Microcapsules and methods for preparing microcapsules

Abstract

This invention relates to core-shell microcapsules. Methods for preparing the above microcapsules are also covered by this invention. Fragrance compositions and consumer products containing the above microcapsules, particularly fragrance consumer products in the form of home care or personal care products, are also part of this invention.

Description

[Technical Field]

[0001] This invention relates to core-shell microcapsules. Methods for preparing the above microcapsules are also covered by this invention. Fragrance compositions and consumer products containing the above microcapsules, particularly fragrance consumer products in the form of home care or personal care products, are also part of this invention.

[0002] Background of the Invention One of the problems facing the fragrance industry is that, due to their volatility, particularly the volatility of "top notes," the olfactory benefits provided by the scented compounds are lost relatively quickly. To regulate the release rate of volatile substances, delivery systems such as microcapsules containing fragrances need to protect the core payload and release it later when triggered. A key requirement from the industry for these systems is that they withstand suspension in a difficult base without physically dissociating or decomposing. This is referred to as the stability of the delivery system. For example, scented personal and household detergents containing high levels of aggressive surfactants present significant challenges to the stability of microcapsules.

[0003] Polyurea and polyurethane-based microcapsule slurries are widely used, for example, in the fragrance industry, because they provide a pleasant, long-lasting olfactory effect after being applied to different substrates. These microcapsules are widely disclosed in the prior art.

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

[0005] Therefore, there remains a need to provide novel microcapsules that use more environmentally friendly materials, without compromising the performance of microcapsules, particularly their stability in challenging media such as consumer product bases, and their ability to deliver active ingredients, such as olfactory properties in the case of fragrance components.

[0006] The present invention proposes a solution to the above-mentioned problems by providing novel microcapsules and a process for preparing said microcapsules.

[0007] Summary of the Invention According to the present invention, it has been found that high-performance core-shell microcapsules encapsulating a hydrophobic material can be obtained by reacting at least one compound having at least two P-Cl functional groups with at least one compound comprising an inorganic moiety. Accordingly, the microcapsules of the present invention provide a solution to the above-mentioned problems, since they make it possible to prepare environmentally friendly microcapsules with the desired stability in challenging bases.

[0008] In a first aspect, the present invention relates to - a core comprising a hydrophobic material, and - a shell comprising a reaction product between at least one compound comprising an inorganic moiety and at least one compound having at least two P-Cl functional groups relates to a core-shell microcapsule.

[0009] Another subject of the present invention is a core-shell microcapsule slurry comprising at least one microcapsule, wherein the microcapsule comprises - a core comprising a hydrophobic material, and - a shell comprising a reaction product between at least one compound comprising an inorganic moiety and at least one compound having at least two P-Cl functional groups It is a core-shell microcapsule slurry.

[0010] Another subject of the present invention is a process for preparing a core-shell microcapsule slurry, a) optionally, providing at least one compound having at least two P-Cl functional groups, b) A step of mixing at least one hydrophobic material with any compound obtained in step a) to form an oil phase. c) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. d) Optionally, disperse the two-phase dispersion in a continuous phase C2 which optionally contains at least one compound having at least two P-Cl functional groups to form a multiple dispersion. e) A step of curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d) and / or step e). It is a method.

[0011] The present invention also relates to flavored consumer products and flavored food products comprising microcapsules or microcapsule slurries as defined above.

[0012] Detailed description of the invention Unless otherwise specified, percentages (%) refer to weight percentages of the composition.

[0013] "Active ingredient" refers to a single compound or a combination of ingredients.

[0014] "Fragrance oil or flavor oil" means a single fragrance or flavoring compound or a mixture of multiple fragrance or flavoring compounds.

[0015] "Consumer product" or "final product" means a product that is ready for distribution, sale, and use by consumers.

[0016] For clarity, the term "dispersion" in this invention refers to a system in which particles are dispersed in a continuous phase of different compositions, and specifically includes suspensions or emulsions.

[0017] In the present invention, "microcapsule" or its synonym means that a core-shell microcapsule has a particle size distribution in the micron range (for example, a particle size distribution in the range of an average diameter (d(v,0.5)) preferably about 1 to 3000 microns, more preferably 1 to 500 microns) and comprises an outer solid polymer shell and an inner continuous oil phase surrounded by the outer shell.

[0018] A "microcapsule slurry" refers to microcapsules dispersed in a liquid. In one embodiment, the slurry is an aqueous slurry, meaning the microcapsules are dispersed in the aqueous phase.

[0019] The terms "dispersion medium phase" and "continuous phase" can be used interchangeably in this invention.

[0020] [Core-shell microcapsules] In the first aspect, the present invention is - A core containing hydrophobic material, - A shell comprising a reaction product between at least one compound containing an inorganic moiety and at least one compound having at least two P-Cl functional groups. This relates to core-shell microcapsules, including those mentioned above.

[0021] (Hydrophobic materials) According to one embodiment, the core is an oil-based core.

[0022] The hydrophobic material according to the present invention may be an "inert" material such as a solvent or an active ingredient.

[0023] A "hydrophobic material" refers to any hydrophobic material that forms a two-phase dispersion when mixed with water. Hydrophobic materials are typically liquid at around 20°C.

[0024] According to one embodiment, the hydrophobic material is a hydrophobic active component.

[0025] When the hydrophobic material is the active ingredient, it is preferably selected from the group consisting of flavors, flavor components, fragrances, fragrance components, nutritional supplements, cosmetics, pest control agents, biocides, agricultural chemical components, and mixtures thereof.

[0026] According to certain embodiments, the hydrophobic material includes a phase change material (PCM).

[0027] According to a particular embodiment, the hydrophobic material comprises a mixture of a fragrance and another component selected from the group consisting of nutritional supplements, cosmetics, pest control agents, and biocides.

[0028] According to a particular embodiment, the hydrophobic material comprises a mixture of a biocide and another component selected from the group consisting of fragrances, nutritional supplements, cosmetics, and pest control agents.

[0029] According to a particular embodiment, the hydrophobic material comprises a mixture of an insecticide and another component selected from the group consisting of fragrances, nutritional supplements, cosmetics, and biocides.

[0030] According to certain embodiments, the hydrophobic material includes a fragrance.

[0031] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0032] According to a particular embodiment, the hydrophobic material comprises a biocide.

[0033] According to a particular embodiment, the hydrophobic material comprises an insecticide.

[0034] In this specification, “fragrance” (or “fragrance oil”) means an ingredient or composition that is liquid at about 20°C. According to any one of the embodiments described above, the fragrance oil may be a single fragrance component or a mixture of components in the form of a fragrance composition. In this specification, “fragrance component” means a compound used primarily for the purpose of imparting or modulating a scent. In other words, such a component that should be considered a fragrance component should be recognized by those skilled in the art not merely as having a scent, but as being able to impart or modify the scent of a composition in a positive or pleasant way. For the purposes of the present invention, fragrance oils also include combinations of fragrance components with substances that together improve, enhance or modify the delivery of the fragrance component, such as fragrance precursors, modifiers, emulsions or dispersions, as well as combinations that impart additional benefits beyond modifying or imparting a scent, such as long-lasting effects, blooming, odor neutralization, antimicrobial effects, microbial stability, and pest control.

[0035] While this specification does not guarantee a more detailed description of the properties and types of fragrance components present in the oil phase, and would not be able to cover them all anyway, those skilled in the art can select them based on their general knowledge, according to the intended use or application and the desired sensory stimulation effect. Generally speaking, these fragrance components belong to various chemical classes such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds, and essential oils (e.g., thyme oil), and these fragrance auxiliary components may be of natural or synthetic origin. Many of these auxiliary components are listed in reference texts such as S. Arctander's book, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest edition, or other papers of similar nature, as well as in the extensive patent literature in the field of fragrances.

[0036] In particular, fragrance components commonly used in fragrance formulations, for example: - Aldehyde components: decanal, dodecanal, 2-methyl-undecinal, 10-undecenal, octanal, nonanal and / or nonenal; - Aromatic-herbal ingredients: Eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0 2,7 Undecane-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxatian, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undecane-8-en-1-one, menthol and / or alpha-pinene; - Balsamic components: Coumarin, ethyl vanillin and / or vanillin; - Citrus components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpene, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-mentadiene; - Floral components: Methyldihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (1E (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one Ten-1-one, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexen-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate, geraniol, p-mentha-1-en-8-ol , 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis-methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, verdyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, propyl(S)-2-(1,1-dimethylpropoxy)propanoate, 2-methoxynaphthalene, 2,2,A mixture of 2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamaldehyde, 8-decene-5-olido, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, verdyl isobutyrate and / or methyl ionone isomers; - Fruit components: γ-Undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxatian, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl[3-ethyl-2-oxyranyl]acetate and / or diethyl 1,4-cyclohexanedicarboxylate; - Green components: 2-methyl-3-hexanone(E)-oxime, 2,4-dimethyl-3-cyclohexen-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styraryl acetate, allyl(2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; - Musk components: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecene-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecene-2-one, 1-oxa-13-cyclohexadecene-2-one, (9Z)-9-cycloheptadecene-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3-methyl-5-cyclo Pentadecene-1-one, 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, oxacyclohexadecane-2-one, and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate; - Woody components: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxiran-2,9'-tricyclo[6.2.1.0 2,7 Undeca[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undeca-8-ene-1-ylacetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, Clearwood®, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopentene-1'- Il)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methylcedyl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalene-2-yl)ethane-1-one and / or isobornyl acetate; - Other ingredients (e.g., amber, powdery spicy, or watery): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal One could list these:

[0037] It is also understood that the above components may be compounds known to release various types of fragrance compounds, also known as pro-fragrances or pro-scent agents, in a controlled manner. Non-limiting examples of preferred pro-fragrances include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, and 2-(dodecylthio) Octane-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hexa-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-ylhexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2 -((2-methylundeca-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, (3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, 1-(((Z)-hexa-3-en-1-yl)oxy)-2-methylundeca-1-ene, (2-((2-methylundeca-1-en-1-yl) (L)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undeca-1-ene, 1-methoxy-4-(1-phenoxypropa-1-en-2-yl)benzene, 1-methyl-4-(1-phenoxypropa-1-en-2-yl)benzene, 2-(1-phenethoxypropa-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,Examples include 7-dimethylocta-6-en-1-yl)oxy)propa-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde, or mixtures thereof.

[0038] The fragrance components may be dissolved in solvents currently used in the fragrance industry. The solvent is preferably not an alcohol. Examples of such solvents include diethyl phthalate, isopropyl myristate, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is highly hydrophobic and sterically hindranced, such as Abalyn® or benzyl benzoate. Preferably, the fragrance contains less than 30% solvent. More preferably, the fragrance contains less than 20% solvent, and even more preferably less than 10%, all of which are determined by weight relative to the total weight of the fragrance. Most preferably, the fragrance is essentially solvent-free.

[0039] Preferred fragrance components are those with high steric hindrance, particularly those belonging to the following groups: - Group 1: Fragrance components comprising a cyclohexane, cyclohexene, cyclohexanone, or cyclohexenone ring substituted with at least one linear or branched C1-C4 alkyl or alkenyl substituent; - Group 2: Fragrance components comprising a cyclopentane, cyclopentene, cyclopentanone, or cyclopentenone ring substituted with at least one linear or branched C4-C8 alkyl or alkenyl substituent; - Group 3: Fragrance components containing a phenyl ring, or fragrance components containing a cyclohexane, cyclohexene, cyclohexanone, or cyclohexenone ring substituted with at least one linear or branched C5-C8 alkyl or alkenyl substituent or at least one phenyl substituent and optionally one or more linear or branched C1-C3 alkyl or alkenyl substituents; - Group 4: Fragrance components containing at least two condensed or bonded C5 and / or C6 rings; - Group 5: Fragrance components containing a camphor-like ring structure; - Group 6: At least one C7~C 20 Fragrance components containing a ring structure; - Group 7: Fragrance components having a logP value greater than 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent. It is from one of them.

[0040] Examples of components from each of these groups are as follows: - Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (manufacturer: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomentone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (manufacturer: Firmenich SA, Geneva, Switzerland), neron, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-p-mentadiene-7-ol (manufacturer: Firmenich Firmenich SA, Geneva, Switzerland), 1-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-mentanyl acetate, (1R,2S,4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (manufacturer: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanediethyl dicarboxylate (manufacturer: Firmenich SA, Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethylbenzo[B]furan-2-one (manufacturer: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethylbenzo[B]furan-2-one (manufacturer: Firmenich SA (Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde; - Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (Manufacturer: Givaudan SA, Bernier, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (Manufacturer: Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol (Manufacturer: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentaneacetate (Manufacturer: Firmenich Firmenich SA, Geneva, Switzerland; 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (manufacturer: Firmenich SA, Geneva, Switzerland); 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Firmenich SA, Geneva, Switzerland); 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (manufacturer: Givaudan SA, Bernier, Switzerland); - Group 3: Damascone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), (1'R)-2-[2-(4'-methyl-3'-cyclohexen-1'-yl)propyl]cyclopentanone, α-ionone, β-ionone, damascenone, mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (manufacturer: Firmenich Firmenich SA, Geneva, Switzerland, (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate (Manufacturer: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (Manufacturer: International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (Manufacturer: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (Manufacturer: Firmenich SA, Geneva, Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpenyl isobutyrate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate (manufacturer: Firmenich SA, Geneva, Switzerland), 8-methoxy-1-p-menthen, (1S,1'R)-2-[1-(3',3'-Dimethyl-1'-Cyclohexyl)Ethoxy]-2-Methylpropylpropanoate (Manufacturer: Firmenich SA, Geneva, Switzerland), para-tert-butylcyclohexanone, mententhiol, 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allylcyclohexylpropionate, cyclohexyl salicylate, 2-Methoxy-4-methylphenyl methyl carbonate, ethyl 2-methoxy-4-methylphenyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate; - Group 4: Methylcedyl ketone (Manufacturer: International Flavors and Fragrances, USA), (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6 Deca-3-en-8-yl 2-methylpropanoate and (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0 2,6Mixture with deca-4-en-8-yl 2-methylpropanoate, vetyverol, vetyverone, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone (manufactured by International Flavors and Fragrances, USA), (5RS,9RS,10SR)-2,6,9,10-tetramethyl-1-oxaspiro[4.5]deca-3,6-diene and (5RS,9SR,10RS) isomers, 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]deca-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indenone (manufactured by International Flavors and Fragrances (USA), mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (Manufacturer: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undeca-4-en-9-spiro-2'-oxirane (Manufacturer: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (Manufacturer: Firmenich SA, Geneva, Switzerland), octarinol (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan, Manufacturer: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]deca-3-en-8-ylacetate and tricyclo[5.2.1.0(2,6)]deca-4-en-8-ylacetate and tricyclo[5.2.1.0(2,6)]deca-3-en-8-ylpropanoate and tricyclo[5.2.1.0(2,6)]deca-4-en-8-ylpropanoate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptan-3-spiro-2'-cyclohexen-4'-one; - Group 5: Camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]octa-5-en-2-carbaldehyde, pinene, camphene, 8-methoxysedran, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (manufacturer: Firmenich SA, Geneva, Switzerland), sedrene, sedrenol, sedrol, 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0 2,7 Mixture with undecane-4-one (manufacturer: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (manufacturer: Firmenich SA, Geneva, Switzerland); - Group 6: (Trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (Manufacturer: Firmenich SA, Geneva, Switzerland), 9-Hexadecene-16-Olide (Manufacturer: Firmenich SA, Geneva, Switzerland), Pentadecenolide (Manufacturer: Firmenich SA, Geneva, Switzerland), 3-Methyl-(4 / 5)-cyclopentadecenone (Manufacturer: Firmenich SA, Geneva, Switzerland), 3-Methylcyclopentadecanone (Manufacturer: Firmenich SA, Geneva, Switzerland), Pentadecanolide (Manufacturer: Firmenich SA, Geneva, Switzerland), Cyclopentadecanone (Manufacturer: Firmenich SA, Geneva, Switzerland), 1-Ethoxyethoxy)cyclododecane (Manufacturer: Firmenich SA, Geneva, Switzerland, 1,4-dioxacycloheptadecane-5,17-dione, 4,8-cyclododecadiene-1-one; - Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (Manufacturer: Givaudan SA, Bernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate That is the case.

