Polyamide microcapsules

Abstract

The present invention relates to a new method for preparing polyamide microcapsules. The polyamide microcapsules are also an object of the present invention. Fragrance compositions containing said microcapsules and consumer products, in particular perfumed consumer products in the form of home care products or personal care products, are also part of the present invention.

Description

Technical Field

[0001] The present invention relates to a new method for preparing polyamide microcapsules. The polyamide microcapsules are also an object of the present invention. Fragrance compositions containing said microcapsules and consumer products, in particular perfumed consumer products in the form of home care products or personal care products, are also part of the present invention.

[0002] Background Art One of the problems faced by the cosmetics industry is that the olfactory benefits provided by odor compounds are lost relatively rapidly due to the volatility of the odor compounds, particularly the volatility of "top notes". In order to regulate the release rate of volatile substances, delivery systems such as microcapsules containing fragrances are necessary to protect the core payload when triggered and release it later. An important requirement from the industry regarding these systems is to withstand suspension in difficult bases without physically dissociating or decomposing. This is referred to as the stability of the delivery system. For example, perfumed personal detergents and household cleaners containing high levels of aggressive surfactants are very difficult for the stability of microcapsules.

[0003] In addition to performance regarding stability and odor performance, consumer demands for environmentally friendly delivery systems are becoming increasingly important, driving the development of new delivery systems.

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

[0005] The present invention proposes a solution to the above problems by providing new polyamide microcapsules and a method for preparing said microcapsules.

[0006] Summary of the Invention Surprisingly, it has been found that performing core-shell microcapsules encapsulating a hydrophobic material can be obtained by reacting at least one acyl chloride with at least one oligopeptide. Thus, the method of the present invention provides a solution to the above-mentioned problems as it enables the preparation of microcapsules having the desired stability in difficult bases.

[0007] A first object of the present invention is a core containing a hydrophobic material, preferably a perfume oil, and a polyamide shell containing the reaction product between at least one acyl chloride and at least one oligopeptide and a polyamide core-shell microcapsule.

[0008] Another object of the present invention is a microcapsule slurry containing the microcapsules defined above.

[0009] Another object of the present invention is a method for preparing a polyamide core-shell microcapsule slurry, comprising the following steps: a) dispersing an oil phase containing a hydrophobic material and at least one acyl chloride in a dispersion phase to form a two-phase dispersion, preferably a water-in-oil emulsion; and b) performing a curing step to form microcapsules in the form of a slurry wherein at least one stabilizer is added to the oil phase and / or the dispersion phase, and at least one oligopeptide is added to the dispersion phase and / or the oil phase and / or the two-phase dispersion.

[0010] Another object of the present invention is a polyamide core-shell microcapsule slurry obtained by the method defined above.

[0011] ​(i) a hydrophobic material containing a fragrance, the microcapsules or microcapsule slurry as defined above, and (ii) at least one component selected from the group consisting of a fragrance carrier and a fragrance base, and (iii) optionally, at least one fragrance preparation adjuvant A fragrance composition comprising is another object of the present invention.

[0012] Another object of the present invention is a personal care active ingredient base, and the microcapsules or microcapsule slurry as defined above or the fragrance composition as defined above comprising, a consumer product in the form of a personal care composition.

[0013] Another object of the present invention is a home care or fabric care active ingredient base, and the microcapsules or microcapsule slurry as defined above or the fragrance composition as defined above comprising, a consumer product in the form of a home care or fabric care composition.

[0014] Mode for Carrying Out the Invention Unless otherwise specified, percentages (%) mean weight percentages of the composition.

[0015] "Active ingredient" means a single compound or a combination of components.

[0016] "Fragrance or flavor oil" means a single fragrance or flavor compound, or a mixture of several fragrances or flavor compounds.

[0017] "Consumer product" or "end product" means a manufactured product that is ready for distribution, sale and use by consumers.

[0018] For the sake of clarity, the expression "dispersion" in the present invention means a system in which particles are dispersed in the continuous phase of a different composition, and specifically includes suspensions or emulsions.

[0019] "Microcapsules" or the like in the present invention means that the core-shell microcapsules have a particle size distribution in the micron range (for example, an average diameter (d(v,0.5)) included between about 1 to 3000 microns, preferably 1 to 500 microns), and include an external solid polyamide-based shell and an internal continuous oil phase surrounded by the external shell.

[0020] "Microcapsule slurry" means microcapsules dispersed in a liquid. According to one embodiment, the slurry is an aqueous slurry, that is, the microcapsules are dispersed in the aqueous phase.

[0021] "Polyamide microcapsules" means that the shell of the microcapsules contains a polyamide material. The term "polyamide microcapsules" can also include a shell made of a composite material containing a polyamide material and another material, such as a polymer (such as a protein).

[0022] "Polyamide-based microcapsules" and "polyamide microcapsules" are used interchangeably in the present invention.

[0023] "Salt" means an ionic compound that dissolves in the dispersed phase (typically water) and can form metal ions having one or more valences.

[0024] The terms "dispersed phase" and "continuous phase" can be used interchangeably in the present invention.

[0025] It has been found that polyamide core-shell microcapsules with overall good performance in difficult bases can be obtained when the shell contains a reaction product between at least one acyl chloride and at least one oligopeptide.

Brief Description of the Drawings

[0026]

Figure 1

Figure 2

Figure 3

Figure 4

[0027] Polyamide capsule The first object of the present invention is a core containing a hydrophobic material, preferably a perfume oil, and a polyamide shell containing a reaction product between at least one acyl chloride and at least one oligopeptide and is a polyamide core-shell microcapsule.

[0028] Another object of the present invention is a polyamide core-shell microcapsule slurry containing at least one polyamide core-shell microcapsule, wherein the microcapsule has a core containing a hydrophobic material, preferably a perfume oil, and a polyamide shell containing a reaction product between at least one acyl chloride and at least one oligopeptide and is a polyamide core-shell microcapsule slurry.

[0029] According to one embodiment, the polyamide shell contains a reaction product between at least one acyl chloride, at least one oligopeptide, and at least one free amino acid.

[0030] According to one embodiment, when present, the weight ratio between the free amino acid and the oligopeptide is included between 0.01:1 and 20:1.

[0031] Hydrophobic material The hydrophobic material according to the present invention can be an "inert" material such as a solvent or an active ingredient. The core is preferably an oil-based core.

[0032] "Hydrophobic material" means any hydrophobic material that forms a two-phase dispersion when mixed with a dispersed phase (typically water). The hydrophobic material is typically liquid at about 20 °C.

[0033] According to one embodiment, the hydrophobic material is a hydrophobic active ingredient.

[0034] When the hydrophobic material is an active ingredient, the hydrophobic material is preferably selected from the group consisting of fragrances, fragrance components, perfumes, perfume components, dietary supplements, cosmetics, pest control agents, biocidal active substances, and mixtures thereof.

[0035] According to a particular embodiment, the hydrophobic material comprises a mixture of a perfume and another component selected from the group consisting of dietary supplements, cosmetics, pest control agents, and biocidal active substances.

[0036] According to a particular embodiment, the hydrophobic material comprises a mixture of a biocidal active substance and another component selected from the group consisting of perfumes, dietary supplements, cosmetics, and pest control agents.

[0037] According to a particular embodiment, the hydrophobic material comprises a mixture of a pest control agent and another component selected from the group consisting of perfumes, dietary supplements, cosmetics, and biocidal active substances.

[0038] According to a particular embodiment, the hydrophobic material comprises a perfume.

[0039] According to a particular embodiment, the hydrophobic material consists of a perfume.

[0040] According to a particular embodiment, the hydrophobic material consists of a biocidal active substance.

[0041] According to certain embodiments, the hydrophobic material consists of a pest control agent.

[0042] As used herein, "perfume" (or also "perfume oil") means a component or composition that is liquid at about 20°C. According to any one of the above embodiments, the perfume oil can be a single perfume component or a mixture of components in the form of a perfume composition. As used herein, "perfume component" means a compound used for the main purpose of imparting or modulating an odor. In other words, such a component must be recognized by those skilled in the art as being able to not only have an odor but also at least impart or modify the odor of the composition in a positive or pleasant direction in order to be considered a perfume component. For the purposes of the present invention, the perfume oil also includes a combination of a perfume component with a substance that improves, enhances or modifies the delivery of the perfume component together, such as a perfume precursor, an emulsion or a dispersion, and a combination that imparts additional benefits beyond odor modification or imparting, such as long-term persistence, blooming, malodor prevention, antibacterial effects, microbial stability, pest control, etc.

[0043] The nature and types of perfume components present in the oil phase are not guaranteed by the more detailed description herein, are not exhaustive in any case, and 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 perfume components belong to various chemical classifications such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen or sulfur heterocyclic compounds and essential oils, and the perfume co-components can be of natural or synthetic origin. Many of these co-components are listed in references such as the book, S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent version, or other works of a similar nature, as well as numerous patent documents in the field of cosmetics.

[0044] In particular, the following perfume ingredients generally used in perfume formulations can be mentioned. Aldehyde components: decanal, dodecanal, 2-methyl-undecanal, 10-undecenal, octanal, nonanal and / or nonenal; Aromatic herb components: eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0~2,7~]undecan-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or alpha-pinene; Balsam components: coumarin, ethyl vanillin and / or vanillin; Citrus components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpene, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-menthadiene; Flower stalk components: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamic aldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one, 2,5-dimethyl-2-indanemethanol, 2,6,6-trimethyl-3-cyclohexene-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate, geraniol, p-menth-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-carboxaldehyde, amyl cinnamic aldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, verdyl isobutyrate and / or methyl ionone isomers; Fruit components: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, 3-(3,3 / 1,1-dimethyl-5-indanyl) propanal, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl [3-ethyl-2-oxiranyl] acetate and / or diethyl 1,4-cyclohexanedicarboxylate; Green components: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styralyl acetate, allyl (2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; Jacquemin components: 1,4-dioxo-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3-methyl-5-cyclopentadecen-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-g-2-benzopyran, (1S,1’R)-2-[1-(3’,3’-dimethyl-1’-cyclohexyl)ethoxy]-2-methylpropyl propanoate, oxacyclohexadecan-2-one and / or (1S,1’R)-[1-(3’,3’-dimethyl-1’-cyclohexyl)ethoxycarbonyl]methyl propanoate; Wood components: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4’-dimethylspiro(oxirane-2,9’-tricyclo[6.2.1.02,7]undeca[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, clearwood (registered trademark), (1’R,E)-2-ethyl-4-(2’,2’,3’-trimethyl-3’-cyclopenten-1’-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate; Other components (e.g., amber, powdery spice or aqueous): either dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and 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.

[0045] According to certain embodiments, the fragrance or fragrance formulation includes a fragrance modifier (which can be used in addition to the hydrophobic solvent if present, or as a replacement for the hydrophobic solvent if no hydrophobic solvent is present).

[0046] Preferably, the fragrance modifier has a vapor pressure of less than 0.0008 torr at 22 °C, a clogP of 3.5 or more, preferably 4.0 or more, more preferably 4.5, at least two Hansen solubility parameters selected from the first group consisting of an atomic dispersive force of 12 to 20, a dipole moment of 1 to 7, and a hydrogen bond of 2.5 to 11, and when in a solution containing 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 an atomic dispersive force of 14 to 20, a dipole moment of 1 to 8, and a hydrogen bond of 4 to 11 and is defined as a fragrance material.

[0047] Preferably, by way of example, the following components can be listed as fragrance regulators, but this list is not limited to the following materials: Alcohol C12, Oxacyclohexadec-12 / 13-en-2-one, 3-[(2’,2’,3’-Trimethyl-3’-cyclopentene-1’-yl)methoxy]-2-butanol, Cyclohexadecanone, (Z)-4-Cyclopentadecen-1-one, Cyclopentadecanone, (8Z)-Oxacycloheptadec-8-en-2-one, 2-[5-(Tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, Muguet aldehyde, 1,5,8-Trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene, (+-)-4,6,6,7,8,8-Hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (+)-(1S,2S,3S,5R)-2,6,6-Trimethylspiro[bicyclo[3.1.1]heptane-3,1’-cyclohexane]-2’-en-4’-one, Oxacyclohexadecane-2-one, 2-{ (1S)-1-[(1R)-3,3-Dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, (+)-(4R,4aS,6R)-4,4a-Dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, Amyl cinnamic aldehyde, Hexyl cinnamic aldehyde, Hexyl salicylate, (1E)-1-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-1,6-heptadien-3-one, (9Z)-9-Cycloheptadecen-1-one.

[0048] It is also understood that the components may also be compounds known to release various types of fragrance compounds, also known as pro-fragrances or pro-fragrances, in a controlled manner. Non-limiting examples of suitable pro-fragrances can include the following. 4-(Dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1-yl oxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl) succinate, (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-en, (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-en, 1-methoxy-4-(1-phenethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,(7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or mixtures thereof.,

[0049] The fragrance component may be dissolved in a solvent currently used in the fragrance industry. The solvent is preferably not an alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, Abalyn® (a rosin resin available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffin. Preferably, the solvent is very hydrophobic and highly sterically hindered, such as, for example, Abalyn® or benzyl benzoate. Preferably, the fragrance contains less than 30% solvent. More preferably, the fragrance contains less than 20%, even more preferably less than 10% solvent, all of these percentages being defined by weight relative to the total weight of the fragrance. Most preferably, the fragrance is essentially solvent-free.

[0050] According to certain embodiments, the fragrance contains at least 35% of fragrance components having a logP greater than 3.

[0051] LogP is the common logarithm of the estimated octanol-water partition coefficient, known as a measure of lipophilicity.

