0.2% fragrance.

[0749] Table 28: Body wash composition

[0750] Element Amount (weight %) Function Deionized water 52.40 solvent <![CDATA[Sodium EDTA 1) > 0.10 chelating agents Sodium benzoate 0.50 preservative Propylene glycol 2.00 solvent <![CDATA[Sodium C12 - C15 alcohol polyether sulfate 2) > 35.00 surfactants <![CDATA[Cocamidopropyl betaine 3) > 8.00 surfactants <![CDATA[Polyquaternium-7 4) > 0.20 Conditioner Citric acid (40%) 1.00 pH adjusters Sodium chloride 0.80 Viscosity regulator

[0751] 1) EDETA B powder; Trademark and source: BASF

[0752] 2) ZETESOL AO 328U; Trademark and source: ZSCHIMMER & SCHWARZ

[0753] 3) TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0754] 4) MERQUAT 550; Trademark and source: LUBRIZOL

[0755] The ingredients were mixed and the pH was adjusted to 4.5 (viscosity: 3000 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0756] Example 29

[0757] Shower gel composition

[0758] Sufficient exemplary microcapsules were weighed and mixed into the following composition to add the equivalent of 0.2% fragrance.

[0759] Table 29: Body wash composition

[0760]

[0761]

[0762] 1) EDETA B powder; Trademark and source: BASF

[0763] 2) Texapon NSO IS; Trademark and Source: COGNIS

[0764] 3) MERQUAT 550; Trademark and source: LUBRIZOL

[0765] 4) DEHYTON AB-30; Trademark and source: COGNIS

[0766] 5) GLUCAMATE LT; Trademark and source: LUBRIZOL

[0767] 6) EUPERLAN PK 3000AM; Trademark and source: COGNIS

[0768] 7) CREMOPHOR RH 40; Trademark and source: BASF

[0769] The ingredients were mixed and the pH was adjusted to 4.5 (viscosity: 4000 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0770] Example 30

[0771] Hand dishwashing detergent

[0772] Sufficient exemplary microcapsules were weighed and mixed into the following composition to add the equivalent of 0.2% fragrance.

[0773] Table 30: Hand Dishwashing Detergent Composition

[0774] Element Amount (weight %) Function <![CDATA[Linear alkylbenzene sulfonic acid (1) > 20 Anionic surfactants <![CDATA[Diethanolamide (2) > 3.5 Foam enhancer <![CDATA[Sodium hydroxide (50%) (3) > 3.4 pH adjuster / neutralizer <![CDATA[Secondary alcohol ethoxolate (4) > 2.5 nonionic surfactants Sodium xylenesulfonate 6.3 hydrotrope water 64.3 solvent

[0775] 1) Biosoft Trademark and source: Stepan Company

[0776] 2) Ninol Trademark and source: Stepan Company

[0777] 3) Stepanate Trademark and source: Stepan Company

[0778] 4) Tergitol Trademark and source: Dow Chemical Company

[0779] Mix water with sodium hydroxide and diethanolamide. Add LAS. After neutralizing the LAS, add the remaining ingredients. Check the pH (=7-8) and adjust if necessary.

[0780] Example 31

[0781] Soap bar formulations

[0782] Soap bar compositions including the exemplary microcapsules were prepared at a concentration of 7.5% w / w.

[0783] Table 31: Composition of soap formulations

[0784] Element Soap formulation (%) surfactants Sodium linear alkylbenzene sulfonate soap 10 to 25 α-Olefin Sulfonate (AOS) Sodium lauryl sulfate detergent sodium carbonate 5 to 15 Sodium tripolyphosphate zeolite filler sodium sulfate 5 to 30 talc 5 to 30 dolomite 5 to 50 porcelain clay 5 to 50 Calcite - calcium carbonate Sodium chloride 5 to 20 Structural ingredients aluminum sulfate 0.5 to 5 Alkali silicates 1 to 5 other pigment 0.1 to 1 spices 0.1 to 1 Moisture 5 to 15

[0785] Example 32

[0786] Toothpaste formulations

[0787] A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor was encapsulated) was weighed and mixed into the following composition to add the equivalent of 0.2% flavor.

[0788] Table 32: Toothpaste formulation

[0789] Element Amount (weight %) polyethylene glycol 400 2.0％ Xanthan gum 0.6％ Sorbitol 70% solution 50％ Sodium fluoride 0.220％ Sodium benzoate 0.2％ water 15.230％ <![CDATA[Hydrated silica 1) > 22.0％ <![CDATA[Hydrated silica 2) > 7.0％ Titanium Dioxide CI77891 0.5％ Sodium lauryl sulfate 1.250％ flavorings 1.2％ total 100％

[0790] 1) Tixosil 73

[0791] 2) Tixosil 43

[0792] Example 33

[0793] Dicalcium phosphate-based toothpaste formulations

[0794] A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor was encapsulated) was weighed and mixed into the following composition to add the equivalent of 0.2% flavor.