[0041] Preferably, the fragrance contains at least 30%, preferably at least 50%, and more preferably at least 60% of a component selected from groups 1 to 7 as defined above. More preferably, the fragrance contains at least 30%, preferably at least 50%, of a component from groups 3 to 7 as defined above. Most preferably, the fragrance contains at least 30%, preferably at least 50%, of a component from groups 3, 4, 6, or 7 as defined above.

[0042] According to another preferred embodiment, the fragrance contains at least 30%, preferably at least 50%, and more preferably at least 60%, of components whose logP is greater than 3, preferably greater than 3.5, and more preferably greater than 3.75.

[0043] According to certain embodiments, the fragrance used in the present invention contains less than 10% primary alcohol by weight, less than 15% secondary alcohol by weight, and less than 20% tertiary alcohol by weight. Advantageously, the fragrance used in the present invention does not contain primary alcohol and contains less than 15% secondary and tertiary alcohol.

[0044] According to one embodiment, the oil phase (or oil-based core) is - Fragrance oils containing 25-100% by weight, with at least 15% by weight of high-impact fragrance ingredients with Log T < -4, and - 0-75% by weight, 1.07 g / cm³ 3 Density-adjusting material with ultra-high density Includes.

[0045] "High-impact fragrance ingredients" should be understood as fragrance ingredients with LogT < -4. The odor threshold concentration of a chemical substance is partially determined by its shape, polarity, partial charge, and molecular weight. For convenience, the odor threshold concentration is presented as the common logarithm of the threshold concentration, i.e., Log[threshold] ("LogT").

[0046] "Density adjustment material" refers to 1.07 g / cm³ 3It should be understood as a material having a density greater than that, and preferably being low-odor or odorless.

[0047] The odor threshold concentration of a perfuming compound is determined using a gas chromatograph ("GC"). Specifically, the gas chromatograph is calibrated using k reference materials with known concentrations and chain length distributions, to determine the exact volume of the perfume oil component injected from the syringe, the exact split ratio, and the hydrocarbon response. The air flow rate is accurately measured, and the sampled volume is calculated on the assumption that human inhalation lasts for 12 seconds. Since the exact concentration at the detector at any point in time is known, the mass per inhaled volume is known, and thus the concentration of the perfuming compound is known. To determine the threshold concentration, a solution at the back-calculated concentration is sent to the sniff port. A panelist sniffs the GC effluent and identifies the residence time when the odor is perceived. The average across all panelists determines the odor threshold concentration of the perfuming compound. The determination of the odor threshold 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 (Volume 33, September 2008, pages 54-61).

[0048] High-impact perfume materials with LogT < -4 and 1.07 g / cm 3 The properties of density-adjusting materials having a greater density are described in International Publication No. 2018115250, the content of which is incorporated by reference.

[0049] According to one embodiment, the high-impact fragrance raw materials with LogT<-4 include (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenylacetate, pyrazobutyle, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl)pyridine, and 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-phenylpropyl Penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; a mixture containing (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[b]furan-2-one and (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[b]furan-2-one; (+-)-1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one, (1'S,3'R)-1-methyl-2-[(1 ',2',2'-trimethylbicyclo[3.1.0]hexa-3'-yl)methyl]cyclopropyl}methanol, (+-)-3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-buten-1-one, H-methyl-2h-1,5-benzodioxepin-3(4H)-one, (2E,6Z)-2,6-nonadien-1-ol, (4Z)-4-dodecenal, (+-)-4-hydroxy-2,5-dimethyl-3(2H)-flavor Non, a mixture containing methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methyl indole, (+-)-perhydro-4α,8β-dimethyl-4a-naphthalenol, patchulol, 2-methoxy-4-(1-propenyl)phenol, (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylene-2-phenyl-2H-pyran, 4-methylene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,A mixture containing 6-dihydro-2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonylenealdehyde, 2-methoxy-4-propylphenol, 3-methyl-5-phenyl-2-pentennitrile, 1-(spiro[4.5]deca-6 / 7-en-7-yl)-4-penten-1-one,2-methoxynaphthalene, (-)-(3aR,5AS,9AS,9BR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 5-nonanolide, (3aR,5AS,9AS,9BR)-3a,6,6,9a-te Tramethyl dodecahydronaphtho[2,1-b]furan, 7-isopropyl-2H,4H-1,5-benzodioxepin-3-one, coumarin, 4-methylphenylisobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, beta,2,2,3-tetramethyl-delta-methylene-3-cyclopenten-1-butanol, delta-damascone((2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one) (+-)-3,6-dihydro-4,6-dimethyl-2-phenyl-2h-pyran, anisaldehyde, paracresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2-aminobenzoate, ethylmethylphenylglycidate, octalactone gamma, ethyl 3-phenyl-2-propenoate, (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, paracresil acetate, dodecalactone, tricyclon, (+)-(3R,5Z) -3-methyl-5-cyclopentadecene-1-one, undecalactone, (1R,4R)-8-mercapto-3-p-mentanone, (3S,3AS,6R,7AR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, β-ionone, (+-)-6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1,3,5-undecatriene, 10-undecenal, (9E)-9-undecenal (9Z)-9-undecenal, (Z)-4-decenal, (+-)-ethyl 2-methylpentanoate, 1,2-Diallyl disulfane, 2-Tridecennitrile, 3-Tridecennitrile, (+-)-2-Ethyl-4,4-Dimethyl-1,3-Oxatian, (+)-(3R,5Z)-3-Methyl-5-Cyclopentadecene-1-one, 3-(4-Tert-Butylphenyl)propanal, Allyl(Cyclohexyloxy)acetate, Methylnaphthylketone, (+-)-(4E)-3-methyl -4-Cyclopentadecene-1-one, (+-)-5E3-methyl-5-cyclopentadecene-1-one, cyclopropylmethyl3-hexenoate, (4E)-4-methyl-5-(4-methylphenyl)-4-pentenal, (+-)-1-(5-propyl-1,3-benzodioxol-2-yl)ethanone, 4-methyl-2-pentylpyridine, (+-)-(E)-3-methyl-4-( 2,6,6-Trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan, (2S,5R)-5-methyl-2-(2-propanyl)cyclohexanone oxime, 6-Hexyltetrahydro-2H-pyran-2-one, (+-)-3-(3-isopropyl (Lu-1-phenyl)butanal, methyl 2-(3-oxo-2-pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohexa-2-enyl)penta-1-en-3-one, indole, 7-propyl-2H,4H-1,5-benzodioxepin-3-one, ethylpraline, (4-methylphenoxy)acetaldehyde, ethyltricyclo[5.2.1.0., 2,6]decane-2-carboxylate, (+)-(1'S,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol, (4E)-3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-isopropyl-6-methyl -Bicyclo[2.2.2]octa-5-en-2-carbaldehyde, methylnonylacetaldehyde, 4-formyl-2-methoxyphenyl 2-methylpropanoate, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, (1R,5R)-4,7,7-trimethyl-6-thiabi Cyclo[3.2.1]octa-3-ene, (1R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1,6-octadiene-3-ol, (E)-3-phenyl-2-propennitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopene Selected from the group consisting of ten-1-yl)-4-penten-2-ol, allyl(2 / 3-methylbutoxy)acetate, (+-)-(2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1-penten-3-one, and mixtures thereof.

[0050] According to one embodiment, the fragrance raw material with LogT < -4 is selected from the group consisting of aldehydes, ketones, alcohols, phenols, ester lactones, ethers, epoxides, nitriles, and mixtures thereof.

[0051] According to one embodiment, the LogT<-4 fragrance raw material contains at least one compound selected from the group consisting of alcohols, phenols, ester lactones, ethers, epoxides, nitriles, and mixtures thereof, preferably in an amount between 20% and 70% by weight based on the total weight of the LogT<-4 fragrance raw material.

[0052] According to one embodiment, the fragrance raw material with LogT < -4 contains aldehydes, ketones, and mixtures thereof in an amount between 20% and 70% by weight, based on the total weight of the fragrance raw material with LogT < -4.

[0053] Therefore, the remaining flavoring ingredients in the oil-based core may have a Log T > -4.

[0054] According to one embodiment, the fragrance raw materials for Log T>-4 are ethyl 2-methyl butyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropional, verdylpropionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl) acetate, (+-)-(E)-4-methyl-3-decen-5-ol, 2,4-dimethyl-3-cyclohexen-1-carbaldehyde, 1,3,3-trimethyl-2-oxabicyclo[2.2.2] Octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa-12 / 13-cyclohexadecene-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, aldehyde C11, (+-)-2,6-dimethyl-7-octen-2-ol, allyl 3-cyclohexylpropanoate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, allylheptanoate, 2-(2-methyl-2 -Propanyl)cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl butyrate, geranyl acetate, neryl acetate, (+-)-1-phenylethyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, ethyl 3-oxobutanoate, (2Z)-ethyl 3-hydroxy-2-butenoate, 8-p-menthanol, 8-p-mentanyl acetate, 1-p-mentanyl acetate, (+-)-2-(4-methyl-3-cyclohexenyl-1- (+-)-2-propanyl acetate, (+-)-2-methylbutylbutanoate, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3,5,6-trimethyl-3-cyclohexen-1-carbaldehyde, 2,4,6-trimethyl-3-cyclohexen-1-carbaldehyde, 2-cyclohexylethyl acetate, octanal, ethylbutanoate, (+-)-(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, ethylhexanoate, undecanal, decanal, 2-phenylethyl acetate, (1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]Heptan-2-ol), (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2-propanylidene)cyclohexene, (+)-(R)-4-(2-methoxypropan-2-yl)-1-methylcyclohexa-1-ene, Verdyl acetate, (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1 The following are selected from the group consisting of -[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3R)-1-[(1S,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (+)-(1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, and mixtures thereof.

[0055] According to one embodiment, the core is - 0-60% by weight of hydrophobic solvent (based on the total weight of the fragrance mixture) - A fragrance oil comprising 40-100% by weight (based on the total weight of the fragrance blend), with the following characteristics: • A fragrance component having a logP greater than 3, preferably greater than 3.5, comprising at least 35%, preferably at least 40%, preferably at least 50%, and more preferably at least 60%. • At least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40%, of bulk materials from groups 1 to 6, preferably groups 3 to 6, as defined herein. • At least 15%, preferably at least 20%, more preferably at least 25%, and even more preferably at least 30% of high-impact fragrance materials with LogT < -4 A fragrance oil having at least two, preferably all, of the following: Optionally, further hydrophobic active ingredients Contains fragrance compounds.

[0056] According to a particular embodiment, the fragrance contains 0 to 60% by weight of a hydrophobic solvent.

[0057] According to a particular embodiment, the hydrophobic solvent is preferably a density-modifying material selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethylphenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylate, benzyl cinnamate, and mixtures thereof.

[0058] In certain embodiments, the hydrophobic solvent has a Hansen solubility parameter that is compatible with the captured fragrance oil.

[0059] The term "Hansen solubility parameter" is understood to refer to the solubility parameter approach proposed by Charles Hansen, used to predict the solubility of polymers, and was developed on the basis that the total energy of vaporization of a liquid consists of multiple individual parts. To calculate the "weighted Hansen solubility parameter," the effects of (atomic) dispersion forces, (molecular) permanent inter-dipole forces, and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen solubility parameter" is (δD 2 +δP 2 +δH 2 ) 0.5 The calculation is performed as follows: in the formula, δD is the Hansen dispersion value (hereinafter also called atomic dispersion force), δP is the Hansen polarization value (hereinafter also called dipole moment), and δH is the Hansen hydrogen bond ("h-bonding") value (hereinafter also called hydrogen bond). For a more detailed explanation of the parameters and values, please refer to Charles Hansen, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, Danish Technical Press (Copenhagen, 1967).

[0060] The Euclidean difference in the solubility parameter between the fragrance and the solvent is (4 * ( δD solvent -δD fragrance ) 2 +(δΡ solvent -δΡfragrance ) 2 +(δH) solvent -δH fragrance ) 2 ) 0.5 Calculated as follows, in the formula, δD solvent , δP solvent , δH solvent These are the Hansen dispersion value, Hansen polarization value, and Hansen h-bond value of the solvent, respectively; δD fragrance , δP fragrance and δH fragrance These are the Hansen dispersion value, Hansen polarization value, and Hansen h-bond value of the fragrance, respectively.

[0061] In certain embodiments, the fragrance oil and hydrophobic solvent have at least two Hansen solubility parameters selected from a first group consisting of 12–20 atomic dispersion forces (δD), 1–8 dipole moments (δP), and 2.5–11 hydrogen bonds (δH).