[0052] The LogP values of many flavor compounds are reported, for example, in the Pomona92 database available from Daylight Chemical Information Systems, Inc. (Daylight CIS) in Irvine, California, which also includes citations to the original literature. The LogP values are most conveniently calculated by the "CLOGP" program also available from Daylight CIS. This program also lists experimental logP values when available in the Pomona92 database. "Calculated logP" (cLogP) is determined by the fragmental approach of Hansch and Leo (see A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and C.A.Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragmental approach is based on the chemical structure of each flavor oil component and takes into account the number and type of atoms, atomic connectivity, as well as chemical bonds. The cLogP value is the most reliable and widely used estimate for this physicochemical property and is preferably used in place of the experimental LogP value in the selection of flavor compounds useful in the present invention.

[0053] In certain embodiments, the flavor oil comprises at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight of components having a logP greater than 3, preferably greater than 3.5, even more preferably greater than 3.75.

[0054] Preferably, the flavor oil contains less than 10% by weight of the primary alcohol itself, less than 15% by weight of the secondary alcohol itself, and less than 20% by weight of the tertiary alcohol itself. Advantageously, the flavor used in the present invention contains no primary alcohol and contains less than 15% by weight of secondary and tertiary alcohols.

[0055] According to certain embodiments, the fragrance comprises at least 20% by weight, preferably at least 25% by weight, more preferably at least 40% by weight of a bulky material from groups 1 - 6, preferably 3 - 6.

[0056] The term "bulky material" is understood herein as a fragrance component having a high steric hindrance, i.e., having a substitution pattern that provides high steric hindrance, and thus the bulky material is in particular from one of the following groups. Group 1: A fragrance component comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one substituent, preferably at least one linear or branched C1 - C4 alkyl or alkenyl substituent, and substituted with 1 - 4 nodes. Group 2: A fragrance component comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted with at least one substituent, preferably at least one linear or branched substituent of length C4 or more, preferably a C4 - C8 alkyl or alkenyl substituent, and substituted with 4 or more nodes. Group 3: A fragrance component comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one substituent, preferably at least one linear or branched substituent of length C5 or more, preferably a C5 - C8 alkyl or alkenyl substituent, and substituted with 5 or more nodes or with at least one phenyl substituent, and optionally, preferably one or more linear or branched C1 - C3 alkyl or alkenyl substituents, and substituted with 1 - 3 nodes. Group 4: A fragrance component comprising at least two fused or linked 5 - or 6 - membered rings, preferably at least two fused or linked C5 and / or C6 rings. Group 5: A fragrance component comprising a camphor - like ring structure, i.e., two 5 - or 6 - membered rings fused in a bridged - type manner. Group 6: A fragrance component comprising at least one 7 - to 20 - membered ring, preferably at least one C7 or C20 ring structure.

[0057] The term node, as understood in this context, means any atom that can provide at least two, preferably at least three, more preferably four bonds to further atoms. Specific examples of nodes as understood herein are carbon atoms (up to four bonds to further atoms), nitrogen atoms (up to three bonds to further atoms), oxygen atoms (up to two bonds to further atoms) and sulfur (up to two bonds to further atoms). Specific examples of further atoms as understood in this context can be carbon atoms, nitrogen atoms, sulfur atoms, oxygen atoms and hydrogen atoms.

[0058] Examples of components from each of these groups are as follows. Group 1: 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (manufacturer: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (manufacturer: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpanyl acetate, dihydroterpanyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-p-menthadien-7-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 1-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-menthanyl acetate, (1R,2S,4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (manufacturer: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanedicarboxylic acid diethyl ester (manufacturer: Firmenich SA, Geneva, Switzerland), (3ARS,6SR,7ASR)-perhydro-3,6-dimethyl-benz[B]furan-2-one (manufacturer: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethyl-benz[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-carboxaldehyde; Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Givaudan SA, Vernier, Switzerland), (1’R,E)-2-ethyl-4-(2’,2’,3’-trimethyl-3’-cyclopenten-1’-yl)-2-buten-1-ol (manufacturer: Firmenich SA, Geneva, Switzerland), (1’R,E)-3,3-dimethyl-5-(2’,2’,3’-trimethyl-3’-cyclopenten-1’-yl)-4-penten-2-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentaneacetate (manufacturer: Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (manufacturer: Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (manufacturer: Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (manufacturer: Givaudan SA, Vernier, Switzerland); Group 3: Damascone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), Nectalactone ((1’R)-2-[2-(4’-methyl-3’-cyclohexen-1’-yl)propyl]cyclopentanone), Alpha-ionone, Beta-ionone, Damasconen, mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (manufacturer: Firmenich SA, Geneva, Switzerland), (1S,1’R)-[1-(3’,3’-dimethyl-1’-cyclohexyl)ethoxycarbonyl]methyl propanoate (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-menthene, (1S,1’R)-2-[1-(3’,3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propanoate (manufacturer: Firmenich SA, Geneva, Switzerland), para-tert-butylcyclohexanone, menthenethiol, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allyl cyclohexyl propionate, cyclohexyl salicylate, 2-methoxy-4-methylphenyl methyl carbonate, ethyl 2-methoxy-4-methylphenyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate;, Group 4: Methyl cedryl ketone (manufacturer: International Flavors and Fragrances, USA), a mixture of (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0~2,6~]dec-3-en-8-yl 2-methylpropanoate and (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0~2,6~]dec-4-en-8-yl 2-methylpropanoate, vetiverol, vetivenone, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone (manufacturer: International Flavors and Fragrances, USA), (5RS,9RS,10SR)-2,6,9,10-tetramethyl-1-oxaspiro[4.5]dec-3,6-diene and the (5RS,9SR,10RS) isomer, 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]dec-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indenone (manufacturer: International Flavors and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (manufacturer: Firmenich SA, Geneva, Switzerland), 3’,4-dimethyl-tricyclo[6.2.1.0(2,7)]undec-4-en-9-spiro-2’-oxirane (manufacturer: Firmenich SA, Geneva, Switzerland), 9 / 10-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (manufacturer: Firmenich SA, Geneva, Switzerland), octalinol, (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan, manufacturer: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl acetate, and tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl propanoate and tricyclo[5.2.1.0(2,6)]Deca-4-en-8-yl propanoate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptane-3-spiro-2'-cyclohexene-4'-one;. Group 5: Camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedrene, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (manufacturer: Firmenich SA, Geneva, Switzerland), cedrene, cedrenol, cedrol, 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecan-4-one and a mixture of 10-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecan-4-one (manufacturer: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (manufacturer: Firmenich SA, Geneva, Switzerland); Group 6: (Trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (manufacturer: Firmenich SA, Geneva, Switzerland), ambrettolide LG ((E)-9-hexadecene-16-olide, manufacturer:: Firmenich SA, Geneva, Switzerland), pentadecenolide (manufacturer: Firmenich SA, Geneva, Switzerland), muscone (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-5,17dione, 4,8-cyclododecadien-1-one; Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (manufacturer: Givaudan SA, Vernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0059] Preferably, the fragrance comprises at least 30%, preferably at least 50%, more preferably at least 60% of the components selected from Groups 1 to 7 as defined above. More preferably, the fragrance comprises at least 30%, preferably at least 50% of the components from Groups 3 to 7 as defined above. Most preferably, the fragrance comprises at least 30%, preferably at least 50% of the components from Groups 3, 4, 6 or 7 as defined above.

[0060] According to another preferred embodiment, the fragrance comprises at least 30%, preferably at least 50%, more preferably at least 60% of the components having a logP greater than 3, preferably greater than 3.5, even more preferably greater than 3.75.

[0061] Preferably, the fragrance used in the present invention contains less than 10% by weight of the primary alcohol itself, less than 15% by weight of the secondary alcohol itself, and less than 20% by weight of the tertiary alcohol itself. Advantageously, the fragrance used in the present invention contains no primary alcohol and contains less than 15% of secondary and tertiary alcohols.

[0062] According to one embodiment, the oil phase (or oil-based core) comprises 25 to 100% by weight of a fragrance oil containing at least 15% by weight of a high-impact fragrance raw material having LogT < -4, 0 to 75% by weight of a density equalizing material having a density greater than 1.07 g / cm 3 and is included.

[0063] "High-impact fragrance raw material" should be understood as a fragrance raw material having LogT < -4. The odor threshold concentration of a chemical compound is partially determined by its shape, polarity, partial charge, and molecular mass. For convenience, the threshold concentration is expressed as the common logarithm of the threshold concentration, i.e., Log[Threshold] ("LogT").

[0064] "Density equalization material" should be understood as a material having a density preferably exceeding 1.07 g / cm3 and preferably having low odor or no odor.

[0065] The density of a component is defined as the ratio (g / cm3) between its mass and its volume.

[0066] Several methods are available for determining the density of a component.

[0067] For example, the ISO 298:1998 method can be referred to for measuring the d20 density of essential oils.

[0068] The odor threshold concentration of a fragrance compound is determined using a gas chromatograph (“GC”). Specifically, the gas chromatograph is calibrated to determine the exact volume, exact split ratio, and hydrocarbon response of the fragrance oil components injected by syringe using hydrocarbon standards of known concentration and chain length distribution. The air flow rate is accurately measured and the sampled volume is calculated assuming a 12-second duration of human inhalation. Since the exact concentration at the detector at any point in time is known, the mass per volume inhaled, and thus the concentration of the fragrance compound, can be determined. To determine the threshold concentration, the solution is delivered to the sniff port at the back-calculated concentration. The panelist sniffs the GC effluent and identifies the retention time at which the odor is perceived. The odor threshold concentration of the fragrance compound is determined by averaging across all panelists. 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, Vol. 33, September, 2008, pages 54-61.

[0069] According to one embodiment, high-impact fragrance raw materials having LogT < -4 are (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenyl acetate, pyrazobutyl, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl)pyridine, 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, a mixture containing (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethylbenzofuran-2-one and (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzofuran-2-one, (+-)-1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one, (1’S,3’R)-1-methyl-2-[(1’,2’,2’-trimethylbicyclo[3.1.0]hex-3’-yl)methyl]cyclopropyl}methanol, (+-)-3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, H-methyl-2h-1,5-benzodioxepin-3(4H)-one, (2E,6Z)-2,6-nonadien-1-ol, (4Z)-4-dodecenal, (+-)-4-hydroxy-2,5-dimethyl-3(2H)-furanone, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4alpha,8beta-dimethyl-4a-naphthalenol, patchoulol, 2-methoxy-4-(1-propenyl)phenol, a mixture containing (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylene-2-phenyl-2H-pyran, 4-methylene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,A mixture containing 6-dihydro-2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonylenal, 2-methoxy-4-propylphenol, 3-methyl-5-phenyl-2-pentenennitrile, 1-(spiro[4.5]deca-6 / 7-ene-7-yl)-4-penten-1-one, 2-methoxynaphthalene, (-)-(3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 5-nonanolid, (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 7-isopropyl-2H,4H-1,5-benzodioxepin-3-one, coumarin, 4-methylphenyl isobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, beta,2,2,3-tetramethyl-delta-methylene-3-cyclopentene-1-butanol, delta-damascone ((2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one), (+-)-3,6-dihydro-4,6-dimethyl-2-phenyl-2H-pyran, anisaldehyde, p-cresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2-aminobenzoate, ethyl methylphenyl glycidate, octalactone gamma, ethyl 3-phenyl-2-propenoate, (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopentene-1-yl]-2-buten-1-ol, p-cresyl acetate, dodecalactone, tricyclon, (+)-(3R,5Z)-3-methyl-5-cyclopentadecen-1-one, undecalactone, (1R,4R)-8-mercapto-3-p-menthanone, (3S,3aS,6R,7aR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, beta-ionone, (+-)-6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1,3,5-undecatriene, 10-undecenal, (9E)-9-undecenal (9Z)-9-undecenal, (Z)-4-decenal, (+-)-ethyl 2-methylpentanoate, 1,2-Diallyl disulfide, 2-tridecenenitrile, 3-tridecenenitrile, (+-)-2-ethyl-4,4-dimethyl-1,3-oxathiane, (+)-(3R,5Z)-3-methyl-5-cyclopentadecen-1-one, 3-(4-tert-butylphenyl)propanal, allyl(cyclohexyloxy)acetate, methylnaphthyl ketone, (+-)-(4E)-3-methyl-4-cyclopentadecen-1-one, (+-)-5E3-methyl-5-cyclopentadecen-1-one, cyclopropylmethyl 3-hexenoate, (4E)-4-methyl-5-(4-methylphenyl)-4-pentenal, (+-)-1-(5-propyl-1,3-benzodioxol-2-yl)ethanone, 4-methyl-2-pentylpyridine, (+-)-(E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, (2S,5R)-5-methyl-2-(2-propanyl)cyclohexanone oxime, 6-hexyltetrahydro-2H-pyran-2-one, (+-)-3-(3-isopropyl-1-phenyl)butanal, methyl 2-(3-oxo-2-pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohex-2-enyl)penta-1-en-3-one, indole, 7-propyl-2H,4H-1,5-benzodioxepin-3-one, ethyl praline, (4-methylphenoxy)acetaldehyde, ethyl tricyclo[5.2.1.0.2,6]decane-2-carboxylate, (+)-(1’S,2S,E)-3,3-dimethyl-5-(2’,2’,3’-trimethyl-3’-cyclopenten-1’-yl)-4-penten-2-ol, (4E)-3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, methylnonylacetaldehyde, 4-formyl-2-methoxyphenyl 2-methylpropanoate, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,Selected from the group consisting of (3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, (1R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]oct-3-ene, (1R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1,6-octadien-3-ol, (E)-3-phenyl-2-propenenitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, allyl (2 / 3-methylbutoxy) acetate, (+-)-(2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1-penten-3-one, and mixtures thereof.,

[0070] According to one embodiment, the fragrance raw material having LogT < -4 is selected from the group consisting of aldehydes, ketones, alcohols, phenols, ester lactones, ethers, epoxides, nitriles and mixtures thereof.