[0795] Table 33: Toothpaste formulation

[0796] Element Amount (weight %) Sodium carboxymethyl cellulose 1.2％ flavorings 1.2％ Deionized water / pure water Remainder to final weight Sodium lauryl sulfate 1.3％ glycerin 20.0％ Saccharin sodium 0.2％ Dicalcium hydrogen phosphate dihydrate 36.0％ Methylparaben 0.2％ <![CDATA[Silicon dioxide 1) > 3.0％ total 100％

[0797] 1) 200

[0798] Example 34

[0799] Alcohol-free mouthwash formulations

[0800] A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor was encapsulated) was weighed and mixed into the following composition to add the equivalent of 0.2% flavor.

[0801] Table 34: Mouthwash Formulations

[0802] Element Amount (weight %) Propylene glycol 10％ flavorings 0.240％ Deionized water / pure water Remainder to final weight Poloxamer 407NF 0.240％ Sodium lauryl sulfate 0.040％ Sorbitol 70% solution 10.0％ Saccharin sodium 0.030％ glycerin 3.0％ Sodium benzoate 0.100％ Sucralose 0.020％ benzoic acid 0.050％ total 100％

[0803] Example 35

[0804] Mouthwash formulations

[0805] A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor was encapsulated) was weighed and mixed into the following composition to add the equivalent of 0.2% flavor.

[0806] Table 35: Mouthwash Formulations

[0807] Element Amount (weight %) Ethanol 190Proof 15.0％ Seasoning 0.240％ Deionized water / pure water Remainder to final weight Poloxamer 407NF 0.240％ Sodium lauryl sulfate 0.040％ Sorbitol 70% solution 10.0％ Saccharin sodium 0.030％ glycerin 3.0％ Sodium benzoate 0.100％ Sucralose 0.020％ benzoic acid 0.050％ total 100％ .

Claims

1. A core-shell microcapsule comprising: - a core comprising a hydrophobic material, preferably a perfume oil, and - a polymer shell comprising: - Polymeric materials, and a coacervate comprising a first polyelectrolyte and a second polyelectrolyte, The first polyelectrolyte comprises plant protein.

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

3. The microcapsule according to 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. The microcapsule according to claim 3 , wherein the plant protein is potato protein.

5. The microcapsule according to any one of the preceding claims, wherein the second polyelectrolyte is selected from the group consisting of gum arabic, alginates, cellulose derivatives, guar gum, pectinates, pectin, carrageenan, polyacrylic and methacrylic acids, cellulose derivatives, xanthan gum, microbial exopolysaccharides and mixtures thereof. The microcapsule according to claim 5 , wherein the second polyelectrolyte is gum arabic.

7. The microcapsule according to any one of the preceding claims, wherein the polymeric material is selected from the group consisting of polyureas, polyesters, polyurethanes, polyamides, polyacrylates, polysiloxanes, polycarbonates, polysulfonamides, poly(β-amino esters), polylactic acid, poly(thiol-acrylates), 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 microcapsule according to any one of the preceding claims, wherein it comprises: - a kernel containing a fragrance oil, and - a shell comprising polyurea and a coacervate comprising potato protein and gum arabic.

9. The microcapsule of any one of the preceding claims, wherein the polymeric material is present in an amount of less than 10 wt. %, based on the total weight of the microcapsule.

10. A method for preparing core-shell microcapsules, comprising the following steps: (i) providing a hydrophobic phase comprising a hydrophobic material and at least one multifunctional monomer; (ii) mixing a first polyelectrolyte and a second polyelectrolyte in a dispersed phase under conditions sufficient not to form a complex coacervate suspension; 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 initiate interfacial polymerization to form a core-shell microcapsule slurry.

11. A consumer product comprising: - Base materials for consumer products, and - microcapsules as defined in any one of claims 1 to 9, in, The consumer product is preferably in the form of a household care product or a personal care product.

12. The consumer product according to claim 11, wherein it is in the form of a fabric softener composition comprising: - 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 (esterquats), 1,2-stearoyl-3-trimethylammonium-propane (chloride salts), TEAQ (triethanolamine quaternary ammonium salts), silicones 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, - 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.

13. The consumer product according to claim 11, wherein it is in the form of a liquid detergent composition comprising: - a liquid detergent active base; preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucamides, the active base preferably being used in an amount of 85 to 99.95% by weight, 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.

14. The consumer product according to claim 11, wherein it is in the form of a solid detergent composition comprising: a solid detergent active base; preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucamides, the active base preferably being used in an amount of 85 to 99.95% by weight, 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.

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