[0062] In certain embodiments, the fragrance oil and hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of an atomic dispersion force (δD) of 12-20, preferably 14-20, a dipole moment (δP) of 1-8, preferably 1-7, and hydrogen bonds (δH) of 2.5-11, preferably 4-11.

[0063] In certain embodiments, at least 90%, preferably at least 95%, and most preferably at least 98% of the fragrance oil has at least two Hansen solubility parameters selected from a first group consisting of atomic dispersion forces (δD) of 12–20, dipole moments (δP) of 1–8, and hydrogen bonds (δH) of 2.5–11.

[0064] In certain embodiments, the fragrance oil and hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of an atomic dispersion force (δD) of 12-20, preferably 14-20, a dipole moment (δP) of 1-8, preferably 1-7, and hydrogen bonds (δH) of 2.5-11, preferably 4-11.

[0065] According to one embodiment, the fragrance compound includes a fragrance modifier (which may be used in addition to the hydrophobic solvent if present, or in place of the hydrophobic solvent if it is not present).

[0066] Preferably, the fragrance modifier is i. Vapor pressure less than 0.0008 Torr at 22°C; ii. clogP of 3.5 or higher, preferably 4.0 or higher, more preferably 4.5 iii. At least two Hansen solubility parameters selected from the first group consisting of atomic dispersion forces of 12-20, dipole moments of 1-7, and hydrogen bonds of 2.5-11, iv. When dissolved in a compound having a vapor pressure range of 0.0008 to 0.08 Torr at 22°C, at least two Hansen solubility parameters selected from the second group consisting of 14 to 20 atomic dispersion forces, 1 to 8 dipole moments, and 4 to 11 hydrogen bonds are found. It is defined as a fragrance material having [a certain characteristic].

[0067] Preferably, the following components may be used as modifiers, but the list is not limited to the following materials: alcohol C12, oxacyclohexadeca-12 / 13-en-2-one, 3-[(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecene-1-one, cyclopentadecanone (8Z)-Oxacycloheptadeca-8-en-2-one, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, mugaldehyde, 1,5,8-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene, (+-)-4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8- Hexahydrocyclopenta[g]isochromene, (+)-(1S,2S,3S,5R)-2,6,6-trimethylspiro[bicyclo[3.1.1]heptan-3,1'-cyclohexane]-2'-en-4'-one, oxacyclohexadecan-2-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, (+)-(4R,4 aS,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amyl cinnamaldehyde, hexyl cinnamaldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadiene-3-one, (9Z)-9-cycloheptadecene-1-one.

[0068] According to a particular embodiment, the hydrophobic material does not contain any active ingredients (e.g., fragrances). According to this particular embodiment, it comprises, preferably consisting of, a hydrophobic solvent selected from the group consisting of isopropyl myristate, triglycerides (e.g., Neobee® MCT oil, vegetable oils), D-limonene, silicone oils, mineral oils, and mixtures thereof, and optionally having a hydrophilic solvent selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol, glycol ethers, and mixtures thereof.

[0069] The term "biocide" refers to a chemical substance that can kill an organism (e.g., a microorganism) or reduce or prevent its growth and / or accumulation. Biocides are commonly used in medicine, agriculture, and forestry, as well as in industries such as preventing fouling of water, agricultural products including seeds, and oil pipelines. Biocides include pesticides, including fungicides, herbicides, insecticides, algicides, mollusk repellents, acaricides, and rodenticides; and / or antimicrobial agents, such as fungicides, antibiotics, antimicrobial agents, antivirals, antifungals, antiprotozoa, and / or antiparasitic agents.

[0070] As used herein, "pest control agent" refers to a substance that repels or attracts pests and reduces, inhibits, or promotes their proliferation, development, or activity. Pests include any organism that invades or harms plants or animals, whether animals, plants, or fungi, and include insects, especially arthropods, mites, spiders, fungi, weeds, bacteria, and other microorganisms.

[0071] "Flavor oil" as used herein means a specific mixture of flavoring components or mixtures of flavoring components, solvents, or auxiliaries currently used for the preparation of flavored formulations, i.e., a specific mixture of components intended to be added to an edible composition or chewable product to impart, improve, or modify its sensory properties, in particular its flavor and / or taste. Flavoring components are well known to those skilled in the art, and their properties are not guaranteed to be detailed herein, nor will they be exhaustive in any case; however, a skilled flavorist may select them based on their general knowledge, in accordance with the intended use or application and the sensory stimulation effect to be achieved. Many of these flavoring components are listed in reference texts, such as S. Arctander's book *Perfume and Flavor Chemicals*, 1969, Montclair, NJ, USA, or its latest edition, or in other similar papers, such as *Fenaroli's Handbook of Flavor Ingredients*, 1975, CRC Press, or *Synthetic Food Adjuncts*, 1947, by MB Jacobs, van Nostrand Co., Inc. The solvents and auxiliaries currently used for the preparation of flavoring formulations are also well known in the art.

[0072] In certain embodiments, the flavor is mint. In more specific embodiments, the mint is selected from the group consisting of peppermint and spearmint.

[0073] In further embodiments, the flavor is a cooling agent or a mixture thereof.

[0074] In another embodiment, the flavor is menthol flavor.

[0075] Flavors derived from or based on fruits in which citric acid is the main natural acid include, but are not limited to, citrus fruits (e.g., lemon, lime), limonene, strawberries, oranges, and pineapples. In one embodiment, the flavored food is lemon, lime, or orange juice extracted directly from the fruit. Further embodiments of the flavor include juice or liquid extracted from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, and any other citrus fruits, or their varieties or hybrids. In certain embodiments, the flavor includes liquid extracted or distilled from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, any other citrus fruits, or their varieties or hybrids, pomegranates, kiwifruits, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruit, mangoes, pears, tomatoes, and strawberries.

[0076] In certain embodiments, the flavor comprises a composition containing limonene, and in certain embodiments, the composition is a citrus fruit further containing limonene.

[0077] In another specific embodiment, the flavor includes a flavor selected from the group including strawberry, orange, lime, tropical, berry mix, and pineapple.

[0078] The term "flavor" includes not only flavors that impart or alter the smell of food, but also ingredients that impart or alter the taste. The latter do not necessarily have a taste or smell themselves, but can alter the taste produced by other ingredients, such as ingredients that enhance saltiness, sweetness, umami, or bitterness.

[0079] In further embodiments, suitable sweeteners may be included in the particles described herein. In certain embodiments, the sweeteners are selected from the group consisting of sugar (e.g., sucrose, but not limited to), stevia components (e.g., stevioside or rebaudioside A, but not limited to), sodium cyclamate, aspartame, sucralose, sodium saccharin, and acesulfame K, or mixtures thereof.

[0080] (Compounds having at least two P-Cl functional groups) According to the present invention, the shell of the microcapsule contains a reaction product between at least one compound having at least two P-Cl functional groups and a compound having an inorganic moiety.

[0081] The phrase "a compound having at least two P-Cl functional groups" should be understood to mean that the P-Cl functional groups may be located on the same P atom or on two different P atoms within the same molecule.

[0082] According to one embodiment, the term "P-Cl functional group" refers to the covalent bond between a P atom and a Cl atom.

[0083] According to one embodiment, at least two Cl functional groups are located on the same P atom.

[0084] According to one embodiment, a compound having at least two P-Cl functional groups includes a P atom bonded to at least two Cl atoms via a covalent bond.

[0085] A compound having at least two P-Cl functional groups is given by the formula PXCl3[wherein X is O, S, or NH or NR]. 1 And R 1The compound having [a hydrocarbon group which optionally contains a heteroatom] can be selected from the group consisting of compounds. Preferably, compounds having at least two P-Cl functional groups include phosphorus oxytrichloride (POCl3), phosphorus thiotrichloride (PSCl3), phosphorimide trichloride (PNHCl3), and N-substituted phosphorimide trichloride (PNR3). 1 Cl3), phosphorus trichloride, phosphorus pentachloride, hexachlorocyclophosphazene (HCCP) and its derivatives, R 1 OPXCl2 (wherein X is O, NH, NR) 1 (or S), for example alkyl phosphorodic chloride (R 1 OPOCl2) and / or alkyldichlorothiophosphate (R 1 OPSCl2) (wherein R1 may be any hydrocarbon group having a heteroatom); can be selected from the group consisting of poly(dichlorophosphazene), 3,9-dichloro-2,4,8,10-tetraoxa-3λ5,9λ5-diphosphaspiro[5.5]undecane 3,9-dioxide, and mixtures thereof.

[0086] According to one embodiment, the hydrocarbon group is functional or non-functional C1-C 50 It is a hydrocarbon group.

[0087] Compounds having at least two P-Cl functional groups are those of the formulas PXCl3, PNHCl3, and PNR 1 Cl3[wherein X is O, S and R 1 The compound having [a hydrocarbon group which optionally contains a heteroatom] can be selected from the group consisting of compounds. Preferably, compounds having at least two P-Cl functional groups include phosphorus oxytrichloride (POCl3), phosphorus thiotrichloride (PSCl3), phosphorimide trichloride (PNHCl3), and N-substituted phosphorimide trichloride (PNR3). 1Cl3), phosphorus trichloride, phosphorus pentachloride, hexachlorocyclophosphazene (HCCP), 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene (TCPA), copolymer of hexa-(4-aldehyde-phenoxy)-cyclo-triphosphazene and 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene (HACP-co-TCPA), R 1 OPXCl2 (wherein X is O, NH, NR) 1 (or S), for example alkyl phosphorodic chloride (R 1 OPOCl2) and / or alkyldichlorothiophosphate (R 1 OPSCl2) (wherein R1 may be any hydrocarbon group having a heteroatom); can be selected from the group consisting of poly(dichlorophosphazene), 3,9-dichloro-2,4,8,10-tetraoxa-3λ5,9λ5-diphosphaspiro[5.5]undecane 3,9-dioxide, and mixtures thereof.

[0088] "...hydrocarbon group..." means that the above group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i.e., a linear or branched saturated hydrocarbon (e.g., alkyl group), a linear or branched unsaturated hydrocarbon (e.g., alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g., cycloalkyl), or an unsaturated cyclic hydrocarbon (e.g., cycloalkenyl or cycloalkynyl), or an aromatic hydrocarbon, i.e., an aryl group, or a mixture of the above types of groups, and it is understood that, for example, a particular group may include linear alkyl, branched alkenyl (e.g., having one or more carbon-carbon double bonds), (poly)cycloalkyl, and aryl moieties unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of two or more topologies (e.g., linear, cyclic, or branched) and / or being saturated or unsaturated (e.g., alkyl, aromatic, or alkenyl), it also means a group that may have any one of the topologies described above, or a portion that is saturated or unsaturated. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of one saturated or unsaturated (e.g., alkyl), it means that the group may be in any kind of topology (e.g., linear, cyclic, or branched), or may have several portions having various topologies.

[0089] The term "hydrocarbon group optionally containing..." is understood to mean that the hydrocarbon group optionally contains one, two, three or more heteroatoms. These groups may be bonded laterally to the hydrocarbon by substituting a hydrogen atom of the hydrocarbon group, or (if chemically possible) inserted into the hydrocarbon chain by substituting a carbon atom of the hydrocarbon group. For example, the -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group containing an alcohol group (hydrogen atom substitution), i.e., a C4 hydrocarbon containing an oxygen atom; the -CH2-CH2-COO-CH2-CH2CH2-CH2- group represents a C7 hydrocarbon group containing one ester group (carbon atom substitution / insertion into the hydrocarbon chain), i.e., a C7 hydrocarbon containing two oxygen atoms; similarly, the -CH2-CH2-O-CH2-CH2-O-CH2-CH2- group represents a C6 hydrocarbon group containing two ether groups, i.e., a C6 hydrocarbon containing two oxygen atoms.

[0090] According to certain embodiments, the compound having at least two P-Cl functional groups is hexachlorocyclophosphazene (HCCP) or a derivative thereof or a polymer thereof.

[0091] According to certain embodiments, compounds having at least two P-Cl functional groups are hexachlorocyclophosphazene (HCCP), 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene (TCPA), copolymers of hexa-(4-aldehyde-phenoxy)-cyclo-triphosphazene (HACP) and 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene (HACP-co-TCPA), or mixtures thereof.

[0092] According to one embodiment, the compound having at least two P-Cl functional groups is only PCl5 when the inorganic part is not silicone or Ca(OH)2, or when the compound having the inorganic part does not contain a hydrocarbon part.

[0093] According to one embodiment, a compound having at least two P-Cl functional groups is not PCl5.

[0094] (Compounds containing inorganic parts) According to one embodiment, the term inorganic part refers to a non-carbon structural unit, and in particular, the bonding does not depend on the carbon skeleton.

[0095] According to one embodiment, a compound having an inorganic portion has a small number of carbon-carbon bonds and / or carbon-hydrogen bonds (based on the total number of bonds, preferably 50% or less, preferably 30% or less, more preferably 20% or less, 10% or less, and more preferably 4% or less), or even a compound that does not have carbon-carbon bonds and / or carbon-hydrogen bonds.

[0096] According to one embodiment, a compound having an inorganic portion has a small number of carbon-carbon bonds and carbon-hydrogen bonds (30% or less, preferably 20% or less, 10% or less, more preferably 4% or less based on the total number of bonds, preferably covalent bonds), or is a compound that does not have carbon-carbon bonds and carbon-hydrogen bonds.

[0097] According to one embodiment, the compounds having an inorganic portion are monomers, polymers, oligomers, particles, and mixtures thereof.

[0098] When the compound containing the inorganic portion is a particle, it can be selected from the group consisting of calcium phosphate, silica, silicates, titanium dioxide, aluminum oxide, zinc oxide, iron oxide, mica, kaolin, montmorillonite, laponite, bentonite, perlite, dolomite, diatomite, vermiculite, hectorite, gibbsite, illite, kaolinite, aluminosilicate, gypsum, bauxite, magnesite, talc, magnesium carbonate, calcium carbonate, diatomaceous earth, and mixtures.

[0099] According to one embodiment, the compound having an inorganic moiety is 1,3,5-triaza-2λ5,4λ5,6λ5-triphosphacyclohexahexa-1,3,5-triene-2,2,4,4,6,6-hexamine.

[0100] According to one embodiment, the compound having an inorganic portion is a silicon-containing monomer, polymer, oligomer, particle, or mixture thereof, and is preferably selected from the group consisting of amino-functionalized silanes, sulfur-functionalized silanes, non-functionalized silanes, and mixtures thereof.