[0071] According to one embodiment, the fragrance raw material having LogT < -4 contains at least one compound selected from the group consisting of alcohols, phenols, ester lactones, ethers, epoxides, nitriles and mixtures thereof, in an amount preferably between 20 and 70% by weight based on the total weight of the fragrance raw material having LogT < -4.

[0072] According to one embodiment, the fragrance raw material having LogT < -4 contains 20 to 70% by weight of aldehydes, ketones and mixtures thereof, based on the total weight of the fragrance raw material having LogT < -4.

[0073] Therefore, the remaining fragrance raw materials contained in the oil-based core may have LogT > -4.

[0074] According to one embodiment, flavor raw materials having LogT > -4 are ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal, benzyl propionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate, (+-)-(E)-4-methyl-3-decen-5-ol, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 1,3,3-trimethyl-2-oxabicyclo[2.2.2] Octane, Tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, Dodecanal, 1-oxa-12 / 13-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, Allyl heptanoate, 2-(2-methyl-2-propanyl)cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl butyrate, Geranyl acetate, Neryl acetate, (+-)-1-phenylethyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, Ethyl 3-oxobutanoate, (2Z)-Ethyl 3-hydroxy-2-butenoate, 8-p-menthanol, 8-p-menthanyl acetate, 1-p-menthanyl acetate, (+-)-2-(4-methyl-3-cyclohexen-1-yl)-2-propanyl acetate, (+-)-2-methylbutyl butanoate, 2-{ (1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3,5,6-trimethyl-3-cyclohexene-1-carbaldehyde, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde, 2-cyclohexylethyl acetate, Octanal, Ethyl butanoate, (+-)-(3E)-4-(2,6,6-trimethyl-1 / 2-cyclohexen-1-yl)-3-buten-2-one, 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, Ethyl hexanoate, Undecanal, Decanal, 2-phenylethyl acetate, (1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1) selected from the group consisting of heptan-2-ol, (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2-propanilidene) cyclohexene, (+)-(R)-4-(2-methoxypropan-2-yl)-1-methylcyclohex-1-ene, verdyl acetate, (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3R)-1-[(1S,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (+)-(1S,1’R)-2-[1-(3’,3’-dimethyl-1’-cyclohexyl)ethoxy]-2-methylpropyl propanoate, and mixtures thereof.

[0075] The properties of the high-impact fragrance raw material having LogT < -4 and the density equalizing material having a density exceeding 1.07 g / cm3 are described in International Publication No. 2018115250, the content of which is incorporated by reference.

[0076] The term "biocide" refers to a chemical substance that can kill organisms (e.g., microorganisms) or reduce or prevent their growth and / or accumulation. Biocides are commonly used in medicine, agriculture, forestry, and industries such as preventing fouling of, for example, water, agricultural products including seeds, and oil pipelines. Biocides can be pest control agents including fungicides, herbicides, insecticides, algicides, molluscicides, acaricides, and rodenticides, and / or antimicrobial agents such as bactericides, antibiotics, antibacterial agents, antiviral agents, antifungal agents, antiprotozoal agents, and / or antiparasitic agents.

[0077] As used herein, "pest control agent" refers to a substance that repels or attracts pests and helps to reduce, inhibit or promote their growth, development or their activity. A pest refers to any organism that is invasive or troublesome to a plant or animal, regardless of whether it is an animal, plant or fungus, and pests include insects, especially arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0078] According to one embodiment, the fragrance formulation comprises 0 to 60% by weight (based on the total weight of the fragrance formulation) of a hydrophobic solvent, and 40 to 100% by weight (based on the total weight of the fragrance formulation) of a fragrance oil having the following characteristics at least 35%, preferably at least 40%, preferably at least 50%, more preferably at least 60% of fragrance components having a logP greater than 3, preferably greater than 3.5, at least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40% of the bulky materials of groups 1 to 6 as defined above, preferably groups 3 to 6, and at least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least 30% of high-impact fragrance materials having a LogT of T < -4 as defined above, optionally, further hydrophobic active ingredients and a fragrance oil having at least two, preferably all, thereof.

[0079] According to a particular embodiment, the fragrance comprises 0 to 60% by weight of a hydrophobic solvent.

[0080] According to a particular embodiment, the hydrophobic solvent is preferably a density-balancing material selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylate, benzyl cinnamate, and mixtures thereof.

[0081] In certain embodiments, the hydrophobic solvent has Hansen solubility parameters that are compatible with the encapsulated fragrance oil.

[0082] The term "Hansen solubility parameter" refers to the solubility parameter approach proposed by Charles Hansen for predicting polymer solubility and is understood to be developed based on the total energy of vaporization of a liquid consisting of several individual parts. To calculate the "weighted Hansen solubility parameter", the effects of (atomic) dispersion forces, (molecular) permanent dipole-permanent dipole forces, and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen solubility parameter" is calculated as (δD2 + δΡ2 + δΗ2)0.5, where δD is the Hansen dispersion value (hereinafter also referred to as the atomic dispersion force), δP is the Hansen polarizability value (hereinafter also referred to as the dipole moment), and δH is the Hansen hydrogen bonding ("h-bonding") value (hereinafter also referred to as hydrogen bonding). For a more detailed explanation of the parameters and values, see Charles Hansen, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, Danish Technical Press (Copenhagen, 1967).

[0083] The Euclidean difference in solubility parameters between the fragrance and the solvent is calculated as (4*(δDsolvent - δDfragrance)2 + (δPsolvent - δPfragrance)2 + (δHsolvent - δHfragrance)2)0.5, where δDsolvent, δPsolvent, and δHsolvent are the Hansen dispersion value, Hansen polarizability value, and Hansen h-bonding value of the solvent, respectively, and δDfragrance, δPfragrance, and δHfragrance are the Hansen dispersion value, Hansen polarizability value, and Hansen h-bonding value of the fragrance, respectively.

[0084] In certain embodiments, the flavor oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the first group consisting of an atomic dispersion force (δD) of 12 to 20, a dipole moment (δP) of 1 to 8, and a hydrogen bond (δH) of 2.5 to 11.

[0085] In certain embodiments, the flavor oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the second group consisting of an atomic dispersion force (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δP) of 1 to 8, preferably 1 to 7, and a hydrogen bond (δH) of 2.5 to 11, preferably 4 to 11.

[0086] According to certain embodiments, the hydrophobic material does not contain an active ingredient (such as a fragrance). According to this particular embodiment, the hydrophobic material preferably comprises, optionally in combination with a hydrophobic solvent preferably selected from the group consisting of isopropyl myristate, triglycerides (e.g., Neobee® MCT oil, vegetable oil), D-limonene, silicone oil, mineral oil, and mixtures thereof, a hydrophilic solvent preferably selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol, glycol ether, and mixtures thereof, preferably consisting of them.

[0087] Acyl chloride According to certain embodiments, the acyl chloride has the following formula (I),

Chemical formula

[0088] "… hydrocarbon group …" means that the group consists of hydrogen and carbon atoms and can be in the form of an aliphatic hydrocarbon, i.e., a straight-chain or branched saturated hydrocarbon (e.g., an alkyl group), a straight-chain or branched unsaturated hydrocarbon (e.g., an alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g., cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g., cycloalkenyl or cycloalkynyl), or can be in the form of an aromatic hydrocarbon, i.e., an aryl group, or can be in the form of a mixture of the above types of groups. For example, a particular group can include a straight-chain alkyl, a branched alkenyl (e.g., having one or more carbon-carbon double bonds), a (poly)cycloalkyl, and an aryl moiety, 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., straight-chain, cyclic or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic or alkenyl), it also means a group that can include a portion having any one of the topologies described above or a portion that is saturated or unsaturated, as described above. Similarly, in all embodiments of the present invention, when a group is referred to as being in one type of saturated or unsaturated form (e.g., alkyl), it means that the group can be of any type of topology (e.g., straight-chain, cyclic or branched) or can have several portions having different topologies.

[0089] The term "hydrocarbon group optionally containing..." is understood to mean that the hydrocarbon group optionally contains heteroatoms and forms ethers, thioethers, amines, nitriles or carboxylic acid groups and derivatives (including, for example, esters, acids, amides). These groups can replace the hydrogen atoms of the hydrocarbon group and thus be attached laterally to the hydrocarbon, or replace the carbon atoms of the hydrocarbon group (where chemically possible) and thus be inserted into the hydrocarbon chain or ring.

[0090] According to one embodiment, the acyl chloride is selected from the group consisting of diacyl chlorides, triacyl chlorides and mixtures thereof.

[0091] According to certain embodiments, the acyl chloride is selected from the group consisting of benzene-1,3,5-tricarbonyl trichloride (trimesityl trichloride), benzene-1,2,4-tricarbonyl trichloride, benzene-1,2,4-tricarbonyl trichloride, benzene-1,2,4,5-tetracarbonyl tetrachloride, cyclohexane-1,3,5-tricarbonyl trichloride, propane-1,2,3-tricarbonyl trichloride, cyclohexane-1,2,4,5-tetracarbonyl tetrachloride, 2,2'-disulfanediylbis(succinyl dichloride), 2-(2-chloro-2-oxo-ethyl)sulfanylbutanedioyl dichloride, (4-chloro-4-oxobutanoyl)-L-glutamoyl dichloride, (S)-4-((1,5-dichloro-1,5-dioxopentan-2-yl)amino)-4-oxobutanoic acid, 2,2-bis[(4-chloro-4-oxo-butanoyl)oxymethyl]butyl 4-chloro-4-oxo-butanoate, [2-[2,2-bis[(4-chloro-4-oxo-butanoyl)oxymethyl]butoxymethyl]-2-[(4-chloro-4-oxo-butanoyl)oxymethyl]butyl] 4-chloro-4-oxo-butanoate, 2,2-bis[(2-chlorocarbonylbenzoyl)oxymethyl]butyl 2-chlorocarbonyl-benzoate, [2-[2,2-bis[(2-chlorocarbonylbenzoyl)oxymethyl]butoxymethyl]-2-[(2-chlorocarbonylbenzoyl)oxymethyl]butyl] 2-chlorocarbonylbenzzoate, 4-(2,4,5-trichlorocarbonylbenzoyl)oxybutyl 2,4,5-trichlorocarbonyl-benzoate, propane-1,2,3-triyltris(4-chloro-4-oxobutanoate), propane-1,2-diylbis(4-chloro-4-oxobutanoate), and mixtures thereof.

[0092] According to one embodiment, the acyl chloride is a diacyl chloride, preferably selected from the group consisting of terephthaloyl chloride, diglycolyl dichloride, phthaloyl chloride, isophthaloyl chloride, adipoyl chloride, sebacoyl chloride, succinyl chloride, glutaroyl chloride, pimeloyl chloride, dodecanedioyl dichloride, suberoyl chloride, azelaoyl chloride, malonyl chloride, fumaryl chloride, oxyallyl chloride, 4,4'-oxybis(benzoyl chloride), 2,2'-oxydiacetyl chloride, 4,4'-biphenyldicarbonyl chloride, azobenzene-4,4'-dicarbonyl dichloride, 2,5-furandicarbonyl dichloride, and mixtures thereof.

[0093] According to a particular embodiment, the acyl chloride is used in an amount comprised between 0.1 and 50% by weight, preferably between 0.5 and 15% by weight, based on the total weight of the core.

[0094] Oligopeptide According to the present invention, an "oligopeptide" is a homo-oligopeptide containing only one type of repeating amino acid unit linked by peptide bonds. According to one embodiment, the oligopeptide contains from 2 to 30, preferably from 2 to 25, amino acid units (also called residues) linked by peptide bonds.

[0095] According to one embodiment, an "oligopeptide" is a homo-oligopeptide containing only one type of repeating amino acid unit, and is defined as a (one or more) molecule consisting of at least 2 and less than 25 amino acid units (also called residues) linked by peptide bonds.

[0096] The oligopeptide according to the present invention has an average molecular weight of less than 4000 g / mol.

[0097] The terms "oligopeptide", "homo-oligopeptide", "homo-oligopeptide mixture" or "oligopeptide mixture" may be used interchangeably in the present invention. According to the present invention, an oligopeptide mixture contains at least one oligopeptide.

[0098] In other words, according to the present invention, the term "oligopeptide" or "oligopeptide mixture" may also include a mixture of an oligopeptide and a free amino acid.

[0099] The terms "amino acid" and "free amino acid" may be used interchangeably in the present invention.

[0100] The terms "oligopeptide" and "peptide" may be used interchangeably in the present invention.

[0101] According to the present invention, a polyamino acid (such as polylysine) is not part of the definition of "oligopeptide" since a polyamino acid is defined as having a molecular weight of 4000 g / mol or more.

[0102] The average molecular weight can be readily determined by those skilled in the art.

[0103] According to one embodiment, the average molecular weight of an oligopeptide can be extracted from 1 H NMR analysis, for example, using a Bruker AV-300 spectrometer.

[0104] According to one embodiment, the oligopeptide has an average molecular weight of less than 4000 g / mol, preferably at most 2000 g / mol, more preferably 200 - 1000 g / mol.

[0105] According to one embodiment, the oligopeptide has an average molecular weight of from 200 to less than 4000 g / mol. According to one embodiment, the oligopeptide has an average molecular weight of from 200 to 2000 g / mol.

[0106] According to one embodiment, the oligopeptide can be linear, branched or random.

[0107] According to one embodiment, at least one oligopeptide has at least two amino groups, preferably at least three amino groups.

[0108] The oligopeptide is preferably selected from the group consisting of oligo-lysine, oligo-arginine, oligo-histidine, oligo-tryptophan, oligo-serine, oligo-glutamine, oligo-threonine, oligo-asparagine, oligo-ornithine, and oligo-citrulline.

[0109] According to one embodiment, the oligo-lysine can be linear, branched or random.

[0110] According to one embodiment, the oligopeptide is selected from the group consisting of oligo-lysine, oligo-arginine, oligo-histidine, oligo-tryptophan, and oligo-ornithine.

[0111] According to one embodiment, the oligopeptide is oligo-lysine, more specifically, linear oligo-lysine or (hyper)branched oligo-lysine.

[0112] According to a particular embodiment, the oligo-lysine can be α-oligo-lysine or ε-oligo-lysine.

[0113] According to a particular embodiment, the oligo-lysine can be oligo-L-lysine, more specifically, α-oligo-L-lysine or ε-oligo-L-lysine; oligo-D-lysine, more specifically, α-oligo-D-lysine or ε-oligo-D-lysine; oligo-D,L-lysine, more specifically, α-oligo-D,L-lysine or ε-oligo-D,L-lysine, and mixtures thereof.

[0114] According to one embodiment, the oligo-lysine can be reacted with an acyl chloride.

[0115] According to certain embodiments, the polyamide shell comprises a reaction product between an oligo-lysine, preferably oligo-L-lysine, and at least one diacyl chloride.

[0116] According to certain embodiments, the polyamide shell comprises a reaction product between an oligo-lysine, preferably oligo-L-lysine, and phthaloyl chloride.

[0117] According to certain embodiments, the polyamide shell comprises a reaction product between an oligo-lysine, preferably oligo-L-lysine, and isophthaloyl chloride.

[0118] According to certain embodiments, the polyamide shell comprises a reaction product between an oligo-lysine, preferably oligo-L-lysine, and terephthaloyl chloride.

[0119] (Tere / iso)phthaloyl chloride means terephthaloyl chloride or isophthaloyl chloride or phthaloyl chloride.

[0120] According to one embodiment, the molar ratio of the average amino groups from the oligopeptide to the acyl chloride groups from the acyl chloride is from 0.05:1 to 65:1, preferably from 0.1:1 to 10:1.

[0121] According to one embodiment, the oligopeptide mixture comprises the oligopeptide defined above and free amino acids.

[0122] The free amino acids can be lysine, arginine, histidine, tryptophan, ornithine, glutamine, asparagine, citrulline, and mixtures thereof.

[0123] According to one embodiment, the nature of the amino acids in the free amino acids is the same as the nature of the amino acids in the amino acid units contained in the oligopeptide.

[0124] According to one embodiment, the properties of the amino acids in the free amino acids are different from the properties of the amino acids in the amino acid units contained in the oligopeptide.

[0125] According to one embodiment, the oligopeptide does not contain free amino acids.

[0126] According to one embodiment, the oligopeptide is present in an amount of at least 20% by weight, preferably at least 50% by weight, based on the total weight of the oligopeptide mixture.

[0127] According to one embodiment, the oligopeptide is present in an amount included between 20% by weight and 100% by weight, preferably between 50% by weight and 95% by weight, based on the total weight of the oligopeptide mixture.

[0128] According to one embodiment, when present, the free amino acids are present in an amount of at least 5% by weight, preferably at least 10% by weight, based on the total weight of the oligopeptide mixture.

[0129] The oligopeptide used in the present invention may be commercially available or may be prepared.

[0130] The oligopeptide can be prepared by enzymatic synthesis, and more specifically, the following steps (i) The step of preparing an aqueous solution of amino acid ester (ii) The step of adding an enzyme solution to the solution of step (i) (iii) The step of applying conditions sufficient to obtain the oligopeptide are included.

[0131] The enzyme can be selected from the list consisting of bromelain, papain, ficin, actinidin, zingibain, legumain, cardosin A or B, enzymes derived from germinated plant seeds such as garlic, mustard, broccoli, enzymes derived from asparagus, enzymes derived from onions, chymotrypsin, trypsin, carboxypeptidase, pepsin, cathepsin, calpain, chymosin, thrombin, serine endopeptidase (Alcalase®), bacterial enzyme (Neutrase®) produced by a selected strain of Bacillus amyloliquefaciens, enzyme isolated from the extracellular fluid of Streptomyces griseus (Pronase®), and a mixture of a serine endopeptidase derived from Bacillus amyloliquefaciens and produced in recombinant B. subtilis (Purafect Prime® L), alkaline enzyme, metalloenzyme, microbial enzyme, and mixtures thereof.

[0132] The amino acid ester can be lysine alkyl ester, arginine alkyl ester, histidine alkyl ester, tryptophan alkyl ester, serine alkyl ester, glutamine alkyl ester, threonine alkyl ester, asparagine alkyl ester, ornithine alkyl ester, citrulline alkyl ester.

[0133] As a non-limiting example, the aqueous amino acid ester solution used in step (i) can be an aqueous amino acid alkyl ester hydrochloride solution.

[0134] Oligo-L-lysine can be prepared by enzymatic synthesis, more specifically, the following steps (i) Preparing a solution of L-lysine alkyl ester dihydrochloride (ii) Adding a bromelain solution to the solution of step (i) (iii) steps of applying conditions sufficient to obtain oligo-L-lysine comprising.

[0135] It should be noted that according to one embodiment, at the end of step (iii), a mixture of oligo-L-lysine, free L-lysine, and free L-lysine alkyl ester with or without hydrochloride can be obtained.

[0136] According to one embodiment, at the end of step (iii), a mixture of oligopeptide, free amino acid with or without hydrochloride, and optionally one salt (derived from the synthesis of the oligopeptide) can be obtained.

[0137] According to one embodiment, when present at the end of step (iii), the free amino acid is present in an amount between 5% and 50% by weight, preferably between 10% and 20% by weight, based on the total weight of the oligopeptide mixture.

[0138] According to one embodiment, at the end of step (iii), a mixture of oligo-L-lysine and free L-lysine with or without hydrochloride can be obtained.

[0139] Those skilled in the art will be able to select appropriate conditions for performing step (iii). Typically, step (iii) includes a step of controlling the reaction temperature to 4 - 70°C, more preferably 25 - 55°C. The heating step can be carried out in step (iii).

[0140] Oligo-lysine can also be prepared according to organic synthesis as disclosed in, for example, RSC Adv., 2015, 5, 84947 - 84958, Macromolecules 2007, 40, 5726 - 5734.

[0141] Stabilizer According to one embodiment, the polyamide shell comprises the reaction product between at least one acyl chloride and at least one oligopeptide in the presence of a stabilizer.

[0142] According to the properties of the stabilizer, the stabilizer can be part of the shell. The stabilizer can react with acyl chloride and oligopeptide.

[0143] Thus, according to one embodiment, the polyamide shell comprises a reaction product between at least one acyl chloride, at least one oligopeptide, and at least one stabilizer.

[0144] According to one embodiment, the polyamide shell comprises a reaction product between at least one acyl chloride, at least one oligopeptide, at least one free amino acid, and at least one stabilizer.

[0145] According to one embodiment, the microcapsules or microcapsule slurry comprise a stabilizer.

[0146] The stabilizer is defined as follows.

[0147] Biodegradability In certain embodiments, the shell material is a biodegradable material.

[0148] In certain embodiments, the shell has at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradability within 60 days according to OECD301F.

[0149] In certain embodiments, the core-shell microcapsules have at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% biodegradability within 60 days according to OECD301F.

[0150] Thus, it is understood that core-shell microcapsules containing all components such as core, shell and optionally coating can have biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD301F.

[0151] In certain embodiments, an oil-based core, preferably a fragrance oil, has biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD301F.

[0152] OECD301F is a standard test method for biodegradability by the Organization for Economic Cooperation and Development.

[0153] A typical method for extracting the shell to measure biodegradability is disclosed in Gasparini and all in Molecules 2020,25,718.

[0154] Optional outer coating According to certain embodiments of the present invention, the microcapsules comprise an outer coating, the outer coating comprising a coating material selected from the group consisting of non-ionic polysaccharides, cationic polymers, polysuccinimide derivatives (e.g., described in WO 2021185724) and mixtures thereof for forming the outer coating on the microcapsules.

[0155] Non-ionic polysaccharide polymers are well known to those skilled in the art and are described, for example, on page 29, lines 1 to 25 of WO 2012 / 007438 and on pages 2, lines 12 to 19 and 4, lines 3 to 12 of WO 2013 / 026657. Preferred non-ionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

[0156] 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, and preferably less than about 7 meq / g, more preferably less than about 6.2 meq / g. The cationic charge density of the cationic polymer can be determined under chemical tests for nitrogen determination by the Kjeldahl method described in the United States Pharmacopeia. Preferred cationic polymers are selected from those containing units comprising primary, secondary, tertiary and / or quaternary amine groups that can form part of the main polymer chain or be carried by pendant substituents directly attached thereto. The weight average (Mw) molecular weight of the cationic polymer is preferably from 10,000 to 3.5 million Daltons, more preferably from 50,000 to 1.5 million 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-imidazol-3-ium chloride), vinylpyrrolidone, acryamidopropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride are used. Preferably, the copolymer is selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium 10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride.Specific examples of commercially available products include Salcare® SC60 (a cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, manufacturer: BASF), or Luviquat®, for example PQ 11N, FC 550 or Style (polyquaternium-11 to 68, or a quaternized copolymer of vinylpyrrolidone, manufacturer: BASF), or Jaguar® (C13S or C17, manufacturer: Rhodia).

[0157] According to any one of the above embodiments of the present invention, an amount of the above polymer contained between about 0% w / w and 5% w / w, or even between about 0.1% w / w and 2% w / w, is added, and 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 part of the added polymer is incorporated into the microcapsule shell / deposited on the microcapsule shell.

[0158] Optional components When the microcapsules are in the form of a slurry, the microcapsule slurry can contain auxiliary components selected from the group of thickeners / rheology modifiers, antibacterial agents, opacity formers, mica particles, salts, pH stabilizers / buffer components, preferably in an amount contained between 0 and 15% by weight based on the total weight of the slurry.

[0159] According to another embodiment, the microcapsule slurry of the present invention contains additional free (i.e., non-encapsulated) fragrance, preferably in an amount contained between 5 and 50% by weight based on the total weight of the slurry.

[0160] In a specific embodiment, the core-shell microcapsules are isolated by drying the resulting core-shell microcapsule slurry. Drying can be achieved by subjecting the resulting core-shell microcapsule slurry to a drying step such as spray drying, providing the microcapsules as they are, i.e., in powder form.

[0161] It is understood that any standard method known to those skilled in the art for carrying out such drying is also applicable. In particular, the slurry can be spray-dried in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, plant gums, pectin, xanthan, alginate, carrageenan or cellulose derivatives to provide microcapsules in powder form.

[0162] According to certain embodiments, the carrier material contains a free perfume oil which may be the same as or different from the perfume from the core of the microcapsules.

[0163] Method for preparing polyamide microcapsules Another object of the present invention is a method for preparing a polyamide core-shell microcapsule slurry, comprising the following steps: a) dispersing an oil phase containing a hydrophobic material and at least one acyl chloride in a dispersion phase to form a two-phase dispersion; b) performing a curing step to form microcapsules in the form of a slurry and at least one stabilizer is added to the oil phase and / or the dispersion phase, at least one oligopeptide is added to the dispersion phase and / or the oil phase and / or the two-phase dispersion.

[0164] According to one embodiment, the method comprises the following steps: a) dispersing an oil phase containing a hydrophobic material and at least one acyl chloride in an aqueous phase to form a water-in-oil emulsion; b) performing a curing step to form microcapsules in the form of a slurry and at least one stabilizer is added to the oil phase and / or the aqueous phase, at least one oligopeptide is added to the aqueous phase and / or the oil phase and / or the water-in-oil emulsion.

[0165] The embodiments previously disclosed with respect to polyamide core - shell microcapsules, and more particularly hydrophobic materials, oligopeptides, and acyl chlorides, are also applicable to the method for preparing said microcapsules.

[0166] According to one embodiment, the dispersed phase contains water and preferably consists of water.

[0167] According to one embodiment, the dispersed phase is an aqueous phase.

[0168] According to one embodiment, the two - phase dispersion is an oil - in - water emulsion.

[0169] According to one embodiment, the dispersed phase contains water and an alcohol such as glycerol, 1,4 - butanediol, ethylene glycol, and mixtures thereof.

[0170] According to one embodiment, the pH of the dispersed phase is included between 7 and 13, particularly between 9 and 11.

[0171] The acyl chloride can be directly dissolved / dispersed in the flavor oil or pre - dispersed or pre - dissolved in an inert solvent or any inert flavor solvent / component such as benzyl benzoate, triethyl citrate, ethyl acetate, hexyl salicylate, or Neobee before mixing with the flavor oil.

[0172] According to the present invention, at least one stabilizer is added to the dispersed phase and / or the oil phase to form an emulsion.

[0173] "Stabilizer" means a compound that can stabilize the oil / dispersed - phase interface (typically the oil / water interface) as an emulsion.

[0174] "Stabilizer" or "emulsifier" can be used interchangeably in the present invention.

[0175] According to one embodiment, the stabilizer is a colloidal stabilizer.

[0176] The colloidal stabilizer can be a polymer emulsifier (standard emulsion), a surfactant, or solid particles (pickering emulsion).

[0177] The "polymer emulsifier" means an emulsifier having both a polar group (hydrophilic) having an affinity for the dispersed phase (typically water) and a non-polar group (hydrophobic) having an affinity for oil. The hydrophilic part dissolves in the dispersed phase, and the hydrophobic part dissolves in the oil phase, providing a film around the droplets.