[0101] The amino-functional silanes can be selected from the group consisting of bis[3-(triethoxysilyl)propyl]amine, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 1,1,1-triethoxysilaneamine and its polymers, and mixtures thereof.

[0102] Sulfur-functionalized silanes can be selected from the group consisting of 3-mercaptopropyltriethoxysilanes.

[0103] Non-functional silanes can be selected from the group consisting of 1,2-bis(triethoxysilyl)ethane, silicones, 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, triethoxysilanes, and mixtures thereof.

[0104] According to one embodiment, a compound having an inorganic portion is not a mineral.

[0105] According to one embodiment, the compound having an inorganic portion is not an inert mineral.

[0106] According to one embodiment, the compound having an inorganic portion and the compound having at least two P-Cl functional groups are not the same molecule.

[0107] According to one embodiment, the shell includes an inorganic part and an organic part, preferably consisting of both.

[0108] According to one embodiment, the shell contains at least 10% inorganic material.

[0109] According to one embodiment, the shell contains at least 20% inorganic material.

[0110] According to one embodiment, the shell contains at least 30% inorganic material.

[0111] According to one embodiment, the shell contains at least 40% inorganic material.

[0112] According to one embodiment, the shell is substantially inorganic.

[0113] "Substantially inorganic" should be understood as the shell containing at least 50%, preferably at least 70%, more preferably at least 90%, and most preferably 100% inorganic components.

[0114] (Nucleophile) According to a particular embodiment, the shell comprises a reaction product between at least one compound containing an inorganic moiety, at least one compound having at least two P-Cl functional groups, and at least one nucleophile.

[0115] According to the present invention, a nucleophile is defined as a chemical species that, in relation to a reaction, donates an electron pair to an electrophile to form a chemical bond.

[0116] The nucleophile can be selected from the group consisting of nitrogen nucleophiles, sulfur nucleophiles, oxygen nucleophiles, carbon nucleophiles, phosphorus nucleophiles, and mixtures thereof.

[0117] The nitrogen nucleophile may have at least one functional group selected from the group consisting of ammonia, azide, amine, nitrite, hydroxylamine, hydrazine, carbazide, phenylhydrazine, semicarbazide, and amide, as well as mixtures thereof.

[0118] The sulfur nucleophile compound may have at least one functional group selected from the group consisting of hydrogen sulfide and its salts, thiols (RSH), thiolate anions (RS-), thiol carboxylic acid anions (RC(O)-S-), and dithiocarbonate (RO-C(S)-S-) and dithiocarbamate (R2N-C(S)-S-) anions, and mixtures thereof.

[0119] The oxygen nucleophile may have at least one functional group selected from the group consisting of water, hydroxide anions, alcohols, alkoxide anions, carboxylate anions, carbonates, sulfonates, sulfates, sodium phosphate, sodium silicate, borax, sodium tetraborate, and mixtures thereof.

[0120] The carbon nucleophile compound may have at least one functional group selected from the group consisting of enol carbon nucleophiles, malonates, and acetoacetates.

[0121] The phosphorus nucleophile may have at least one functional group selected from the group consisting of phosphine, phosphite anion, and mixtures thereof.

[0122] According to one embodiment, the nucleophile is selected from the group consisting of alcohols, amines, thiols, and mixtures thereof.

[0123] "Alcohols" and "polyols" can be used interchangeably in the present invention.

[0124] According to a particular embodiment, the amine is selected from the group consisting of cystamine, EDA, DETA, pentamethylenediamine, hexamethylenediamine, poly(L-lysine) (which may be modified), L-lysine, L-lysine ethyl ester, cystine dimethyl ester, and mixtures thereof.

[0125] According to certain embodiments, the amine is cystamine, cystamine hydrochloride, cystine, cystine hydrochloride, cystine dialkyl ester, cystine dialkyl ester hydrochloride, xylylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, polyetheramine, ethylenediamine, diethylenetriamine, spermine, spermidine, polyamidoamine (PAMAM), guanidine carbonate, chitosan, tris-(2-aminoethyl)amine, 1,4-diaminobutane, 2,2-dimethyl-1,3-propanediamine, 1,3-diaminopentane (Dytek EP diamine), 1,2-diaminopropane, triethylenetetraamine, 1,3-diaminopropane; urea; ethyleneurea; aminoguanidine bicarbonate; 1-(2-aminoethyl)imidazolidined-2-one; N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine; N1-(2-aminoethyl)-N1-dodecyl-1,2-ethanediamine; aminoethylethanolamine; N1-(3-aminopropyl)propane-1,3-diamine, polyethyleneimine, C36-alkylenediamine (e.g., Priamine(trademark)-(1E,19E)-10,1 The following are selected from the group consisting of 1-dioctylicosa-1,19-diene-1,20-diamine (low viscosity, bio-based, dimeric diamine), hexaaminocyclotriphosphazene, amino acids such as lysine, arginine, leucine, histidine, tryptophan, serine, glutamine, threonine, alanine, asparagine, aspartic acid, cysteine, glutamic acid, glycine, isoleucine, methionine, phenylalanine, proline, tyrosine, valine, 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene (TCPA), and mixtures thereof.

[0126] According to certain embodiments, the alcohol (or polyol) is selected from the group consisting of phloroglucinol, hydroquinone, hydroquinone bis(2-hydroxyethyl) ether, 1,4-cyclohexanedimethanol, resorcinol, isosorbide, pentaerythritol, erythritol, trimethylolpropane, di-trimethylolpropane, sorbitol, mannitol, xylitol, triethanolamine, diglycerol, triglycerol and its corresponding partial esters, polyglycerol and its corresponding partial esters, and mixtures thereof.

[0127] According to certain embodiments, thiols (or polythiols) include ethylene glycol bis-mercaptoacetate, dithiothreitol, trimethylolpropanetris(3-mercaptopropionate), 2,2'-thiodiethanethiol, pentaerythritol tetrakis(3-mercaptopropionate), 2-mercaptoethanol, 3-aminopropane-1-thiol, 3-aminopropane-1-thiol hydrochloride, 3-mercapto-1,2-propanediol, and 3-mercapto-1-pro Selected from panol, 1-mercapto-2-propanol, 6-mercapto-1-hexanol, 4-mercaptoacetoxy-butyl mercaptoacetate, 1-thioglycerol, 2-{2-[2-(2-mercaptoethoxy)ethoxy]ethoxy}ethanol, cysteamine, cysteamine hydrochloride, 4-mercaptophenol, 4,6-diamino-2-pyrimidinethiol, 4,6-dihydroxy-2-mercaptopyrimidine, propane-1,3-dithiol, and mixtures thereof.

[0128] According to one embodiment, the nucleophile and the compound having at least two P-Cl functional groups are the same molecule.

[0129] According to one embodiment, the nucleophile and the compound having at least two P-Cl functional groups are the same molecule, and the molecule is 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene.

[0130] According to one embodiment, the nucleophile and the compound having at least two P-Cl functional groups are not the same molecule.

[0131] (biodegradable) In certain embodiments, the shell material is a biodegradable material.

[0132] In certain embodiments, the organic portion of the shell is biodegradable.

[0133] In certain embodiments, the shell is biodegradable by at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98% within 60 days, according to OECD 301F.

[0134] In certain embodiments, the core-shell microcapsules are biodegradable by at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98% within 60 days, according to OECD 301F.

[0135] Therefore, it is understood that, according to OECD 301F, core-shell microcapsules, including all components such as the core, shell, and optionally the coating, may have at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98% biodegradability within 60 days.

[0136] In certain embodiments, the oil core, preferably the fragrance oil, is biodegradable by at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98% within 60 days, according to OECD 301F.

[0137] OECD 301F is a standard test method for biodegradability from the Organization for Economic Co-operation and Development.

[0138] A typical method for extracting shells to measure biodegradability is disclosed in Gasparini and all in Molecules 2020, 25,718.

[0139] (Exterior coating) According to a particular embodiment of the present invention, the microcapsule includes an outer coating, and to form the outer coating on the microcapsule, the outer coating includes a coating material selected from the group consisting of nonionic polymers (such as nonionic polysaccharides), anionic polymers (such as polysaccharides), cationic polymers, polyscinimide derivatives (for example, described in International Publication No. 2021185724), and mixtures thereof.

[0140] According to certain embodiments, the microcapsules do not have an outer coating.

[0141] Nonionic polysaccharide polymers are well known to those skilled in the art and are described, for example, on page 29, lines 1-25 of International Publication No. 2012 / 007438 and on page 2, lines 12-19 and on page 4, lines 3-12 of International Publication No. 2013 / 026657. Preferred nonionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose, and hydroxypropyl methylcellulose.

[0142] Cationic polymers are well known to those skilled in the art. Preferred cationic polymers have a cationic charge density of at least 0.5 meq / g, more preferably at least about 1.5 meq / g, but preferably less than about 7 meq / g, and more preferably less than about 6.2 meq / g. The cationic charge density of a cationic polymer can be measured by the Kjeldahl method under a chemical test for nitrogen measurement, as described in the United States Pharmacopeia. Preferred cationic polymers are selected from those containing units comprising primary, secondary, tertiary, and / or quaternary amine groups, which may form part of the polymer backbone or be present in side chain substituents directly bonded thereto. The weight-average (Mw) molecular weight of a cationic polymer is preferably between 10,000 and 3.5 M Daltons, more preferably between 50,000 and 1.5 M Daltons. According to certain embodiments, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylaminomethacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-imidazole-3-ium chloride), vinylpyrrolidone, acrylamidopropyltrimonium chloride, cassia-hydroxypropyltrimonium chloride, guar-hydroxypropyltrimonium chloride, or polygalactomannan-2-hydroxypropyltrimethylammonium chloride ether, starch-hydroxypropyltrimonium chloride, and cellulose-hydroxypropyltrimonium chloride may be used. Preferred copolymers are selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride, and cellulose hydroxypropyltrimonium chloride.Specific examples of commercially available products include Salcare® SC60 (a cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, supplied by BASF) or Luviquat®, for example PQ 11N, FC 550 or Style (a quaternary copolymer of polyquaternium-11~68 or vinylpyrrolidone, supplied by BASF), or further, Jaguar® (C13S or C17, supplied by Rhodia).

[0143] According to any one of the above embodiments of the present invention, the above polymer is added in an amount between about 0% and 5% (w / w), or further between about 0.1% and 2% (w / w), where the percentage is expressed on a w / w basis relative to the total weight of the slurry. It will be clearly understood by those skilled in the art that only a portion of the above-added polymer will be incorporated into / deposited on the microcapsule shells.

[0144] According to certain embodiments, the microcapsules of the present invention include a mineral layer. The mineral layer preferably comprises a material selected from the group consisting of iron oxide, iron oxyhydroxide, titanium dioxide, zinc oxide, calcium carbonate, calcium phosphate, barium salts, strontium salts, magnesium salts, and mixtures thereof.

[0145] (solid particles) Another subject of the present invention is, - A polymer carrier material, preferably selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, plant gum, pectin, xanthan gum, alginate, carrageenan, cellulose derivatives and mixtures thereof, - Microcapsules as defined above, captured in the above carrier material, - Optionally, free fragrance captured in the above carrier material and It is a solid particle containing [the specified element].

[0146] The solid particles and microcapsule powders defined above can be used without distinction in the present invention.

[0147] [Method for preparing microcapsules] Another subject of the present invention is a method for preparing a core-shell microcapsule slurry, a) Optionally, a step of preparing at least one compound having at least two P-Cl functional groups, b) A step of mixing at least one hydrophobic material with any compound obtained in step a) to form an oil phase. c) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. d) Optionally, disperse the two-phase dispersion in a continuous phase C2 which optionally contains at least one compound having at least two P-Cl functional groups to form a multiple dispersion. e) A step of curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d) and / or step e). It is a method.

[0148] According to the present invention, it should be understood that at least one compound having at least two P-Cl functional groups is added in step a) and / or step d).

[0149] It should also be understood that at least one compound having at least two P-Cl functional groups used in step a) and / or step d) may be used as a pure compound (meaning it does not react with the reactants) or as a modified compound if the reactants are added in step a) and / or step b) and / or step c) and / or step d) and / or step e).

[0150] According to a particular embodiment, the method is a) A step of preparing at least one compound having at least two P-Cl functional groups, b) A step of mixing at least one hydrophobic material with the compound obtained in step a) to form an oil phase. c) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. d) A step of curing the dispersion obtained in step c) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d).

[0151] According to one embodiment, a method for preparing a core-shell microcapsule slurry is: a) A step of preparing a solution containing at least one compound having at least two P-Cl functional groups, b) A step of mixing at least one active ingredient with the solution obtained in step a) to form an oil phase. c) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. d) Optionally, a step of dispersing a two-phase dispersion in a continuous phase C2 to form a multiple dispersion. e) A step of curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).

[0152] According to a particular embodiment, the method is a) A step of preparing at least one compound having at least two P-Cl functional groups, b) A step of mixing at least one hydrophobic material with the compound obtained in step a) to form an oil phase. c) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. d) A step of dispersing a two-phase dispersion in a continuous phase C2 containing at least one compound having at least two P-Cl functional groups to form a multiple dispersion. e) A step of curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).

[0153] The compound having at least two P-Cl functional groups in step d) may be the same as or different from the compound having at least two P-Cl functional groups in step a).

[0154] According to a particular embodiment, the method is a) A step of preparing at least one hydrophobic material and forming an oil phase. b) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. c) A step of dispersing a two-phase dispersion in a continuous phase C2 containing at least one compound having at least two P-Cl functional groups to form a multiple dispersion. d) A step of curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d).

[0155] The embodiments disclosed regarding core-shell microcapsules also apply to methods for preparing core-shell microcapsules. This is particularly applicable to compounds having at least two P-Cl functional groups, hydrophobic materials, compounds having inorganic moieties, or nucleophiles.

[0156] According to one embodiment, the continuous phase C1 contains water, and preferably consists of water.

[0157] According to one embodiment, the continuous phase C1 is an aqueous phase.

[0158] According to one embodiment, the two-phase dispersion is an oil-in-water emulsion.

[0159] According to one embodiment, the two-phase dispersion is a water-in-oil emulsion.

[0160] According to one embodiment, the continuous phase C1 comprises water and alcohols such as glycerol, 1,4-butanediol, ethylene glycol, and mixtures thereof.

[0161] According to one embodiment, the continuous phase C1 consists of an alcohol.

[0162] A stabilizer can be added to the oil phase and / or the continuous phase C1.