[0178] The "surfactant" means a substance having a polar group and a non-polar group that is added to a liquid to lower the surface tension of the liquid.

[0179] 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.

[0180] When the stabilizer is solid particles, the stabilizer can be selected from the group consisting of calcium phosphate, silica, silicate, titanium dioxide, aluminum oxide, zinc oxide, iron oxide, mica, kaolin, montmorillonite, laponite, bentonite, perlite, dolomite, diatomaceous earth, vermiculite, hectorite, gibbsite, illite, kaolinite, aluminosilicate, gypsum, bauxite, magnesite, talc, magnesium carbonate, calcium carbonate, diatomaceous earth, and mixtures thereof.

[0181] According to a particular embodiment, the stabilizer is a biopolymer.

[0182] "Biopolymer" means a biopolymer produced by organisms. Biopolymers are characterized by a molecular weight distribution in the range of 1,000 (one thousand) to 1,000,000,000 (one billion) daltons. These macromolecules may be carbohydrates (sugar-based), proteins (amino acid-based), or a combination of both (gums), and may be linear or branched.

[0183] According to one embodiment, the stabilizer is a polymer emulsifier preferably selected from the group consisting of gum arabic, modified starch, polyvinyl alcohol, polyvinyl pyrrolidone (PVP), carboxymethyl cellulose (CMC), anionic polysaccharides, acrylamide copolymers, proteins such as soy protein, rice protein, whey protein, ovalbumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudo-collagen, silk protein, sericin powder, potato protein, chickpea protein, pea protein, algal protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, and mixtures thereof.

[0184] Potato protein is typically extracted from potato tubers (Solanum tuberosum). According to one embodiment, the potato protein is natural potato protein, preferably patatin.

[0185] According to a particular embodiment, the stabilizer is not a protein. According to one embodiment, no protein is added at any stage of the method.

[0186] According to one embodiment, the stabilizer is used at a concentration of 0.05 wt% to 20 wt%, preferably 0.1 to 5 wt%, based on a two-phase dispersion, preferably an oil-in-water emulsion.

[0187] According to one embodiment, at least one salt is added to the dispersed phase and / or the oil phase and / or the two-phase dispersion. The presence of the salt can enhance the stability of the polyamide shell.

[0188] The salt can be added especially when a protein is used as a stabilizer.

[0189] The salt is preferably used in an amount included between 0.01% by weight and 10% by weight, based on the two-phase dispersion.

[0190] The salt can be selected from the group consisting of calcium, zinc, sodium, potassium, lithium, magnesium, aluminum, iron, manganese, copper, titanium, barium, sulfates, phosphates, nitrates, bromides, chlorides, iodides, acetates, and ammonium salts.

[0191] According to one embodiment, the salt is CaCl 2 , NaCl, KCl, ZnCl 2 , ZnSO 4 , Zn(NO 3 ) 2 , LiCl, Ca(NO 3 ) 2 , MgCl 2 , CaBr 2 , CaI 2 , NaBr, NaI, NaNO 3 , KBr, KI, KNO 3 , LiBr, LiI, MgBr 2 , CuCl 2 , FeCl 2 , FeCl 3 , TiCl 4 , MnCl 2 and is selected from the group consisting of their mixtures.

[0192] According to one embodiment, the salt is CaCl 2 , NaCl, KCl, ZnCl 2 , LiCl, Ca(NO 3 ) 2 , MgCl 2Selected from the group consisting of and mixtures thereof.

[0193] According to one embodiment, the acyl chloride is used at a concentration of 0.1 wt% to 50 wt%, preferably 0.5 to 15 wt%, based on the oil phase.

[0194] According to one embodiment, the pH of the stabilizer solution is included between 7 and 13, particularly between 9 and 11.

[0195] According to one embodiment, in addition to the oligopeptide, an amino compound is added to the dispersed phase and / or the two-phase dispersion.

[0196] The amino compound can be an amino acid and is preferably selected from the group consisting of lysine, arginine, histidine, tryptophan, ornithine, glutamine, asparagine, citrulline and mixtures thereof.

[0197] The amino compound can typically be added in an amount included between 0.1 and 10 wt% based on the two-phase dispersion.

[0198] According to another embodiment, the amino compound can be selected from the group consisting of 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,9-diaminononane, 1,12-diaminododecane, 4,9-dioxa-1,12-dodecanediamine, 3,3'-diamino-N-methyldipropylamine, xylylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, L-lysine ethyl ester, Jeffamine®, ethylenediamine, diethylenetriamine, spermine, spermidine, polyamidoamine (PAMAM), guanidine carbonate, chitosan, oligo-chitosan, tris-(2-aminoethyl)amine, 3-aminopropyltriethoxysilane, arginine alkyl ester, histidine alkyl ester, tryptophan alkyl ester, ornithine alkyl ester, polylysine, polyhistidine, polyornithine and mixtures thereof.

[0199] According to one embodiment, no additional amino compound is added at any stage of the method.

[0200] According to one embodiment, at least one additional polyfunctional monomer is added to the method, and at least one additional polyfunctional monomer is not an acyl chloride.

[0201] According to one embodiment, at least one additional polyfunctional monomer is added to the oil phase of step a) and / or the dispersion phase of step b), preferably to the oil phase of step a).

[0202] According to one embodiment, the polyfunctional monomer is selected from the group consisting of at least one isocyanate, anhydride or maleic anhydride, epoxide, (meth)acrylate monomer, alkoxysilane and mixtures thereof.

[0203] Suitable polyisocyanates for use in accordance with the present invention can include aromatic polyisocyanates, aliphatic polyisocyanates, and mixtures thereof. The polyisocyanate contains at least 2, preferably at least 3, isocyanate functional groups, but may contain a maximum of 6, or even only 4, isocyanate functional groups. According to a particular embodiment, a triisocyanate (3 isocyanate functional groups) is used.

[0204] According to one embodiment, the polyisocyanate is an aromatic polyisocyanate.

[0205] As used herein, the term "aromatic polyisocyanate" is meant to encompass any polyisocyanate containing an aromatic moiety. Preferably, the aromatic moiety contains a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety, more preferably a tolyl or xylyl moiety. Preferred aromatic polyisocyanates are biurets, polyisocyanurates and trimethylolpropane adducts of diisocyanates, more preferably containing one of the specific aromatic moieties described above. More preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® RC), a trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the trade name Desmodur® L75), a trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the trade name Takenate® D-110N). In the most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

[0206] According to another embodiment, the polyisocyanate is an aliphatic polyisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain an aromatic moiety. Preferred aliphatic polyisocyanates are trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate (available from Mitsui Chemicals) or biurets of hexamethylene diisocyanate (commercially available from Bayer under the trade name Desmodur® N 100), and among these, biurets of hexamethylene diisocyanate are even more preferred.

[0207] According to another embodiment, at least one polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both containing at least two or three isocyanate functional groups, for example, a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate, a mixture of a biuret of hexamethylene diisocyanate and a polyisocyanurate of toluene diisocyanate, and a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of toluene diisocyanate. Most preferably, it is a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate. Preferably, when used as a mixture, the molar ratio of the aliphatic polyisocyanate to the aromatic polyisocyanate is in the range of 80:20 to 10:90.

[0208] According to one embodiment, the additional polyfunctional monomer is present in an amount corresponding to 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 0.8 to 6% by weight, even more preferably 1 to 3% by weight, based on the total amount of the oil phase and / or the dispersed phase.

[0209] According to one embodiment, the hydrophobic material corresponds to about 10% to 99% by weight, based on the total weight of the oil phase. According to another embodiment, the hydrophobic material corresponds to about 10% to 80% by weight, based on the total weight of the oil phase. According to another embodiment, the hydrophobic material corresponds to about 10% to 60% by weight, based on the total weight of the oil phase. According to another embodiment, the hydrophobic material corresponds to about 15% to 45% by weight, based on the total weight of the oil phase.

[0210] The curing step is typically carried out at a temperature of 5°C to 90°C, preferably 40°C to 80°C, for 5 minutes to 40 hours, preferably 30 minutes to 24 hours, with stirring to complete the reaction and form microcapsules in the form of a slurry. However, the heating step can be omitted.

[0211] Multi-capsule system According to one embodiment, the microcapsules (first type of microcapsules) of the present invention can be used in combination with a second type of microcapsules.

[0212] Another object of the present invention is the microcapsules of the present invention as the first type of microcapsules, a second type of microcapsules, wherein the first type of microcapsules and the second type of microcapsules are different in their hydrophobic materials and / or their wall materials and / or their coating materials, and a microcapsule delivery system comprising the same.

[0213] According to a particular embodiment, the microcapsule delivery system is in the form of a slurry.

[0214] The wall of the second type of microcapsules can vary. By way of non-limiting example, the polymer shell of the second type of microcapsules comprises a material selected from the group consisting of polyurea, polyurethane, polyamide, polyhydroxyalkanoate, polyacrylate, polyester, polyaminoester, polyepoxide, organosilicon, polycarbonate, polysulfonamide, a shell wall of gelatin / arabic gum, and mixtures thereof.

[0215] The second type of microcapsules can comprise an oil-based core containing a hydrophobic active substance, preferably a fragrance, and a composite material shell containing a first material and a second material, the first material being different from the second material, the first material being coacervate and the second material being a polymer material. In certain embodiments, the weight ratio of the first material to the second material is included between 50:50 and 99.9:0.1. In certain embodiments, the coacervate preferably comprises a first polyelectrolyte selected from proteins (such as gelatin), polypeptides or polysaccharides (such as chitosan), most preferably gelatin, and, preferably, a second polyelectrolyte selected from alginates, cellulose derivative guar gum, pectates, carrageenan, polyacrylic acid and methacrylic acid or xanthan gum, or further plant gums such as acacia gum (arabic gum), most preferably arabic gum. The first material, which is coacervate, can be chemically hardened using a suitable cross-linking agent such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin, or can be enzymatically hardened using an enzyme such as transglutaminase. The second polymer material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, organosilicon, polycarbonate, polysulfonamide 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.

[0216] As a non-limiting example, the shell of the second type of microcapsule can be polyurea-based or polyurethane-based. The shell of the second type of microcapsule may be a hybrid, i.e., an organic-inorganic hybrid, for example, a hybrid shell composed of at least two types of cross-linked inorganic particles, or a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0217] According to another aspect, the shell of the second type of microcapsule is, for example, but not limited to, polyurea-based made from isocyanate-based monomers and amine-containing cross-linking agents such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules include a polyurea wall that is a reaction product of polymerization between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from the group consisting of amines (e.g., water-soluble guanidine salts and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of amines can be omitted. According to a particular aspect, the colloidal stabilizer includes an aqueous solution of 0.1% - 0.4% polyvinyl alcohol, 0.6% - 1% of a cationic copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (all percentages are defined by weight relative to the total weight of the colloidal stabilizer). According to another aspect, the emulsifier is an anionic or amphiphilic biopolymer and, in one aspect, can be selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0218] According to a particular embodiment, the second type of microcapsule comprises an oil-based core containing a hydrophobic active substance, preferably a fragrance, and a polyamide shell, preferably containing an amount of acyl chloride between 5 - 98%, preferably 20 - 98%, more preferably 30 - 85% w / w, Preferably, a first amino compound in an amount included between 1% to 50% w / w, preferably between 7 to 40% w / w, Preferably, a second amino compound in an amount included between 1% w / w to 50% w / w, preferably between 2% w / w to 25% w / w, Optionally, preferably, a stabilizer, preferably a biopolymer, in an amount included between 0 to 90%, preferably between 0.1 to 75%, more preferably between 1 to 70%, Optionally, a carbohydrate comprising or obtained from them, a polyamide shell and comprises.

[0219] According to a particular embodiment, the second type of microcapsules is an oil-based core comprising a hydrophobic active substance, preferably a fragrance, and a polyamide shell, wherein an acyl chloride, a first amino compound which is preferably an amino acid selected from the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and / or mixtures thereof, the first amino compound, a second amino compound which is preferably selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine and / or mixtures thereof, the second amino compound, a biopolymer which is preferably selected from the group consisting of potato protein, chickpea protein, pea protein, algal protein, broad bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, soy protein, rice protein, whey protein, egg white albumin, casein, sodium caseinate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudo-collagen, silk protein, sericin powder, gelatin and mixtures thereof, the biopolymer, Optionally, a carbohydrate, preferably an anionic salt of alginic acid, preferably sodium alginate, pectin, lignin, anionic modified starch, carboxymethyl cellulose, carrageenan, and mixtures thereof, a carbohydrate selected from the group consisting of comprising or obtained from them, a polyamide shell and comprises.

[0220] According to another aspect, the shell of the second type of microcapsule is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea-based and polyurethane-based microcapsule slurries are described, for example, in International Patent Application Publication No. WO 2007 / 004166, European Patent Application Publication No. EP 2300146, and European Patent Application Publication No. EP 25799. Typically, a method for preparing a polyurea-based or polyurethane-based microcapsule slurry comprises the following steps: a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase; b) preparing an aqueous solution of an emulsifier or colloid stabilizer to form a dispersion phase; c) adding the oil phase to the dispersion phase to form a water-in-oil type dispersion, wherein the average droplet size is between 1 and 500 μm, preferably between 5 and 50 μm; d) inducing interfacial polymerization and applying conditions sufficient to form microcapsules in the form of a slurry including.

[0221] Flavor compositions and consumer products The microcapsules of the present invention can be used in combination with an active ingredient. Accordingly, the object of the present invention is (i) the microcapsules or microcapsule slurry as defined above, and (ii) An active ingredient, preferably selected from the group consisting of cosmetic ingredients, skin care ingredients, fragrance ingredients, flavor ingredients, malodor preventing ingredients, bactericidal ingredients, fungicidal ingredients, pharmaceutical or agricultural ingredients, disinfecting ingredients, insect repellents or attractants, and mixtures thereof, and A composition containing the same.

[0222] The microcapsules of the present invention exhibit good performance regarding stability in difficult media.

[0223] Another object of the present invention is (i) An oil-containing fragrance, the microcapsules or microcapsule slurry as defined above, and (ii) At least one ingredient selected from the group consisting of cosmetic carriers, cosmetic co-ingredients, and mixtures thereof, and (iii) Optionally, at least one cosmetic adjuvant A fragrance composition containing the same.

[0224] As a liquid cosmetic carrier, non-limiting examples include emulsion systems, i.e., solvent systems and surfactant systems, or solvents commonly used in cosmetics. A detailed description of the nature and types of solvents commonly used in cosmetics is not exhaustive. However, non-limiting examples include solvents most commonly used, such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate. In the case of a composition containing both a cosmetic carrier and a cosmetic co-component, other suitable cosmetic carriers other than those specified above may also be ethanol, a water / ethanol mixture, limonene or other terpenes, isoparaffin, such as those known by the trademark Isopar® (manufacturer: Exxon Chemical), or glycol ethers and glycol ether esters, such as those known by the trademark Dowanol® (manufacturer: Dow Chemical Company). "Cosmetic co-component" as used herein means a compound used in a cosmetic preparation or composition to impart a pleasant effect and which is not a microcapsule as defined above. In other words, such co-components must be recognized by those skilled in the art as being able to not only simply have an odor but also at least impart or modify the odor of the composition in a positive or pleasant direction in order to be considered a fragrance component.

[0225] The nature and types of fragrance co-components present in the fragrance composition are not guaranteed by the more detailed description herein, are not exhaustive in any case, and 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 co-components belong to various chemical classifications such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen or sulfur heterocyclic compounds, and essential oils, and the said fragrance co-components can be of natural or synthetic origin. Many of these co-components are listed in references such as books, S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent version, or other works of a similar nature, as well as numerous patent documents in the field of cosmetics. It is also understood that the said co-components may also be compounds known to release various types of fragrance compounds, also known as pro-fragrances or pro-fragrances, in a controlled manner. Non-limiting examples of suitable 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, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1-yl oxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,(6-dien-1-yl) succinate, (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-pentylcyclopentylidene)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 are mentioned.,

[0226] As used herein, "fragrance adjuvant" means a component that can impart additional benefits such as color, specific lightfastness, chemical stability, etc. Although a detailed description of the nature and types of adjuvants commonly used in fragrance bases is not comprehensive, it should be mentioned that the above components are well known to those skilled in the art.,

[0227] Preferably, the fragrance composition according to the present invention contains 0.01 to 30% by weight of the microcapsules defined above.,

[0228] The microcapsules of the present invention can be advantageously used in many application fields and can be used in consumer products. The microcapsules can be used in a liquid form applicable to liquid consumer products and in a powder form applicable to powder consumer products.

[0229] According to a particular embodiment, the consumer product as defined above is liquid and hereinafter, a) at least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, and b) water or a water-miscible hydrophilic organic solvent, and c) the microcapsule slurry or microcapsules as defined above, and d) optionally, an unencapsulated perfume are included.

[0230] According to a particular embodiment, the consumer product as defined above is in powder form and hereinafter, a) at least one surfactant in an amount of 2 to 65% by weight relative to the total weight of the consumer product, and b) the microcapsule powder as defined above, and c) optionally, a perfume powder different from the microcapsules as defined above are included.

[0231] In the case of microcapsules containing a perfume oil-based core, the products of the present invention can be used in particular in perfumed consumer products such as products belonging to fine fragrances or "functional" cosmetics. Functional cosmetics include in particular personal care products including hair care, body cleansing, skin care, and hygiene care, as well as home care products including laundry care, surface care, and air care. Accordingly, another object of the present invention consists of a perfumed consumer product containing the microcapsules as defined above or the perfume composition as defined above as a perfume ingredient. The perfume element of the consumer product can be a combination of the perfume microcapsules as defined above, free or unencapsulated perfume, and other types of perfume microcapsules other than those disclosed herein.

[0232] In particular, hereinafter, a) at least one surfactant in an amount of 2 to 65% by weight based on the total weight of the consumer product, and b) water or a water-miscible hydrophilic organic solvent, and c) the perfume composition as defined above A liquid consumer product containing the same is another object of the present invention.

[0233] Also, hereinafter, (a) at least one surfactant in an amount of 2 to 65% by weight based on the total weight of the consumer product, and (b) the perfume composition as defined above A powder consumer product containing the same is also part of the present invention.

[0234] Therefore, the microcapsules of the present invention can be added to perfumed consumer products as they are or as part of the perfume composition of the present invention.

[0235] For the sake of clarity, it should be mentioned that "perfumed consumer products" mean consumer products that, among other benefits, are expected to provide a perfume effect on the surface to which they are applied (e.g., skin, hair, textiles, paper or household surfaces) or in the air (air fresheners, deodorants, etc.). In other words, the perfumed consumer products according to the present invention are manufactured products that contain a functional formulation, also called a "base", together with a beneficial agent, in particular an effective amount of the microcapsules according to the present invention.

[0236] The nature and types of other constituents of the perfumed consumer product are not guaranteed by the more detailed description herein, nor are they exhaustive in any case, and those skilled in the art can select them according to the nature of the product and the desired effects based on their general knowledge. The base formulations of consumer products into which the microcapsules of the present invention can be incorporated can be found in the extensive literature on such products. These formulations are not guaranteed by the detailed description herein, nor are they exhaustive in any case. Those skilled in the art of formulating such consumer products can fully select the appropriate components based on their general knowledge and the available literature.

[0237] Non-limiting examples of suitable perfumed consumer products are perfumes, such as fine fragrances, colognes, aftershave lotions, body splashes; fabric care products, such as liquid or solid detergents, tablets and unit doses (single or multiple chambers), fabric softeners, dryer sheets, fabric fresheners, ironing water, or bleaches; personal care products, such as hair care products (e.g., shampoos, hair conditioners, coloring agents or hair sprays), cosmetics (e.g., vanishing creams, body lotions or deodorants or antiperspirants), or skin care products (e.g., perfumed soaps, shower or bath mousses, body washes, oils or gels, bath salts, or hygiene products); air care products, such as air fresheners or "ready-to-use" powdered air fresheners; or home care products, such as all-purpose cleaners, liquid or powdered or tablet dishwashing products, toilet cleaners, or products for cleaning various surfaces, such as sprays and wipes for treating / refreshing fabrics or hard surfaces (floors, tiles, stone floors, etc.); hygiene products, such as sanitary napkins, diapers, toilet paper.

[0238] Another object of the present invention is a personal care active ingredient base, and The microcapsules or microcapsule slurry as defined above or the perfume composition as defined above and comprising is a consumer product in the form of a personal care composition.

[0239] Personal care active substance bases into which the microcapsules of the present invention can be incorporated can be found in the extensive literature on such products. These formulations do not warrant a detailed description herein and are not exhaustive in any case. One skilled in formulating such consumer products can fully select appropriate components based on their general knowledge and the available literature.

[0240] The personal care composition is preferably selected from the group consisting of hair care products (e.g., shampoos, hair conditioners, coloring agents or hair sprays), cosmetics (e.g., vanishing creams, body lotions or deodorants or antiperspirants), or skin care products (e.g., scented soaps, shower or bath mousses, body washes, oils or gels, bath salts or hygiene products). Another object of the present invention is a home care or fabric care active substance base, and the microcapsules or microcapsule slurry as defined above or the perfume composition as defined above and comprising is a consumer product in the form of a home care or fabric care composition.

[0241] Home care or fabric care active substance bases into which the microcapsules of the present invention can be incorporated can be found in the extensive literature on such products. These formulations do not warrant a detailed description herein and are not exhaustive in any case. One skilled in formulating such consumer products can fully select appropriate components based on their general knowledge and the available literature.

[0242] 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, and these percentages are defined by weight relative to the total weight of the consumer product. Of course, the above concentrations can be adapted according to the desired beneficial effects in each product.

[0243] In the case of the liquid consumer products mentioned below, regarding the "active substance base", it should be understood that the active substance base includes an active material (typically including a surfactant) and water.

[0244] In the case of the solid consumer products mentioned below, regarding the "active substance base", it should be understood that the active substance base includes an active material (typically including a surfactant) and auxiliaries (such as bleaching agents, buffers; builders; soil release or soil suspension polymers; granulated enzyme particles, corrosion inhibitors, defoamers, foam suppressants; dyes, fillers, and mixtures thereof).

[0245] Fabric softener The object of the present invention is A fabric softener active substance base, preferably containing at least one active material selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (ester quaternary ammonium salts), Hamburg ester quaternary salts (HEQ), TEAQ (triethanolamine quaternary salts), silicones and mixtures thereof, and preferably used in an amount included between 85 and 99.95% by weight based on the total weight of the composition, and The microcapsules or microcapsule slurry defined above, preferably in an amount included between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight based on the total weight of the composition, of the microcapsules or microcapsule slurry, and Optionally, free perfume oil and A consumer product in the form of a fabric softener composition containing.

[0246] Liquid detergent The object of the present invention is A liquid detergent active substance base, preferably at least one active material selected from the group consisting of anionic surfactants such as alkylbenzene sulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES), and nonionic surfactants such as alkylamine, alkanolamide, fatty alcohol poly(ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymer, amine oxide, alkyl polyglucoside, alkyl polyglucosamide, and is preferably used in an amount contained between 85 and 99.95% by weight based on the total weight of the composition, the liquid detergent active substance base, and The microcapsules or microcapsule slurry defined above, preferably the microcapsules or microcapsule slurry in an amount 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, and Optionally, a free perfume oil and A consumer product in the form of a liquid detergent composition containing.

[0247] Solid detergent The object of the present invention is A solid detergent active substance base, preferably including at least one active material selected from the group consisting of anionic surfactants such as alkylbenzene sulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES), and nonionic surfactants such as alkylamine, alkanolamide, fatty alcohol poly(ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymer, amine oxide, alkyl polyglucoside, alkyl polyglucosamide, and preferably used in an amount contained between 85 and 99.95% by weight based on the total weight of the composition, the solid detergent active substance base, The microcapsule powder or microcapsule slurry defined above, preferably the microcapsule powder or microcapsule slurry in an amount 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 perfume oil A consumer product in the form of a solid detergent composition containing

[0248] Shampoo / Shower gel The object of the present invention is A shampoo or shower gel active substance base, preferably including at least one active material selected from the group consisting of sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside and amino acid-based surfactants and mixtures thereof, and preferably used in an amount contained between 85 and 99.95% by weight based on the total weight of the composition, the shampoo or shower gel active substance base, The microcapsules or microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, of microcapsules or microcapsule slurry, and Optionally, free perfume oil and A consumer product in the form of a shampoo or shower gel composition containing

[0249] Rinse-off conditioner The object of the present invention is A rinse-off conditioner active substance base, preferably containing at least one active material selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, preferably used in an amount between 85 and 99.95% by weight based on the total weight of the composition, of rinse-off conditioner active substance base, and The microcapsules or microcapsule slurry as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, of microcapsules or microcapsule slurry, and Optionally, free perfume oil and A consumer product in the form of a rinse-off conditioner composition containing

[0250] Solid fragrance booster The object of the present invention is A solid carrier, preferably selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, saccharides such as sucrose, monosaccharides, disaccharides and polysaccharides and derivatives such as starch, cellulose, methylcellulose, ethylcellulose, propylcellulose, polyol / sugar alcohol such as sorbitol, maltitol, xylitol, erythritol and isomalt, PEG, PVP, citric acid or any water-soluble solid acid, fatty alcohol or fatty acid and mixtures thereof, a solid carrier, The microcapsules or microcapsule slurry as defined above, in powder form, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition, of microcapsules or microcapsule slurry, Optionally, a free perfume oil A consumer product in the form of a solid fragrance booster composition comprising.

[0251] Liquid fragrance booster The object of the present invention is An aqueous phase, A surfactant system consisting essentially of one or more nonionic surfactants, having an average HLB of 10 to 14, preferably selected from the group consisting of ethoxylated aliphatic alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono- and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxyl esters, alkyl polyglucosides, amine oxides and combinations thereof, a surfactant system, A linker selected from the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxycarboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants having an HLB of less than 10 and mixtures thereof, The microcapsules or microcapsule slurry as defined above, in the form of a slurry, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, of the microcapsules or microcapsule slurry, and Optionally, a free perfume oil and A consumer product in the form of a liquid fragrance booster composition containing the same.

[0252] Hair coloring The object of the present invention is An oxidation phase containing an oxidizing agent, and an alkaline phase containing an alkalizing agent, a dye precursor and a coupling compound, wherein the dye precursor and the coupling compound form an oxidative hair dye in an amount preferably between 85 and 99.95% by weight, based on the total weight of the composition, in the presence of an oxidizing agent, the oxidation phase and the alkaline phase, and Preferably, in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, of the microcapsules or microcapsule slurry as defined above, and Optionally, a free perfume oil and A consumer product in the form of an oxidative hair coloring composition containing the same.

[0253] Perfume composition According to certain embodiments, the consumer product is 0.1 to 30%, preferably 0.1 to 20% of the microcapsules or microcapsule slurry as defined above, and 0 to 40%, preferably 3 to 40% of perfume, and 20 to 90% by weight, preferably 40 to 90% by weight of ethanol, based on the total weight of the perfume composition and In the form of a perfume composition containing the same.

[0254] Next, the present invention will be further described by way of examples. It will be understood that the claimed invention is not intended to be limited by these examples.