[0163] A "stabilizer" refers to a compound that can stabilize an oil / dispersion medium interface (typically an oil / water interface) as an emulsion.

[0164] The stabilizer is preferably used in an amount between 0.05% and 20% by weight, more preferably between 0.1% and 10% by weight, and more preferably between 0.1% and 5% by weight, based on the two-phase dispersion, preferably an oil-in-water emulsion.

[0165] "Stabilizers" or "emulsifiers" can be used interchangeably in the present invention.

[0166] According to one embodiment, the stabilizer can act as a nucleophile. Therefore, according to one embodiment, the stabilizer is the nucleophile of the present invention.

[0167] According to one embodiment, the stabilizer is a colloidal stabilizer.

[0168] The colloidal stabilizer may be a high-molecular-weight emulsifier (standard emulsion), a surfactant, or solid particles (Pickering emulsion).

[0169] A "polymer emulsifier" refers to an emulsifier that has both a polar group (hydrophilic) that has an affinity for water and a nonpolar group (hydrophobic) that has an affinity for oil. The hydrophilic portion dissolves in the aqueous phase, and the hydrophobic portion dissolves in the oil phase, forming a film around the droplet.

[0170] A "surfactant" refers to a substance that has polar and nonpolar groups and is added to a liquid to reduce its surface tension.

[0171] According to one embodiment, the stabilizer is selected from the group consisting of inorganic particles, polymer emulsifiers, such as polysaccharides, proteins, glycoproteins, and mixtures thereof.

[0172] When the stabilizer is a solid particle, it can be selected from the group consisting of calcium phosphate, silica, silicates, titanium dioxide, aluminum oxide, zinc oxide, iron oxide, mica, kaolin, montmorillonite, laponite, bentonite, perlite, dolomite, diatomite, vermiculite, hectorite, gibbsite, illite, kaolinite, aluminosilicate, gypsum, bauxite, magnesite, talc, magnesium carbonate, calcium carbonate, diatomaceous earth, and mixtures thereof.

[0173] According to certain embodiments, the stabilizer is a biopolymer.

[0174] "Biopolymer" refers to biomacromolecules produced by living organisms. Biopolymers are characterized by a molecular weight distribution ranging from 1,000 to 1,000,000,000 daltons. These macromolecules may be carbohydrates (sugar-based), proteins (amino acid-based), or a combination of both (rubber), and may be linear or branched.

[0175] According to one embodiment, the polymer emulsifier is selected from the group consisting of gum arabic, modified starch, polyvinyl alcohol, polyvinylpyrrolidone (PVP), carboxymethylcellulose (CMC), anionic polysaccharides, acrylamide copolymer, proteins such as soy protein, rice protein, whey protein, ovalbumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, potato protein, chickpea protein, pea protein, algal protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupine protein, and mixtures thereof.

[0176] Potato protein is typically extracted from potato tubers (Solanum tuberosum). In one embodiment, the potato protein is natural potato protein, preferably patatin.

[0177] The proteins used in this invention may be natural or partially or completely denatured by any suitable method. Denaturation is a process that alters the conformational structure of a protein by unfolding, i.e., involves the disruption, and sometimes degradation, of both the secondary and tertiary structures of the protein. In practice, denaturation implies the cleavage of many of the weak links or bonds (e.g., hydrogen bonds) within the protein molecule that are responsible for the highly ordered structure of the protein in its natural state. Denaturation can be reversible (the protein can return to its natural state once the effects of denaturation are removed) or irreversible.

[0178] Denaturation can be carried out in various ways. Proteins can be denatured by temperature, radiation, mechanical stress including shear, changes in pH (treatment with bases or acids), treatment with oxidizing or reducing agents, inorganic salts, certain organic solvents, and chaotropic agents (i.e., positive chaotropic values ​​(kJ / kg on the Holdsworth scale)). -1Compounds having a molar content (e.g., guanidine salts, 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) can be denatured by exposure to them.

[0179] The proteins used in this invention may also be derivatized or modified (e.g., derivatized or chemically modified). For example, proteins may be modified by covalently bonding sugars, lipids, peptides, or chemical groups such as phosphates or methyl groups.

[0180] According to one embodiment, the compound having at least two P-Cl functional groups is added in an amount between 0.5 and 10% by weight, preferably between 1 and 5% by weight, based on the total weight of the multiple dispersion.

[0181] According to one embodiment, the compound having an inorganic portion is added in an amount between 1 and 15% by weight, preferably between 1 and 8% by weight, based on the total weight of the multiple dispersion.

[0182] According to one embodiment, a base is added to the continuous phase C1. Preferably, the base is selected from the group consisting of guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof.

[0183] When used, the base is typically used in an amount between 0.1 and 10% by weight, preferably between 3 and 7% by weight, based on the total weight of the continuous phase C1.

[0184] According to one embodiment, a nucleophile selected from the group consisting of nitrogen nucleophiles, sulfur nucleophiles, enol carbon nucleophiles, oxygen nucleophiles, phosphorus nucleophiles, and mixtures thereof is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).

[0185] The nucleophile has already been defined.

[0186] According to one embodiment, the nucleophile can be added to the oil phase and / or continuous phase C1.

[0187] The nucleophile can be added in an amount between 0.5% and 10% by weight, preferably between 1% and 4% by weight, based on the total weight of the two-phase dispersion.

[0188] In step e), the dispersion obtained in step d) or e) is cured to form microcapsules in the form of a slurry.

[0189] Optionally, nonionic polymers (such as nonionic polysaccharides), anionic polymers (such as polysaccharides), cationic polymers, polyscinimide derivatives (e.g., described in International Publication No. 2021185724), and mixtures thereof may be added in or after step e) as defined above to form an outer coating.

[0190] According to a preferred embodiment, in order to improve the reaction rate, the above process is carried out for 1 to 24 hours at a temperature between 5 and 90°C, and optionally under pressure. More preferably, it is carried out at 10 to 80°C for 30 minutes to 5 hours.

[0191] [System of multiple microcapsules] According to one embodiment, the microcapsules of the present invention (first type of microcapsule) can be used in combination with the second type of microcapsule.

[0192] Another subject of the present invention is, • The microcapsule of the present invention as a first type of microcapsule, • A second type of microcapsule and A microcapsule delivery system including, The first type of microcapsule and the second type of microcapsule differ in their hydrophobic material and / or their wall material and / or their coating material. It is a microcapsule delivery system.

[0193] According to a particular embodiment, the microcapsule delivery system is in the form of a slurry.

[0194] The walls of the second type of microcapsules may vary. As a non-limiting example, the polymer shells of the second type of microcapsules include materials selected from the group consisting of polyurea, polyurethane, polyamide, polyhydroxyalkanoate, polyacrylate, polyester, polyaminoester, polyepoxide, organosilicon, polycarbonate, polysulfonamide, urea formaldehyde, melamine formaldehyde resin, melamine formaldehyde resin crosslinked with polyisocyanate or aromatic polyol, melamine urea resin, melamine lyoxal resin, gelatin / gum arabic shell walls, and mixtures thereof.

[0195] The second type of microcapsule may include an oil-based core comprising a hydrophobic surfactant, preferably a fragrance, and a composite shell containing the first and second materials, wherein the first and second materials are different, the first material being a coacervate and the second material being a polymer material. In certain embodiments, the weight ratio of the first material to the second material is between 50:50 and 99.9:0.1. In certain embodiments, the coacervate may include a first polymer electrolyte, most preferably gelatin, selected from proteins (such as gelatin), polypeptides, or polysaccharides (such as chitosan), and a second polymer electrolyte, preferably alginate, cellulose derivative, guar gum, pectinate, carrageenan, polyacrylic acid and methacrylic acid, or xanthan gum, or further, plant rubber, such as acacia gum (gum arabic), most preferably gum arabic. The coacervate of the first material can be chemically cured using a suitable crosslinking agent such as glutaraldehyde, glyoxal, formaldehyde, tannic acid, or genipin, or enzymatically cured using an enzyme such as transglutaminase. The second polymer material may be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, organosilicon, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal, and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount of less than 3% by weight, preferably less than 1% by weight, based on the total weight of the second type of microcapsule slurry.

[0196] As a non-limiting example, the shell of the second type of microcapsule may be aminoplast-based, polyurea-based, or polyurethane-based. The shell of the second type of microcapsule may also be organic-inorganic, such as a hybrid shell consisting of at least two cross-linked inorganic particles, or a shell obtained by hydrolysis and condensation reactions of a polyalkoxysilane macromonomer composition.

[0197] According to one embodiment, the shell of a second type of microcapsule comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine-formaldehyde or melamine-lyoxal.

[0198] In another embodiment, the shell of the second type of microcapsule is polyurea-based, for example, made of an isocyanate-based monomer and an amine-containing crosslinking agent such as guanidine carbonate and / or guanazole. A particular polyurea microcapsule comprises a polyurea wall which is a polymerization reaction product between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (e.g., water-soluble guanidine salts and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of an amine can be omitted. In a particular embodiment, the colloidal stabilizer comprises 0.1% to 0.4% polyvinyl alcohol and 0.6% to 1% aqueous solution of a cationic copolymer of vinylpyrrolidone and quaternized vinylimidazole (all percentages are defined by weight relative to the total weight of the colloidal stabilizer). In another embodiment, the emulsifier is an anionic or amphiphilic biopolymer, which in one embodiment may be selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0199] According to another embodiment, the microcapsule wall material of the second type of microcapsule may contain any suitable resin, particularly melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include reaction products of aldehydes and amines, with suitable aldehydes including formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluryl, and mixtures thereof. Suitable melamines include methylolmelamine, methylated methylolmelamine, iminomelamine, and mixtures thereof. Suitable ureas include dimethylolurea, methylated dimethylolurea, urea-resorcinol, and mixtures thereof. Suitable materials for production can be obtained from one or more of the following companies: Solutia Inc. (St. Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), and Sigma-Aldrich (St. Louis, Missouri USA).

[0200] According to another embodiment, a second type of microcapsule is, 1) A step of mixing a fragrance oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase, 2) A step of dispersing or dissolving an aminoplast resin and optionally a stabilizer in water to form a dispersion medium phase, 3) A step of preparing an oil-in-water dispersion containing an average droplet size between 1 and 100 microns by mixing the oil phase and the dispersion medium phase, 4) A curing process is performed to form the walls of the microcapsules, 5) A step of optionally drying the final dispersion to obtain dried core-shell microcapsules. These are one-shell aminoplast core-shell microcapsules obtained by a process that includes [a specific component / method].

[0201] According to one embodiment, the second type of microcapsule is a formaldehyde-free capsule. A typical process for preparing a slurry of aminoplast formaldehyde-free microcapsules is: 1) a. Polyamine components in the form of melamine, or a mixture of melamine and at least one C1-C4 compound containing two NH2 functional groups. b. Glyoxal, C 4~6 An aldehyde component in the form of a mixture of 2,2-dialkoxy-ethanal and optionally glyoxalate, wherein the mixture contains glyoxal / C between 1 / 1 and 10 / 1. 4~6 An aldehyde component having a molar ratio of 2,2-dialkoxy-ethanal, and c. Proton acid catalyst A step of preparing an oligomer composition containing the reaction products of or obtained by reacting them, 2) The droplet size is between 1 and 600 microns. a. Oil, b.Aqueous medium, c. At least one oligomer composition obtained in step 1, d. i.C4~C 12 Aromatic or aliphatic di- or tri-isocyanates, and their biuretes, triuretes, trimers, trimethylolpropane adducts, and mixtures thereof, and / or ii.Formula: A-(oxiran-2-ylmethyl) n [In the formula, n [where represents 2 or 3, and 1 represents a C2-C6 group containing 2-6 nitrogen and / or oxygen atoms] di- or tri-oxirane compounds At least one crosslinking agent selected from, e. Optionally, C1-C4 compounds containing two NH2 functional groups. A step of preparing an oil-in-water dispersion containing, 3) A step of heating the dispersion, 4) A step of cooling the dispersion and Includes.

[0202] In another specific embodiment, the second type of microcapsule is: - An oil-based core containing a hydrophobic surfactant, preferably a fragrance. - Optionally, an inner shell made of polymerized polyfunctional monomers, - A protein-containing biopolymer shell cross-linked with at least one type of protein. Includes.

[0203] According to a particular embodiment, the protein is selected from the group consisting of milk protein, caseinates 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.

[0204] According to certain embodiments, the protein comprises sodium caseinate, and preferably globular proteins selected from the group consisting of whey protein, β-lactoglobulin, ovalbumin, bovine serum albumin, plant proteins, and mixtures thereof.

[0205] The protein is preferably a mixture of sodium caseinate and whey protein.

[0206] According to a particular embodiment, the biopolymer shell comprises a cross-linking protein selected from the group consisting of sodium caseinate and / or whey protein.

[0207] According to a particular embodiment, the slurry of the second type of microcapsule is - An oil-based core containing a hydrophobic surfactant, preferably a fragrance; - An inner shell made of a polymerized polyfunctional monomer, preferably a polyisocyanate having at least two isocyanate functional groups; - A biopolymer shell containing a protein, wherein at least one protein is crosslinked, and the protein preferably contains a mixture of sodium caseinate and globular protein, preferably whey protein. - Optionally, at least one outer mineral layer It contains at least one microcapsule made of [material name].

[0208] According to one embodiment, sodium caseinate and / or whey protein are cross-linked proteins.

[0209] The weight ratio of sodium caseinate to whey protein is preferably between 0.01 and 100, more preferably between 0.1 and 10, and more preferably between 0.2 and 5.

[0210] In another specific embodiment, the second type of microcapsule is: - An oil-based core containing a hydrophobic surfactant, preferably a fragrance, - Polyamide shell, • Acyl chloride, • The first amino compound, • The second amino compound, Optionally, carbohydrates Polyamide shells containing or derived from them It is a polyamide core-shell polyamide microcapsule containing [the specified ingredient].

[0211] According to a particular embodiment, the second type of microcapsule is, - An oil-based core containing a hydrophobic surfactant, preferably a fragrance, - Polyamide shell, Preferably, an amount of acyl chloride is contained between 5 and 98%, preferably between 20 and 98%, and more preferably between 30 and 85% (w / w). Preferably, the first amino compound is present in an amount between 1% and 50% (w / w), preferably between 7% and 40% (w / w). Preferably, the second amino compound is present in an amount between 1% and 50% (w / w), preferably between 2% and 25% (w / w). Preferably, a stabilizer, preferably a biopolymer, is present in an amount between 0 and 90%, preferably between 0.1 and 75%, and more preferably between 1 and 70%. Optionally, carbohydrates Polyamide shells containing or derived from them Includes.

[0212] According to a particular embodiment, the second type of microcapsule is, - An oil-based core containing a hydrophobic surfactant, preferably a fragrance, - Polyamide shell, • Acyl chloride, Preferably, a first amino compound which is an amino acid selected from the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and / or mixtures thereof. Preferably a second amino compound selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine and / or mixtures thereof, and Preferably, a biopolymer selected from the group consisting of potato protein, chickpea protein, pea protein, algae protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupine protein, soybean protein, rice protein, whey protein, ovalbumin, casein, sodium caseate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soybean protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin, and mixtures thereof. Optionally, a carbohydrate selected from the group consisting of anionic salts of alginate, preferably sodium alginate, pectin, lignin, anionic modified starch, carboxymethylcellulose, carrageenan, and mixtures thereof. Polyamide shells containing or derived from them Includes.

[0213] In another embodiment, the shell of the second type of microcapsule is polyurea or polyurethane-based. Examples of methods for preparing polyurea and polyurethane-based microcapsule slurries are described, for example, in International Publication 2007 / 004166, European Patent Application Publication 2300146, and European Patent Application Publication 25799. Typically, a method for preparing a polyurea or polyurethane-based microcapsule slurry involves the following steps: a) A step of dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase; b) A step of preparing an aqueous solution of an emulsifier or colloidal stabilizer to form a dispersion medium phase; c) Adding the oil phase to the dispersion medium phase to form an oil-in-water dispersion in which the average droplet size is between 1 and 500 μm, preferably between 5 and 50 μm; and d) Applying conditions sufficient to induce interfacial polymerization to form microcapsules in the form of a slurry. Includes.

[0214] [Fragrance compositions and consumer products] The present invention - Core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above, - At least one component selected from the group consisting of fragrance carriers and fragrance bases, and - Optionally, at least one fragrance enhancer This also relates to fragrance compositions, including [the specified element].

[0215] In certain embodiments, the composition is - Core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above; - Preferably, the active ingredient is selected from the group consisting of cosmetic ingredients, skincare ingredients, perfume ingredients, flavor ingredients, malodor neutralizing ingredients, bactericide ingredients, fungicide ingredients, pharmaceutical or agrochemical ingredients, sanitizing ingredients, insect repellents or attractants, and mixtures thereof is included.

[0216] In certain embodiments, the core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above can also be added to various perfumed consumer products.

[0217] In certain embodiments, the present invention relates to · The core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above, and · Optionally, free perfume oil a perfuming composition comprising the same.

[0218] Preferably, the perfuming composition according to the present invention comprises between 0.1 and 40% by weight, preferably between 0.1 and 30% by weight, of the core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above.

[0219] As used herein, "free perfume" is understood to mean a perfume or perfume oil that is contained in the perfuming composition and is not entrapped in the core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above.

[0220] In certain embodiments, the total amount of the core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above is 0.05 to 5% by weight (based on the total weight of the perfuming composition), and the total amount of free perfume oil is 0.05 to 5% by weight (based on the total weight of the perfuming composition).

[0221] In certain embodiments, the total fragrance oils and total free fragrance oils of a fragrance formulation obtained by the method according to the present invention or captured in the core-shell microcapsules or core-shell microcapsule slurry described above are present in the fragrance composition in a weight ratio of 1:20 to 20:1, preferably 10:1 to 1:10.

[0222] The fragrance composition may further contain at least one fragrance auxiliary component and optionally a fragrance enhancer.

[0223] "Fragrance auxiliary components" are understood herein to mean compounds used in fragrance preparations or compositions to impart a pleasurable effect, and which are not microcapsules as defined above. In other words, such auxiliary components that should be considered fragrance components should be recognized by those skilled in the art not merely as having an odor, but as being capable of imparting or altering the odor of a composition in a positive or pleasant way. This specification does not guarantee a more detailed description of the properties and types of fragrance auxiliary components present in fragrance compositions, and such a description would be incomplete anyway, but those skilled in the art can select them based on their general knowledge according to the intended use or application and the desired sensory stimulation effect. Generally speaking, these fragrance auxiliary components belong to various chemical classes such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur heterocyclic compounds and essential oils, and these fragrance auxiliary components may be of natural or synthetic origin. Many of these auxiliary components are listed in reference, for example, in the book *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA by S. Arctander, or its latest edition, or other papers of similar nature, as well as in the extensive patent literature in the field of fragrances. It is also understood that the above auxiliary components may be compounds known to release various types of fragrance compounds in a controlled manner. The auxiliary components are 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hexa-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-ylhexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2-((2-methylundeca-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, (3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, 1-(((Z)-hexa-3-en-1-yl)oxy)-2-methylundeca-1-ene, (2-((2-methyl Undeca-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undeca-1-ene, 1-methoxy-4-(1-phenethoxypropa-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxypropa-1-en-2-yl)benzene, 2-(1-phenethoxypropa-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, The following can be selected from the group consisting of 2-(1-((3,7-dimethylocta-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde, or mixtures thereof.

[0224] In this specification, "fragrance additives" are understood to be ingredients that can impart additional benefits such as color, specific lightfastness, and chemical stability. A detailed description of the properties and types of additives commonly used in fragrance bases cannot be exhaustive, but it should be noted that the above ingredients are well known to those skilled in the art.

[0225] The core-shell microcapsules or core-shell microcapsule slurry obtained by the method according to the present invention or described above can be advantageously used in many application fields and can be used in consumer products.

[0226] The present invention - Core-shell microcapsules or core-shell microcapsule slurries obtained by the method according to the present invention or described above, and - Personal care, home care, or fabric care active base This also applies to flavored consumer products, including those containing artificial flavorings.

[0227] The consumer products of the present invention may be used in scented consumer products, particularly those belonging to the category of fine fragrances or "functional" fragrances. Examples of functional fragrances include personal care products, including hair care, body cleansing, skin care, and hygiene care, as well as home care products, including laundry care and air care.

[0228] In particular, liquid consumer products - At least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product. - Water or water-miscible hydrophilic organic solvents, and - A fragrance composition, or a core-shell microcapsule or core-shell microcapsule slurry obtained by the method according to the present invention or described above. Includes.

[0229] Furthermore, powdered consumer products are - At least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, - A fragrance composition, or a core-shell microcapsule or core-shell microcapsule slurry obtained by the method according to the present invention or described above. Includes.

[0230] To clarify, it should be noted that “fragrance consumer products” means consumer products that are expected to deliver a fragrance effect, among various benefits, to the surface to which they are applied (e.g., skin, hair, textiles, paper, or house surfaces) or into the air (air fresheners, deodorizers, etc.). In other words, the fragrance consumer products according to the present invention are manufactured products that contain a functional compound, also called a “base,” together with a beneficial agent, in particular an effective amount of microcapsules according to the present invention.

[0231] While this specification does not guarantee a more detailed description of the properties and types of other components in flavored consumer products, and would not be able to cover them all anyway, those skilled in the art can select them based on their general knowledge in accordance with the properties of the product and the desired effect. Base formulations of consumer products into which the microcapsules of the present invention may be incorporated can be found in the abundant literature relating to such products. While this specification does not guarantee a more detailed description of these formulations, and would not be able to cover them all anyway, those skilled in the art who formulate such consumer products can fully select appropriate components based on their general knowledge and available literature.

[0232] Non-limiting examples of suitable perfumed consumer products may be fine perfumes, splash or eau de parfum, colognes, shave or aftershave lotions, liquid or solid detergents, mono- or multi-chamber unit dose detergents, fabric softeners, fabric refreshers, liquid or solid aroma enhancers (PEG / urea or salts), dryer sheets, ironing water, paper, bleaches, carpet-specific detergents, curtain care products, shampoos, coloring preparations, color care products, hair styling products, dental care products, disinfectants, intimate care products, hair sprays, hair conditioning products, vanishing creams, deodorants or antiperspirants, depilatories, tanning or sun protection products, nail products, skin cleansers, makeup products, perfumed soaps, shower or bath mousses, oils or gels, or foot / hand care products, hygiene products, air fresheners, "ready to use" powder air fresheners, mold removers, furniture care, wipes, dish detergents or hard surface detergents, leather care products, and car care products.

[0233] In certain embodiments, the perfumed consumer product is preferably selected from the group consisting of personal care compositions, home care compositions or fabric care compositions, and is most preferably in the form of an antiperspirant, a hair care product such as a shampoo or hair conditioner, a body care product such as a shower gel, an oral care product, a laundry care product, preferably a detergent or fabric softener.

[0234] Another subject of the present invention is - a personal care active base, and - the microcapsules or microcapsule slurries defined above, or the perfuming compositions defined above which is a consumer product in the form of a personal care composition.

[0235] Personal care active bases into which the microcapsules of the present invention may be incorporated can be found in the extensive literature relating to such products. This specification does not guarantee a more detailed description of these formulations, nor would it be possible to cover them all. Those skilled in the art who formulate such consumer products can fully select appropriate ingredients based on their general knowledge and available literature.

[0236] The personal care composition is preferably selected from the group consisting of hair care products (e.g., shampoo, hair conditioner, coloring preparation or hair spray), cosmetic preparations (e.g., vanishing cream, body lotion or deodorant or antiperspirant), or skin care products (e.g., scented soap, shower or bath mousse, body wash, oil or gel, bath salt, or hygiene product).

[0237] Another subject of the present invention is, - Home care or fabric care active base, and - Microcapsules or microcapsule slurry as defined above, or fragrance composition as defined above. It is a consumer product that includes and is in the form of a home care or fabric care composition.

[0238] Home care or fabric care active bases into which the microcapsules of the present invention may be incorporated can be found in the extensive literature relating to such products. This specification does not guarantee a more detailed description of these formulations, nor would it be exhaustive in any case. Those skilled in the art formulating such consumer products can fully select appropriate ingredients based on their general knowledge and available literature.

[0239] Preferably, the consumer product contains 0.1 to 15% by weight, more preferably 0.2 to 5% by weight, of the microcapsules of the present invention, where these percentages are defined by weight relative to the total weight of the consumer product. Naturally, the above concentrations can be adapted according to the desired beneficial effects of each product.

[0240] Regarding the liquid consumer products described below, "active base" should be understood as the active base containing an active ingredient (typically a surfactant).

[0241] With regard to the solid consumer products described below, the term "active base" should be understood to mean that the active base contains active materials (typically including surfactants) and auxiliary agents (bleaching agents, buffers; builders; stain removers or stain suspension polymers; granular enzyme particles, rust inhibitors, defoamers, foam inhibitors; dyes, fillers, and mixtures thereof, etc.).

[0242] The home or fabric care composition is preferably selected from the group consisting of fabric softeners, liquid detergents, powder detergents, liquid fragrance enhancers, and solid fragrance enhancers.

[0243] [Fabric softener] The subject of this invention is, - Preferably comprising at least one active material selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (ester quats), Hamburg ester quats (HEQ), TEAQ (triethanolamine quats), silicones, and mixtures thereof, and preferably used in an amount between 85 and 99.95% by weight of the total weight of the composition, as a fabric softener active base. - Preferably an amount of the above-defined microcapsules or microcapsule slurry contained between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. - Optionally, free fragrance oil It is a consumer product in the form of a fabric softener composition containing [the specified ingredient].

[0244] [Liquid detergent] The subject of this invention is, - Preferably comprising an anionic surfactant, such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and a nonionic surfactant, such as at least one active material selected from the group consisting of alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, and alkyl polyglucosamides, and used in an amount between 85 and 99.95% by weight of the total weight of the composition, as a liquid detergent active base. - Preferably an amount of the above-defined microcapsules or microcapsule slurry contained between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. - Optionally, free fragrance oil It is a consumer product in the form of a liquid detergent composition containing [the specified ingredient].

[0245] [Solid detergent] The subject of this invention is, - Preferably comprising an anionic surfactant, such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants, such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, and alkyl polyglucosamides, and used in an amount between 85 and 99.95% by weight of the total weight of the composition, a solid detergent active base. - Preferably an amount of the above-defined microcapsule powder or microcapsule slurry contained in between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. - Optional free fragrance oil It is a consumer product in the form of a solid detergent composition, which includes [the specified ingredient].

[0246] [Shampoo / Shower Gel] The subject of this invention is, - A shampoo or shower gel active base, preferably comprising at least one active material selected from the group consisting of sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoteric acetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside, amino acid-based surfactants, and mixtures thereof, and preferably used in an amount between 85 and 99.95% by weight based on the total weight of the composition. - Preferably an amount of the above-defined microcapsules or microcapsule slurry contained between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. - Optionally, free fragrance oil It is a consumer product in the form of a shampoo or shower gel composition containing [the specified ingredient].

[0247] [Rinse-off conditioner] The subject of this invention is, - A rinse-off conditioner active base preferably comprising at least one active material selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, and preferably used in an amount between 85 and 99.95% by weight based on the total weight of the composition. - Preferably an amount of the above-defined microcapsules or microcapsule slurry contained between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. - Optionally, free fragrance oil It is a consumer product in the form of a rinse-off conditioner composition, which includes [the specified ingredient].

[0248] [Solid fragrance enhancer] The subject of this invention is, - Preferably a solid carrier selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, polysaccharides, e.g., sucrose, monosaccharides, disaccharides and polysaccharides and derivatives, e.g., starch, cellulose, methylcellulose, ethylcellulose, propylcellulose, polyols / sugar alcohols, e.g., sorbitol, maltitol, xylitol, erythritol and isomalt, PEG, PVP, citric acid or any water-soluble solid acid, fatty alcohol or fatty acid and mixtures thereof. - Preferably, an amount of the above-defined microcapsules or microcapsule slurry in powder form, contained between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition. - Optionally, free fragrance oil It is a consumer product in the form of a solid aroma enhancer composition containing [the specified ingredient].

[0249] [Liquid fragrance enhancer] The subject of this invention is, - aqueous phase, - A surfactant system consisting essentially of one or more nonionic surfactants, having an average HLB between 10 and 14, preferably selected from the group consisting of ethoxylated aliphatic alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxyl esters, alkyl polyglucosides, amine oxides, and combinations thereof. - Linkers selected from the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxylcarboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants having an HLB of less than 10, and mixtures thereof, and - Preferably an amount between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, of the total weight of the composition, in the form of a slurry, of the microcapsules or microcapsule slurry as defined above. - Optionally, free fragrance oil It is a consumer product in the form of a liquid fragrance enhancer composition containing [the specified ingredient].