[0255] Examples Example 1 Method for preparing an oligo-lysine mixture First, 180 mL of an aqueous solution of 0.9 M lysine ethyl ester dihydrochloride was prepared, heated to 40 °C, and stirred at 350 rpm. To the lysine ethyl ester solution, 24 mL of an aqueous bromelain solution (initial enzyme activity = 3.73×10 5 CDU / mL) (manufacturer: Enzyme Development Corporation) was added. The reaction solution was stirred at 40 °C for 1.5 hours (pH = 7.8), then heated to 80 °C for 15 minutes, cooled to room temperature, centrifuged or filtered, and freeze-dried or vacuum-dried. The resulting solid, called an oligo-lysine mixture, was used without further purification.

[0256] Example 2 Method for preparing microcapsules according to the present invention Microcapsule A: 1.6 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 60.8 g of water containing 0.8 g of gum arabic (Superstab AA, manufacturer: Nexira) (emulsifier solution). The pH of the emulsifier solution was raised to 10 with 10% NaOH. 16 g of flavor oil A (see Table 1A) containing 0.8 g of TPCl (terephthaloyl chloride, manufacturer: Alfa Aesar) was mixed with the emulsifier solution and homogenized at 15000 rpm for 2 minutes using an Ultraturrax T-25. Then, the resulting oil-in-water emulsion was stirred at 60 °C for 3 hours to obtain a microcapsule slurry.

[0257] The morphology of the capsule slurry was observed under an SEM microscope (see Figure 1).

[0258] [Table 1-1]

[0259] [Table 1-2]

[0260] Microcapsule B 1.6 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 59.8 g of water containing 0.8 g of gum arabic and 1 g of L-lysine (manufacturer: Acros) (emulsifier solution). The pH of the emulsifier solution was raised to 10 with a small amount of 10% NaOH. 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 2 minutes using an Ultraturrax T-25. Then, the formed oil-in-water emulsion was stirred at 60 °C for 3 hours to obtain a microcapsule slurry.

[0261] The morphology of the capsule slurry was observed under an SEM microscope (see Figure 2).

[0262] Microcapsule C An emulsifier solution was prepared by dissolving 0.8 g of gum arabic and 1 g of lysine (manufacturer: Sigma Aldrich) in 59.8 g of water. The pH of the emulsifier solution was raised to 10 with 10% NaOH. 1.6 g of the oligo-lysine mixture (prepared in Example 1) was pulverized into fine powder and dispersed in 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) at 60 °C for 20 minutes. Then, the oil phase was mixed with the emulsifier solution and homogenized at 18,000 rpm for 2 minutes using an Ultraturrax T-25. Then, the formed oil-in-water emulsion was stirred at 60 °C for 3 hours to obtain a microcapsule slurry.

[0263] Microcapsule D 1.6 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 59.8 g of water containing 0.8 g of gum arabic and 1 g of lysine, and labeled as an emulsifier solution. 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) was mixed with the emulsifier solution and homogenized using an Ultraturrax T-25 at 20,000 rpm for 30 seconds and at 10,000 rpm for 1.5 minutes. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours to obtain a microcapsule slurry.

[0264] Microcapsule E1 1.6 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 58.3 g of water containing 1.1 g of potato protein (Solanic® 200 - manufacturer: AVEBE) and 1 g of lysine. A salt solution containing 0.22 g of CaCl 2 2H 2 O in 1 g of water was added to the emulsifier solution. 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) was mixed with the emulsifier solution and homogenized using an Ultraturrax T-25 at 18,000 rpm for 2 minutes. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours and then the temperature was raised to 80 °C for 15 minutes to obtain a microcapsule slurry.

[0265] Microcapsule E2 3.0 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 60.7 g of water containing 1.38 g of potato protein (Solanic® 200 - manufacturer: AVEBE) and 1.9 g of lysine to prepare an emulsifier solution. A salt solution containing 0.28 g of CaCl 2 2H 2 O in 1.25 g of water was added to the emulsifier solution. 30 g of flavor oil B containing 1.5 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized using an Ultraturrax T-25 at 18,000 rpm for 2 minutes. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours and then the temperature was raised to 80 °C for 15 minutes to obtain a microcapsule slurry.

[0266] Microcapsule E3: 3.0 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 62.2 g of water containing 1.38 g of potato protein (Solanic® 200 - manufacturer: AVEBE) and 1.9 g of lysine to prepare an emulsifier solution. 30 g of flavor oil B containing 1.5 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 2 minutes using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours and then the temperature was raised to 80 °C for 15 minutes to obtain a microcapsule slurry.

[0267] Microcapsule E4: 2.0 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 72.8 g of water containing 1.38 g of potato protein (Solanic® 200 - manufacturer: AVEBE) and 1.3 g of lysine to prepare an emulsifier solution. A salt solution containing 0.28 g of CaCl 2 2H 2 O in 1.25 g of water was added to the emulsifier solution. 20 g of flavor oil B containing 1.0 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 2 minutes using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours and then the temperature was raised to 80 °C for 15 minutes to obtain a microcapsule slurry.

[0268] Microcapsule F (control) 0.8 g of lysine monohydrochloride (manufacturer: Acros Organics) was dissolved in 61.6 g of water containing 0.8 g of gum arabic and labeled as an emulsifier solution. The pH of the emulsifier solution was raised to 10 with 10% NaOH. 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) was mixed with the emulsifier solution and homogenized at 15,000 rpm for 2 minutes using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 3 hours.

[0269] The morphology of the capsule slurry was observed under an optical microscope (see Figure 3), indicating that stable capsules were not formed.

[0270] Microcapsule G (control) 0.8 g of lysine monohydrochloride was dissolved in 60.6 g of water containing 0.8 g of gum arabic and 1 g of lysine, and labeled as an emulsifier solution. The pH of the emulsifier solution was raised to 10 with 10% NaOH. 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 2 minutes using an Ultraturrax T-25. Then, the formed oil-in-water emulsion was stirred at 60°C for 3 hours.

[0271] Microcapsule H 2.6 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 54.6 g of water containing 1.24 g of potato protein (Solanic® 200 - manufacturer: AVEBE) and 1.72 g of L-lysine (manufacturer: ACROS) (emulsifier solution). 0.25 g of calcium chloride dihydrate was dissolved in 1.13 g of water to form a salt solution, which was then mixed with the emulsifier solution. 27 g of flavor oil B containing 1.35 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 30 seconds using an Ultraturrax T-25. Then, the formed oil-in-water emulsion was stirred at 60°C for 2 hours to obtain a microcapsule slurry.

[0272] Microcapsule I 2.7 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 55 g of water containing 0.9 g of gum arabic and 1.73 g of L-lysine (manufacturer: ACROS) (emulsifier solution). 0.25 g of calcium chloride dihydrate was dissolved in 1.13 g of water to form a salt solution, which was then mixed with the emulsifier solution. 27 g of flavor oil B containing 1.35 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 30 seconds using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours to obtain a microcapsule slurry.

[0273] Microcapsule J (control): Microcapsules prepared with epsilon-polylysine 1.1 g of ε-polylysine was dissolved in 61.3 g of water containing 0.8 g of gum arabic (emulsifier solution). The pH of the emulsifier solution was adjusted to 10 with 10% NaOH. 16 g of flavor oil A containing 0.8 g of TPCl (see Table 1A) was mixed with the emulsifier solution and homogenized at 15,000 rpm for 2 minutes using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2.5 hours.

[0274] For the slurry with phase separation and gelation, intense aggregation was observed.

[0275] Microcapsule K 2.7 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 54.6 g of water containing 1.24 g of potato protein (Solanic® 200 - manufacturer: AVEBE) and 1.72 g of lysine, labeled as the emulsifier solution. 1.38 g of an aqueous zinc chloride solution (18.1%) was added to the emulsifier solution. 27 g of flavor oil B containing 1.35 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 30 seconds using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours, then heated to 80 °C for 15 minutes, and then cooled to room temperature to obtain a microcapsule slurry.

[0276] Microcapsule L 2.75 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 54 g of water containing 0.9 g of potato protein (Solanic® 200 - manufacturer: AVEBE), 0.9 g of gum arabic, and 1.72 g of lysine, and labeled as an emulsifier solution. 1.38 g of an aqueous zinc chloride solution (18.1%) was added to the emulsifier solution. 27 g of flavor oil B containing 1.35 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 30 seconds using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours, then heated to 80 °C for 15 minutes, and then cooled to room temperature to obtain a microcapsule slurry.

[0277] Microcapsule M 3.7 g of the oligo-lysine mixture (prepared in Example 1) was dissolved in 55.3 g of water containing 1.24 g of potato protein (Solanic® 200 - manufacturer: AVEBE), and labeled as an emulsifier solution. 1.38 g of an aqueous zinc chloride solution (18.1%) was added to the emulsifier solution. 27 g of flavor oil B containing 1.35 g of TPCl (see Table 1B) was mixed with the emulsifier solution and homogenized at 18,000 rpm for 30 seconds using an Ultraturrax T-25. Subsequently, the formed oil-in-water emulsion was stirred at 60 °C for 2 hours, then heated to 80 °C for 15 minutes, and then cooled to room temperature to obtain a microcapsule slurry.

[0278] Example 3 Stability performance The microcapsules of the present invention are dispersed in the fabric softener composition described in Table 2 to obtain a 0.2% encapsulated flavor oil concentration.

[0279] [Table 2]

[0280] Weigh 2 g of the sample (the base containing the capsules) into a 20 mL vial. Add 10 mL of the extraction solvent isooctane containing the internal standard 1,4-dibromobenzene with an accurately known concentration of approximately 90 ng / μL to the vial. Shake at 40 RPM for 45 minutes to extract the free fragrance. Remove the solvent phase.

[0281] To measure the leakage of the base, use an Agilent GCFID7890A, set the injector to 250 °C, use helium as the carrier gas at a flow rate of 1 mL / min, program the oven temperature from 120 °C, hold for 5 minutes, increase to 170 °C at 10 °C / min, then increase to 220 °C at 25 °C / min, and then increase to 260 °C at 25 °C / min. Apply a subsequent run at 260 °C to end the measurement.

[0282] Prepare calibration solutions with fragrance oils at 100, 300, and 600 ng / μL in isooctane. It is important that the fragrance oil used to create the calibration curve is from the same batch as that used to manufacture the microcapsules.

[0283]

Table 3

[0284] Example 4 Functional performance Dilute the microcapsule slurry 100-fold using deionized water, then add 100 μL of the diluted slurry to a circle (d = 2.5 cm) on a blotting paper (7.5×6 cm). Prepare a free oil control sample by diluting with a 10% ethanol / water mixture to the same fragrance oil concentration as the diluted microcapsule slurry oil concentration, and then add 100 μL of the diluted free oil sample to a circle on the blotting paper (7.5×6 cm). Dry the samples in air at room temperature for 16 hours. The sensory test was performed by smelling each sample before and after rubbing with a gloved fingertip.

[0285] From Figure 4, it can be concluded that the microcapsules of the present invention can hold the perfume oil well and exhibit a burst release (pop effect) of the fragrance oil during friction.

[0286] Example 5 Biodegradability of the microcapsules according to the present invention Shell extraction (the following method disclosed in Gasparini and all in Molecules 2020, 25, 718) Microcapsule slurries E4 and H were lyophilized. The recovered solid was ground for 30 seconds using an IKA tube - mill control grinder. The resulting paste (fragrance oil + polymer shell) was suspended in 300 mL of ethyl acetate, and the mixture was stirred at room temperature for 1 hour. The solid was collected by filtration under vacuum using a Gooch filtering crucible (porosity 4). This extraction step was repeated 5 times to remove the maximum amount of fragrance oil from the shell. The powder was dried under vacuum (10 mBar) at 50 °C until the weight of the polymer, monitored by weighing, became constant. The obtained powder was ground for 1 minute and 30 seconds using an IKA tube - mill control grinder, suspended in Di water (0.5% w / w), and stirred at 300 RPM for 24 hours at room temperature. The water was removed by filtration under vacuum using a Gooch filtering crucible (porosity 4), and the powder was dried at room temperature for 2.5 days and then under vacuum (10 mBar) at 50 °C overnight. Finally, the obtained powder was ground for 1 minute and 30 seconds using an IKA tube - mill control grinder and extracted 5 more times with ethyl acetate as described above. The final powder was dried under vacuum (10 mBar) at 50 °C overnight. To ensure complete removal of the fragrance, the sample was analyzed by GC pyrolysis and sent for biodegradation measurement according to the OECD 301F method.

[0287] The biodegradability of the shells of microcapsules E4 and H exceeded 50% after a 60 - day test.

[0288] Example 6 Liquid detergent composition Disperse sufficient amounts of the microcapsule slurries A - E, H - M of the present invention in the liquid detergent base described below to obtain a concentration of encapsulated perfume oil of 0.22%.

[0289]

Table 4

[0290] Example 7 Rinse - off conditioner Incorporate sufficient amounts of the microcapsule slurries A - E, H - M of the present invention into the rinse - off base at the required dosage (equivalent to 0.5% encapsulated perfume oil) (see below).

[0291]

Table 5

[0292] Mix the components of Phase A until a homogeneous mixture is obtained. Completely dissolve the tyrosin. Then heat the mixture to 70 - 75°C. Combine the components of Phase B and melt them at 70 - 75°C. Then add the components of Phase B to Phase A while stirring well and continue mixing until cooled to 60°C. Then, stir the components of Phase C and add them while continuing to mix until the mixture is cooled to 40°C. Adjust the pH with a citric acid solution until the pH reaches 3.5 - 4.0.

[0293] Example 8 Preparation of spray - dried microcapsules Prepare emulsions 1 - 5 having the following components.