[0250] [Hair coloring agent] The subject of this invention is, - Preferably, an oxidizing phase containing an oxidizing agent and an alkaline phase containing an alkalizing agent, a dye precursor and a coupling compound in an amount between 85 and 99.95% by weight of the total weight of the composition (the dye precursor and the coupling compound form an oxidizing hair dye in the presence of the oxidizing agent), - Preferably, a microcapsule or microcapsule slurry as defined above, contained in 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 It is a consumer product in the form of an oxidative hair coloring composition containing [the specified ingredient].

[0251] [Fragrance composition] According to a particular embodiment, consumer products are - 0.1 to 30%, preferably 0.1 to 20%, of the previously defined microcapsules or microcapsule slurry. - 0-40%, preferably 3-40%, of fragrance, and - 20-90% by weight, preferably 40-90% by weight, of ethanol based on the total weight of the fragrance composition. It is a form of fragrance composition containing [the specified ingredient].

[0252] The present invention will be further illustrated by examples. It will be understood that the claimed invention is not intended to be limited in any way by these examples. [Examples]

[0253] Example 1 Modification of HCCPs with silane-containing monomers In a 500 mL round-bottom flask, dissolve hexachlorocyclophosphazene (HCCP; manufacturer: Sigma Aldrich, Switzerland) (15 g, 43 mmol) in dry ethyl acetate (150 mL). Maintain the solution under a nitrogen stream and cool to 0°C using an ice bath. Meanwhile, prepare a solution of bis[3-(triethoxysilyl)propyl]amine (manufacturer: Gelest, Switzerland) (19 mL, 43 mmol) and triethylamine (6 mL, 43 mmol) in dry ethyl acetate (150 mL). Add this solution dropwise to the HCCP solution over approximately 1 hour and 30 minutes. Next, heat the reaction medium to 60°C and maintain at 60°C for 3 hours. The reaction mixture is then cooled to room temperature and filtered. Collect the filtrate and concentrate under reduced pressure to obtain an orange / brownish viscous oil (approximately 30 g).

[0254] Example 2 Preparation of capsules containing HCCP in the oil phase; bis[3-(triethoxysilyl)propyl]amine, sodium hydroxide, and optionally L-lysine and gum arabic in the 80-glycerol / 20-water continuous phase.

[0255] The oil phase is prepared by mixing 30 g of fragrance oil A (see Table 1), hexachlorocyclophosphazene (HCCP), and optionally Solanic 200 (potato protein, manufacturer: Avebe, Netherlands). In a separate container, the continuous phase is prepared by first dissolving L-lysine (manufacturer: Sigma Aldrich, Switzerland), sodium hydroxide, and gum arabic (Acacia gum Superstab AA; manufacturer: Nexira, France) in 14 g of water, and then mixing this solution with 56 g of glycerol (manufacturer: Sigma Aldrich, Switzerland) (80% glycerol / 20% water). Bis[3-(triethoxysilyl)propyl]amine is then introduced into the continuous phase before the emulsification process.

[0256] The continuous phase is introduced into a double-jacketed reactor preheated to 80°C, and the oil phase is poured onto the continuous phase. The mixture is emulsified using a stirring blade at 900 rpm for 2 minutes and 30 seconds to form a glycerol / oil-in-water emulsion. The reaction mixture is then stirred at 80°C for 6 hours. The final product is a milky white dispersion.

[0257] [Table 1]

[0258] [Table 2]

[0259] Example 3: Preparation of capsules containing HCCP and potato protein in the oil phase; bis[3-(triethoxysilyl)propyl]amine, sodium hydroxide, L-lysine, and gum arabic in the 80 glycerol / 20 water continuous phase.

[0260] The oil phase is prepared by mixing 30 g of fragrance oil, 4 g of hexachlorocyclophosphazene (HCCP), and 0.5 g of Solanic 200 (potato protein). In a separate container, the continuous phase is prepared by first dissolving 1 g of L-lysine, 0.7 g of gum arabic, and 0.44 g of sodium hydroxide in 14 g of water, and then mixing this solution with 56 g of glycerol (80% glycerol / 20% water). Then, different amounts of bis[3-(triethoxysilyl)propyl]amine are introduced into the continuous phase before the emulsification process.

[0261] The continuous phase is introduced into a double-jacketed reactor, and the oil phase is poured onto the continuous phase. The mixture is emulsified using a stirring blade at 500 rpm for 2 minutes and 30 seconds to form a glycerol / oil-in-water emulsion. The reaction mixture is then heated to 80°C and stirred at 80°C for 6 hours. The final product is a milky white dispersion.

[0262] [Table 3]

[0263] Example 4 Preparation of capsules containing HCCP in the oil phase; bis[3-(triethoxysilyl)propyl]amine, sodium hydroxide, L-lysine, and gum arabic in the 80 glycerol / 20 water continuous phase.

[0264] The capsules are prepared according to the same procedure as disclosed in Example 3, except that the emulsification process is carried out at 700 rpm. The oil phase consists of fragrance oil and / or a hydrophobic solvent (benzyl benzoate), with the amount of L-lysine varied and the amount of bis[3-(triethoxysilyl)propyl]amine kept constant at 7.3 g.

[0265] [Table 4]

[0266] Example 5: Preparation of capsules containing HCCP and bis[3-(triethoxysilyl)propyl]amine in the oil phase; and sodium hydroxide, L-lysine, and gum arabic in 80 glycerol / 20 water or water as the continuous phase.

[0267] The capsules are prepared according to the same procedure as disclosed in Example 4, except that bis[3-(triethoxysilyl)propyl]amine is introduced into an oil phase consisting of 22.5 g of fragrance oil and 7.5 g of hydrophobic solvent instead of a continuous phase.

[0268] [Table 5]

[0269] Example 6 Shell composition by elemental analysis The polymer shells of the microcapsules from Examples 1-5 were purified according to the protocol published by Gasparini et al. in Molecules (2020), 25(3), 718.

[0270] Elemental analysis of the shell composition revealed that the shells of the exemplified microcapsules contained more than 50% inorganic material.

[0271] Example 7 Preparation of capsules containing HCCP and bis[3-(triethoxysilyl)propyl]amine in the oil phase; sodium hydroxide, L-lysine, and gum arabic in water as the continuous phase.

[0272] The oil phase is prepared by mixing 22.5 g of fragrance oil, 7.5 g of benzyl benzoate, 4 g of hexachlorocyclophosphazene (HCCP), and 7.30 g of bis[3-(triethoxysilyl)propyl]amine. In a separate container, the continuous phase is prepared by dissolving a variable amount of L-lysine, 0.7 g of gum arabic, and 0.44 g of sodium hydroxide in 70 g of water.

[0273] The oil phase is emulsified in the aqueous phase using Ultraturax (10,000 RPM, 2 minutes), and the emulsion is introduced into a double-jacketed reactor. The reaction mixture is then stirred at a given temperature for 6 hours. The final product is a milky white dispersion.

[0274] [Table 6]

[0275] Example 8 Preparation of capsules containing HCCP and bis[3-(triethoxysilyl)propyl]amine in the oil phase; sodium hydroxide, L-lysine, and gum arabic in water as the continuous phase.

[0276] The oil phase is prepared by mixing 22.5 g of fragrance oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP), and 1.83 g of bis[3-(triethoxysilyl)propyl]amine. In a separate container, the continuous phase is prepared by dissolving L-lysine (variable amount), 0.7 g of gum arabic, and sodium hydroxide (variable amount) in 70 g of water.

[0277] The oil phase is emulsified in the aqueous phase using Ultraturax (10,000 RPM, 2 minutes), and the emulsion is introduced into a double-jacketed reactor. The reaction mixture is then stirred at room temperature for 6 hours. The final product is a milky white dispersion.

[0278] [Table 7]

[0279] Example 9 Preparation of capsules containing HCCP and bis[3-(triethoxysilyl)propyl]amine in the oil phase; sodium hydroxide, L-lysine, and gum arabic in water as the continuous phase.

[0280] The procedure is the same as before, except that a variable amount of bis[3-(triethoxysilyl)propyl]amine is introduced into the oil phase. The amounts of L-lysine and sodium hydroxide in the aqueous phase are kept constant at 1.5 g and 0.22 g, respectively.

[0281] [Table 8]

[0282] Example 10 Preparation of capsules containing HCCP and bis[3-(triethoxysilyl)propyl]amine in the oil phase; sodium hydroxide in water as a continuous phase; various amino acids and gum arabic.

[0283] The oil phase is prepared by mixing 22.5 g of fragrance oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP), and 1.83 g of bis[3-(triethoxysilyl)propyl]amine. In a separate container, the continuous phase is prepared by dissolving various amino acids (variable amounts), 0.7 g of gum arabic, and 0.22 g of sodium hydroxide in 70 g of water.

[0284] The oil phase is emulsified in the aqueous phase using Ultraturax (10,000 RPM, 2 minutes), and the emulsion is introduced into a double-jacketed reactor. The reaction mixture is then stirred at room temperature for 6 hours. The final product is a milky white dispersion.

[0285] [Table 9]

[0286] Example 11 Preparation of capsules containing a mixture of HCCP and silane in the oil phase; sodium hydroxide, L-lysine, and gum arabic in water as the continuous phase.

[0287] The oil phase is prepared by mixing 22.5 g of fragrance oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP), and various mixtures (variable amounts) of silane-containing monomers. In a separate container, the continuous phase is prepared by dissolving L-lysine (variable amount), 0.7 g of gum arabic, and sodium hydroxide (variable amount) in 70 g of water.

[0288] The oil phase is emulsified in the aqueous phase using Ultraturax (10,000 RPM, 2 minutes), and the emulsion is introduced into a double-jacketed reactor. The reaction mixture is then stirred at room temperature for 6 hours. The final product is a milky white dispersion.

[0289] [Table 10]

[0290] Example 12 Preparation of capsules containing HCCP, bis[3-(triethoxysilyl)propyl]amine, and a polyfunctional polyol in the oil phase; and sodium hydroxide, L-lysine, and gum arabic in water as the continuous phase.

[0291] The oil phase is prepared by mixing 22.5 g of fragrance oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP), 3.65 g of bis[3-(triethoxysilyl)propyl]amine, and a variable amount of polyfunctional polyol. In a separate container, the continuous phase is prepared by dissolving 1.5 g of L-lysine, 0.7 g of gum arabic, and 0.3 g of sodium hydroxide in 70 g of water.

[0292] The oil phase is emulsified in the aqueous phase using Ultraturax (10,000 RPM, 2 minutes), and the emulsion is introduced into a double-jacketed reactor. The reaction mixture is then stirred at room temperature for 6 hours. The final product is a milky white dispersion.

[0293] [Table 11]

[0294] Example 13 6,6-Dichloro-1,3,5,2l 5 ,4l 5 ,6l 5 Preparation of microcapsules based on triazatriphosphinin-2,2,4,4-tetraamine (TCPA) and HCCP. 6,6-Dichloro-1,3,5,2l 5 ,4l 5 ,6l 5 Preparation of triazatriphosphinin-2,2,4,4-tetraamine (TCPA): A 0.5 M ammonia solution in dioxane (77 mL, 38.5 mmol) was placed in a 250 mL three-necked round-bottom flask equipped with a condenser and stirring rod, and the apparatus was purged with N2. HCCP (1.04 g, 3 mmol) was dissolved in acetone (30 mL) and introduced dropwise through a dropping funnel for 30 minutes. The reaction mixture was stirred for 2 hours, and a white precipitate was formed. The precipitate was then filtered and washed with excess hot acetonitrile. The filtrate was concentrated, and the solid obtained from the filtrate was precipitated with diethyl ether. The product was air-dried overnight to obtain a white powder (m = 0.59 g). [ka]

[0295] Preparation of TCPA / HCCP microcapsules: TCPA (0.55 g) was dissolved in 25 mL of 1 wt% HDK® H30 silica dispersion in DMSO. HCCP (1.1 g) and TBA (2 mL) were dissolved in cyclohexane (8 mL). The 4.5 mL TCPA / SiO2 / DMSO portion and the 0.5 mL HCCP / TBA portion were combined in a 10 mL vial and stirred with an Ultra Turrax for 1 minute. The vial was then placed in a water bath and stirred at 80°C for 8 hours. The mixture was then stirred overnight at room temperature.

[0296] Example 14 Fabric softener composition A sufficient amount of the exemplified microcapsules is weighed and mixed into the fabric softener composition, and 0.116% equivalent amount of fragrance is added.

[0297] [Table 12]

[0298] Example 15 Powder detergent composition Weigh out a sufficient amount of the exemplified microcapsules and mix them into the powder detergent composition, then add 0.2% equivalent amount of fragrance.

[0299] [Table 13]

[0300] Example 16 Preparation of spray-dried microcapsules Prepare emulsions A to E having the following components.

[0301] [Table 14]

[0302] [Table 15]

[0303] Add the polymer matrix components (maltodextrin and Capsul®, or Capsul®, citric acid, and tripotassium citrate) to water at 45-50°C until completely dissolved.

[0304] For emulsion D, free fragrance B is added to the aqueous phase.

[0305] The microcapsule slurry is added to the resulting mixture. The mixture is then gently mixed at 25°C (room temperature).

[0306] Granular powders A-E are prepared by spray-drying emulsions A-E using a Sodeva Spray Dryer (made in France), with the intake temperature set to 215°C and the throughput set to 500 ml per hour. The exhaust temperature is 105°C. The emulsions are at room temperature before spraying.

[0307] Example 17 Liquid fragrance enhancer composition Weigh out a sufficient amount of the example microcapsules and mix them with the liquid fragrance enhancer to add 0.2% equivalent volume of fragrance.

[0308] [Table 16]

[0309] Various ringing gel compositions are prepared according to the following protocol (Compositions 1-6).

[0310] In the first step, the aqueous phase (water), the solvent (propylene glycol) if present, and the surfactant are mixed at room temperature while stirring with a magnetic stirrer at 300 rpm for 5 minutes.

[0311] In the second step, the linker is dissolved in the hydrophobic active ingredient (fragrance) while being stirred with a magnetic stirrer at 300 rpm at room temperature. The resulting mixture is mixed for 5 minutes.

[0312] Next, the aqueous and oil phases are mixed at room temperature for 5 minutes to form a clear or milky ringing gel.

[0313] Example 18 Liquid detergent composition Weigh out a sufficient amount of the exemplified microcapsules, mix them with liquid detergent, and add 0.2% equivalent amount of fragrance.

[0314] [Table 17]

[0315] Example 19 Unit dose formulation Weigh out a sufficient amount of the example microcapsules, mix them into a unit-dose formulation, and add 0.2% equivalent volume of fragrance.

[0316] The unit dose formulation can be incorporated into the PVOH (polyvinyl alcohol) film.

[0317] [Table 18]

[0318] Example 20 Concentrated multi-purpose cleaning agent composition A sufficient amount of the exemplified microcapsules is weighed and mixed into a concentrated multipurpose cleaning agent composition, and 0.2% equivalent volume of fragrance is added.

[0319] [Table 19]

[0320] After mixing all the ingredients, the mixture was diluted with water to 100%.

[0321] Example 21 Solid Aroma Enhancer Composition Prepare the following compositions.

[0322] [Table 20]

[0323] [Table 21]

[0324] Example 22 Shampoo composition Weigh out a sufficient amount of the exemplified microcapsules and mix them into the shampoo composition, then add 0.2% equivalent amount of fragrance.

[0325] [Table 22]

[0326] Disperse polyquaternium-10 in water. Mix the remaining components of phase A separately by adding them sequentially, mixing well after each addition. Then add this premix to the polyquaternium-10 dispersion and mix for 5 minutes. Next, add phase B and premix phase C (heated to melt Monomuls 90L-12 in Texapon NSO IS). Mix the mixture well. Then add phases D and E with stirring. Adjust the pH with citric acid solution until it reaches pH 5.5-6.0.

[0327] Example 23 Shampoo composition Weigh out a sufficient amount of the exemplified microcapsules and mix them into the shampoo composition, then add 0.2% equivalent amount of fragrance.

[0328] [Table 23]

[0329] A premix containing guar hydroxypropyltrimonium chloride and polyquaternium-10 is added to water and tetrasodium EDTA while mixing. Once the mixture is homogeneous, NaOH is added. Then, the components of phase C are added and the mixture is heated to 75°C. The components of phase D are added and mixed until homogeneous. Heating is stopped and the temperature of the mixture is lowered to room temperature. At 45°C, the final viscosity is adjusted with a 25% NaCl solution while mixing in the components of phase E, and the pH is adjusted to 5.5-6 with a 10% NaOH solution.

[0330] Example 24 Rinse-off hair composition Weigh out a sufficient amount of the exemplified microcapsules and mix them into the rinse-off composition, then add 0.2% equivalent amount of fragrance.

[0331] [Table 24]

[0332] Mix the components of Phase A until a homogeneous mixture is obtained. Completely dissolve the tyrose. Then heat the mixture to 70-75°C. Combine the components of Phase B and melt at 70-75°C. Then add the components of Phase B to Phase A while stirring well, and continue mixing until it cools to 60°C. Then add the components of Phase C while stirring, and continue mixing until the mixture cools to 40°C. Adjust the pH with citric acid solution until it reaches pH 3.5-4.0.

[0333] Example 25 Anhydrous composition of antiperspirant spray A sufficient amount of the exemplified microcapsules is weighed and mixed into the anhydrous antiperspirant spray composition, and 0.2% equivalent amount of fragrance is added.

[0334] [Table 25]

[0335] Using a high-speed stirrer, silica and quaternium-18-hectorite are added to the mixture of isopropyl myristate and cyclomethicone. Once fully swollen, aluminum chlorohydrate is added in small amounts under stirring until the mixture is homogeneous and free of lumps. The aerosol can is filled with a 25% suspension and 75% propane / butane (2.5 bar).

[0336] Example 26 Antiperspirant spray emulsion composition A sufficient amount of the exemplified microcapsules is weighed and mixed into the antiperspirant spray emulsion composition, and 0.2% equivalent amount of fragrance is added.

[0337] [Table 26]

[0338] Weigh the components of Part A and Part B separately. Heat the components of Part A to 60°C and the components of Part B to 55°C. Add the components of Part B to Part A in small parts while continuously stirring. Stir the mixture well until it reaches room temperature. Then add the components of Part C. Mix the emulsion and introduce it into an aerosol can. Add the propellant by pressing it into place. Aerosol filling: 30% emulsion: 70% propane / butane 2.5 bar

[0339] Example 27 Deodorizing spray composition A sufficient amount of the exemplified microcapsules is weighed and mixed into the antiperspirant deodorant spray composition, and 0.2% equivalent amount of fragrance is added.

[0340] [Table 27]

[0341] Mix and dissolve all components in the order shown in Table 24. Then, fill and seal the aerosol can and add the propellant (aerosol filling: 40% active solution, 60% propane / butane 2.5 bar).

[0342] Example 28 Antiperspirant roll-on emulsion composition A sufficient amount of the exemplified microcapsules is weighed and mixed into the antiperspirant roll-on emulsion composition, and 0.2% equivalent amount of fragrance is added.

[0343] [Table 28]

[0344] Parts A and B are heated separately to 75°C. Part A is added to Part B while stirring, and the mixture is homogenized for 10 minutes. The mixture is then cooled while stirring, and when the mixture reaches 45°C, Part C is slowly added while stirring, and when the mixture reaches 35°C, Part D is added slowly while stirring. The mixture is then cooled to room temperature.

[0345] Example 29 Antiperspirant roll-on composition A sufficient amount of the exemplified microcapsules is weighed and mixed into the antiperspirant roll-on composition, and 0.2% equivalent amount of fragrance is added.

[0346] [Table 29]

[0347] After mixing the ingredients of Part B in the container, add the ingredients of Part A. Then, dissolve Part C in Parts A and B. Add 1 part Cremophor RH40 to 1 part of the fragrance, mixing well together.

[0348] Example 30 Antiperspirant roll-on composition A sufficient amount of the exemplified microcapsules is weighed and mixed into the antiperspirant roll-on emulsion composition, and 0.2% equivalent amount of fragrance is added.

[0349] [Table 30]

[0350] Part A is prepared by gradually sprinkling hydroxyethylcellulose into water while rapidly stirring with a turbine. Stirring continues until the hydroxyethylcellulose has completely swelled and a clear gel is obtained. Then, part B is gradually poured into part A while continuing to stir until the mixture is homogenized. Part C is then added.

[0351] Example 31 Alcohol-free deodorizing pump Weigh out a sufficient amount of the exemplified microcapsules and mix them with the following composition, adding 0.2% equivalent volume of fragrance.

[0352] [Table 31]

[0353] Mix all ingredients in the order shown in the table, and gently heat the mixture to dissolve the cetyl lactate.

[0354] Example 32 Deodorizing pump containing alcohol Weigh out a sufficient amount of the exemplified microcapsules and mix them with the following composition, adding 0.2% equivalent volume of fragrance.

[0355] [Table 32]

[0356] Mix the ingredients of Part B. Dissolve the ingredients of Part A in the order shown in the table and pour into Part B.

[0357] Example 32 Talc-containing Weigh out sufficient amounts of granules A-E, add them to standard talc base: 100% talc, very slight characteristic odor, white powder, manufacturer: LUZENAC, mix, and add 0.2% equivalent amount of fragrance.

[0358] Example 33 Shower gel reference Weigh out a sufficient amount of the exemplified microcapsules and mix them into the following composition, adding 0.2% equivalent volume of fragrance.

[0359] [Table 33]

[0360] Mix the ingredients and adjust the pH to 6-6.3 (viscosity: 4500 cPo ± 1500 cPo (Brookfield RV / spindle #4 / 20 RPM)).

[0361] Example 34 Shower gel composition Weigh out a sufficient amount of the exemplified microcapsules and mix them into the following composition, adding 0.2% equivalent volume of fragrance.

[0362] [Table 34]

[0363] Mix the ingredients and adjust the pH to 4.5 (viscosity: 3000 cPo ± 1500 cPo (Brookfield RV / spindle #4 / 20 RPM)).

[0364] Example 35 Shower gel composition Weigh out a sufficient amount of the exemplified microcapsules and mix them into the following composition, adding 0.2% equivalent volume of fragrance.

[0365] [Table 35]

[0366] Mix the ingredients and adjust the pH to 4.5 (viscosity: 4000 cPo ± 1500 cPo (Brookfield RV / spindle #4 / 20 RPM)).

[0367] Example 36 bar soap Weigh out a sufficient amount of the exemplified microcapsules and mix them into the solid soap formulation at a concentration of 7.5% w / w.

[0368] [Table 36]

[0369] Example 37 Cosmetic day cream Weigh out a sufficient amount of the exemplified microcapsules and mix them with a cosmetic skin cream (see composition below) at a concentration of 5% w / w.

[0370] [Table 37]

[0371] Example 38 Dish soap for hand washing Weigh out a sufficient amount of the exemplified microcapsules and mix them into the following composition, adding 0.2% equivalent volume of fragrance.

[0372] [Table 38]

[0373] Mix water containing sodium hydroxide and diethanolamide. Add LAS. After the LAS is neutralized, add the remaining ingredients. Check the pH (=7-8) and adjust as needed.

[0374] Example 39 Toothpaste ingredients A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is enclosed) is weighed and mixed with the following composition to add 0.2% equivalent amount of flavor.

[0375] [Table 39]

[0376] Example 40 toothpaste formulations based on dicalcium phosphate A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is enclosed) is weighed and mixed with the following composition to add 0.2% equivalent amount of flavor.

[0377] [Table 40]

[0378] Example 41 Alcohol-free mouthwash formulations A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is enclosed) is weighed and mixed with the following composition to add 0.2% equivalent amount of flavor.

[0379] [Table 41]

[0380] Example 42 Mouthwash ingredients A sufficient amount of microcapsule slurry M (prepared according to the protocol disclosed in Example 1, except that menthol flavor is enclosed) is weighed and mixed with the following composition to add 0.2% equivalent amount of flavor.

[0381] [Table 42]

Claims

1. - A core containing hydrophobic material, - A shell comprising a reaction product between at least one compound containing an inorganic moiety and at least one compound having at least two P-Cl functional groups. Core-shell microcapsules containing these capsules.

2. The core-shell microcapsule according to claim 1, wherein the shell comprises at least 50%, preferably at least 70%, more preferably at least 90%, and most preferably 100% inorganic material.

3. Said compound having at least two P-Cl functional groups is of the formula PXCl ３ [wherein X is O, S, NH or NR １ and R １ is any hydrocarbon group optionally containing a heteroatom], is selected from the group consisting of compounds having the formula, preferably, said compound having at least two P-Cl functional groups is the compound phosphorus oxychloride (POCl ３ ), phosphorus thiochloride (PSCl ３ ), phosphorimidic trichloride (PNHCl ３ ), N-substituted phosphorimidic trichloride (PNR １ Cl ３ ), phosphorus trichloride, phosphorus pentachloride, hexachlorocyclotriphosphazene (HCCP) and derivatives thereof, R １ OPXCl ２ (wherein X is O, NH, NR １ or S), for example alkyl phosphorodichloridate (R １ OPOCl ２ ) and / or alkyl dichlorothiophosphate (R １ OPSCl ２ ), (wherein R １ may be any hydrocarbon group optionally having a heteroatom); the core-shell microcapsule according to claim 1 or 2, which can be selected from the group consisting of poly(dichlorophosphazene), 3,9-dichloro-2,4,8,10-tetraoxa-3λ5,9λ5-diphosphaspiro[5.5]undecane 3,9-dioxide, and mixtures thereof.

4. The core-shell microcapsule according to claim 3, wherein the compound having at least two P-Cl functional groups is hexachlorocyclophosphazene (HCCP) or a derivative thereof or a polymer thereof.

5. The core-shell microcapsule according to any one of claims 1 to 4, wherein the compound having an inorganic portion is a silicon-containing monomer, polymer, oligomer or particle, and mixtures thereof, preferably selected from the group consisting of amino-functionalized silanes, sulfur-functionalized silanes, non-functionalized silanes and mixtures thereof.

6. The core-shell microcapsule according to claim 5, wherein the amino-functionalized silane is selected from the group consisting of bis[3-(triethoxysilyl)propyl]amine, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, N-phenylaminomethyltriethoxysilane, 1,1,1-triethoxysilaneamine and its polymers, and mixtures thereof; the sulfur-functionalized silane is selected from the group consisting of 3-mercaptopropyltriethoxysilane; and the non-functionalized silane is selected from the group consisting of 1,2-bis(triethoxysilyl)ethane, 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane and triethoxysilane, and mixtures thereof.

7. The core-shell microcapsule according to any one of claims 1 to 6, wherein the hydrophobic material contains a fragrance.

8. A method for preparing a core-shell microcapsule slurry, a) Optionally, a step of preparing at least one compound having at least two P-Cl functional groups, b) A step of mixing at least one hydrophobic material with any compound obtained in step a) to form an oil phase. c) A step of dispersing the oil phase in the continuous phase C1 or dispersing the continuous phase C1 in the oil phase to form a two-phase dispersion. d) Optionally, disperse the two-phase dispersion in a continuous phase C2 which optionally contains at least one compound having at least two P-Cl functional groups to form a multiple dispersion. e) A step of curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry. Includes, A compound having an inorganic portion is added in step a) and / or step b) and / or step c) and / or step d) and / or step e). method.

9. The method according to claim 8, wherein a stabilizer is added to the oil phase and / or dispersion medium phase.

10. The method according to claim 8, wherein the stabilizer is selected from the group consisting of inorganic particles, surfactants, polymer emulsifiers, such as polysaccharides, proteins, glycoproteins, and mixtures thereof.

11. The method according to any one of claims 8 to 10, wherein a nucleophile selected from the group consisting of nitrogen nucleophiles, sulfur nucleophiles, enol carbon nucleophiles, oxygen nucleophiles, phosphorus nucleophiles, and mixtures thereof is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).

12. The method according to any one of claims 8 to 11, wherein the compound having at least two P-Cl functional groups is added in an amount between 0.5 and 10% by weight, preferably between 1 and 5% by weight, based on the total weight of the multiple dispersion.

13. The method according to any one of claims 8 to 12, wherein the compound having an inorganic portion is added in an amount between 1 and 15% by weight, preferably between 1 and 8% by weight, based on the total weight of the multiple dispersion.

14. The method according to any one of claims 8 to 13, wherein the multiple dispersion is a two-phase dispersion.

15. A consumer product, preferably in the form of a home care product, a personal care product, or a fabric care product, comprising the microcapsules described in any one of claims 1 to 7.

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