[0294]

Table 6

[0295] Constituent components of the polymer matrix (maltodextrin and capsul (商標)Or capsul(trademark), citric acid and tripotassium citrate) are added to water at 45 - 50°C until completely dissolved.

[0296] In emulsion 4, free fragrance C is added to the aqueous phase.

[0297] The obtained mixture is added with microcapsule slurry. Then, the obtained mixture is gently mixed at 25°C (room temperature).

[0298] Granulation powders 1 - 5 are prepared by spray - drying emulsions A - E using a Sodeva Spray Dryer (manufacturer, France), setting the air inlet temperature at 215°C and the throughput at 500 ml per hour. The air outlet temperature is 105°C. The emulsion before atomization is at ambient temperature.

[0299] Example 9 Liquid fragrance booster composition Weigh sufficient amounts of microcapsule slurries A - E, H - M, mix them in the liquid fragrance booster, and add 0.2% equivalent of fragrance.

[0300]

Table 7

[0301] Prepare different ring - gel compositions (compositions 1 - 6) according to the following protocol.

[0302] In the first step, the aqueous phase (water), the solvent (propylene glycol) if present, and the surfactant are mixed together at room temperature while stirring with a magnetic stirrer at 300 rpm for 5 minutes.

[0303] In the second step, the linker is dissolved in the hydrophobic active ingredient (fragrance) at room temperature while stirring with a magnetic stirrer at 300 rpm. The obtained mixture is mixed for 5 minutes.

[0304] Next, mix the aqueous and oil phases together at room temperature for 5 minutes to form a transparent or milky white ringing gel.

[0305] Example 10 Powder detergent composition Weigh a sufficient amount of granules 1 - 5 and mix them in the powder detergent composition, and add 0.2% equivalent of fragrance.

[0306] [Table 8]

[0307] Example 11 Concentrated multi - purpose cleaner composition Weigh a sufficient amount of microcapsule slurries A - E, H, I and mix them in the concentrated multi - purpose cleaner composition, and add 0.2% equivalent of fragrance.

[0308] [Table 9]

[0309] Mix all the components together, and then dilute the mixture to 100% with water.

[0310] Example 12 Solid fragrance booster composition Weigh a sufficient amount of microcapsules in dry form and mix them with the solid fragrance booster composition, and add 0.2% equivalent of fragrance.

[0311] [Table 10]

[0312] [Table 11]

[0313] Example 13 Shampoo composition Weigh sufficient amounts of microcapsule slurries A - E, H - M, mix them in the shampoo composition, and add 0.2% equivalent of fragrance.

[0314]

Table 12

[0315] Disperse polyquaternium - 10 in water. Mix the remaining components of Phase A separately by sequentially adding them while mixing well after each adjustment. Then, add this preliminary mixture to the polyquaternium - 10 dispersion and mix for 5 minutes. Next, add Phase B and the preliminary mixed Phase C (heated to melt Monomuls 90L - 12 in Texapon NSO IS). Mix the mixture well. Then, add Phase D and Phase E while stirring. Adjust the pH with citric acid solution until the pH reaches 5.5 - 6.0.

[0316] Example 14 Shampoo composition Weigh sufficient amounts of microcapsule slurries A - E, H - M, mix them in the shampoo composition, and add 0.2% equivalent of fragrance.

[0317]

Table 13

[0318] Add a preliminary mixture containing guar hydroxypropyltrimonium chloride and polyquaternium - 10 to water and sodium EDTA tetrasodium while mixing. If the mixture is homogeneous, add NaOH. Then, add the Phase C components and heat the mixture to 75°C. Add the Phase D components and mix until homogeneous. Stop heating and let the temperature of the mixture drop to room temperature. At 45°C, adjust the final viscosity with 25% NaCl solution while mixing the components of Phase E, and adjust the pH to 5.5 - 6 with 10% NaOH solution.

[0319] Example 15 Anhydrous Composition of Antiperspirant Spray Weigh sufficient amounts of microcapsule slurries Microcapsule Slurries A - E, H - M, mix them in the anhydrous composition of antiperspirant spray, and add 0.2% equivalent of fragrance.

[0320]

Table 14

[0321] Using a high - speed stirrer, add silica and quaternium - 18 - hectorite to a mixture of isopropyl myristate and cyclomethicone. Once fully swollen, add aluminum chlorohydrate little by little with stirring until the mixture becomes homogeneous and there are no lumps. Fill the aerosol can with 25% suspension and 75% suspension of propane / butane (2.5 bar).

[0322] Example 16 Emulsion Composition of Antiperspirant Spray Weigh sufficient amounts of microcapsule slurries Microcapsule Slurries A - E, H - M, mix them in the emulsion composition of antiperspirant spray, and add 0.2% equivalent of fragrance.

[0323]

Table 15

[0324] 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. Pour the components of Part B into A little by little while stirring continuously. Stir the mixture well until it reaches room temperature. Then add the components of Part C. Mix the emulsion and introduce it into the aerosol can. Compress and add the propellant.

[0325] Aerosol Filling: 30% Emulsion: 70% Propane / Butane 2.5 bar

[0326] Example 17 Deodorant spray composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A to E, H, and I, mix them in an antiperspirant deodorant spray composition, and add 0.2% equivalent of fragrance.

[0327] [Table 16]

[0328] Mix and dissolve all the components in the order of the above table. Then, fill an aerosol can, compress it, and add a propellant (aerosol filling: 40% active solution, 60% propane / butane, 2.5 bar).

[0329] Example 18 Antiperspirant roll-on emulsion composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A to E, H to M, mix them in an antiperspirant roll-on emulsion composition, and add 0.2% equivalent of fragrance.

[0330] [Table 17]

[0331] Heat Part A and Part B separately to 75°C, add Part A to Part B with stirring, and homogenize the mixture for 10 minutes. Then, cool the mixture with stirring, and slowly add Part C when the mixture reaches 45°C and Part D when the mixture reaches 35°C while stirring. Then, cool the mixture to room temperature.

[0332] Example 19 Antiperspirant roll-on composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A to E, H to M, mix them in an antiperspirant roll-on composition, and add 0.2% equivalent of fragrance.

[0333] [Table 18]

[0334] Mix the components of Part B in a container, then add the components of Part A. Then, dissolve Part C in Parts A and B. Add 1 part of Cremophor RH40 to 1 part of fragrance and add it with thorough mixing.

[0335] Example 20 Antiperspirant roll-on composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix them in an antiperspirant roll-on emulsion composition, and add 0.2% equivalent of fragrance.

[0336] [Table 19]

[0337] Prepare Part A by sprinkling hydroxyethyl cellulose into water little by little while stirring rapidly with a turbine, and continue stirring until the hydroxyethyl cellulose is completely swollen and a clear gel is obtained. Then, pour Part B into Part A little by little while continuing to stir until the whole becomes homogeneous. Add Part C.

[0338] Example 21 Deodorant pump without alcohol formulation Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix them in the following composition, and add 0.2% equivalent of fragrance.

[0339] [Table 20]

[0340] Mix all the components in the order shown in the table and heat the mixture slightly to dissolve cetyl lactate.

[0341] Example 22 Deodorant pump with alcohol formulation Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix in the following composition, and add 0.2% equivalent of fragrance.

[0342]

Table 21

[0343] Mix the components from Part B together. Dissolve the components of Part A in the order shown in the table and pour into Part B.

[0344] Example 23 Deodorant stick without alcohol formulation Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix in the following composition, and add 0.2% equivalent of fragrance.

[0345]

Table 22

[0346] Weigh all the components of Part A, heat to 70 - 75°C. After mixing and heating the other Part A components, add Ceteareth - 25. After Ceteareth - 25 is dissolved, add stearic acid. Prepare Part B by dissolving triclosan in 1,2 - propylene glycol. Add evaporated water. Slowly pour Part B into Part A under mixing. Place in a plastic bag in a bucket for storage and seal after cooling. Fill the mold at about 70°C.

[0347] Example 24 Antiperspirant stick Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix in the following composition, and add 0.2% equivalent of fragrance.

[0348]

Table 23

[0349] Weigh all the components of Part A, heat to 70 - 75 °C, and mix well. Disperse the components of Part B in Part A. Mix the mixture and place it in a tick at 65 °C.

[0350] Example 25 Day cream Weigh sufficient amounts of microcapsule slurries A - E, H - M, mix them in the following composition, and add 0.2% equivalent of fragrance.

[0351]

Table 24

[0352] Example 26 Talc formulation Weigh sufficient amounts of granules 1 - 5, introduce them into a standard talc base: 100% talc, very slight characteristic odor, white powder, manufacturer: LUZENAC, mix them, and add 0.2% equivalent of fragrance.

[0353] Example 27 Shower gel composition Weigh sufficient amounts of microcapsule slurries A - E, H - M, mix them in the following composition, and add 0.2% equivalent of fragrance.

[0354]

Table 25

[0355] Mix the components and adjust the pH to 6 - 6.3 (viscosity: 4500 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0356] Example 28 Shower gel composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix them in the following composition, and add 0.2% equivalent of fragrance.

[0357] [Table 26]

[0358] Mix the components and adjust the pH to 4.5 (viscosity: 3000 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0359] Example 29 Shower gel composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix them in the following composition, and add 0.2% equivalent of fragrance.

[0360] [Table 27]

[0361] Mix the components and adjust the pH to 4.5 (viscosity: 4000 cPo + / - 1500 cPo (Brookfield RV / Spindle #4 / 20 RPM)).

[0362] Example 30 Hair coloring composition Weigh sufficient amounts of microcapsule slurries Microcapsule slurries A - E, H - M, mix them with alkali base A, and add 0.2% equivalent of fragrance.

[0363] Next, mix 2 g of alkali base A with 2 g of oxidizing agent B.

[0364] [Table 28]

[0365] Procedure: All components of Phase A were mixed and heated to 75 °C.

[0366] All components of Phase B were combined and melted at 70 - 75 °C.

[0367] Phase B was added while thoroughly stirring into Phase A (both at 70 - 75 °C).

[0368] Phase C was added and mixing was continued until cooled to room temperature.

[0369] While mixing, the components of Phase D were added at room temperature.

[0370] The remaining components of Phase C were added with stirring.

[0371]

Table 29

[0372] Procedure: All components of Phase A were mixed and heated to 75 °C.

[0373] All components of Phase B were combined and melted at 70 - 75 °C.

[0374] Phase B was added while thoroughly stirring into Phase A (both at 70 - 75 °C), and mixing was continued until cooled to room temperature.

[0375] While mixing, the components of Phase C were added at room temperature.

[0376] Example 31 Dishwashing Detergent for Hand Washing Weigh sufficient amounts of microcapsule slurries Microcapsule Slurries A - E, H - M and mix them in the following composition, and add 0.2% equivalent of fragrance.

[0377]

Table 30

[0378] Mix water containing sodium hydroxide with diethanolamide. Add LAS. After neutralizing the LAS, add the remaining components. Check the pH (= 7 - 8) and adjust if necessary.

[0379] Example 32 Unit - dose formulation Weigh a sufficient amount of the exemplified microcapsules and mix them in the unit - dose formulation to add 0.2% equivalent of fragrance.

[0380] The unit - dose formulation can be included in a PVOH (polyvinyl alcohol) film.

[0381] [Table 31]

[0382] Example 33 Toothpaste formulation Weigh a sufficient amount of microcapsule slurry R (equivalent to microcapsule slurries A - E, H, I of the microcapsules except that the fragrance is encapsulated instead of the perfume) and mix it in the following composition to add 0.2% equivalent of fragrance.

[0383] [Table 32]

[0384] Example 34 Dicalcium phosphate - based toothpaste formulation Weigh a sufficient amount of microcapsule slurry R (equivalent to microcapsule slurries A - E, H, I of the microcapsules except that the fragrance is encapsulated instead of the perfume) and mix it in the following composition to add 0.2% equivalent of fragrance.

[0385] [Table 33]

[0386] Example 35 Mouse Wash Alcohol-Free Formulation Weigh a sufficient amount of Microcapsule Slurry R (equivalent to Microcapsule Slurries A - E, H, I of the microcapsules, except that the fragrance is encapsulated instead of the perfume), and mix it in the following composition to add 0.2% equivalent of fragrance.

[0387] [Table 34]

[0388] Example 36 Mouse Wash Formulation Weigh a sufficient amount of Microcapsule Slurry R (equivalent to Microcapsule Slurries A - E, H, I of the microcapsules, except that the fragrance is encapsulated instead of the perfume), and mix it in the following composition to add 0.2% equivalent of fragrance.

[0389] [Table 35]

Claims

1. (i) a core comprising a hydrophobic material, preferably a perfume oil; (ii) a polyamide shell comprising the reaction product between at least one acyl chloride and at least one oligopeptide; 1. A polyamide core-shell microcapsule comprising:

2. The acyl chloride has the following formula (I): 【Chemistry 1】 wherein n is an integer ranging from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4; In the formula, X represents an (n+1)-valent C optionally containing at least one group selected from the following (i) to (xi): ２ ~C ４５ is a hydrocarbon group, 【Chemistry 2】 2. The microcapsule of claim 1, wherein R is a hydrogen atom or an alkyl group, preferably a hydrogen atom.

3. 3. The microcapsules of claim 2, wherein the acyl chloride is a diacyl chloride, preferably selected from the group consisting of terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, adipoyl chloride, sebacoyl chloride, succinyl chloride, glutaryl chloride, pimeloyl chloride, dodecandioyl dichloride, suberoyl chloride, azelaoyl chloride, malonyl chloride, fumaryl chloride, oxyallyl chloride, 4,4'-oxybis(benzoyl chloride), 2,2'-oxydiacetyl chloride, 4,4'-biphenyldicarbonyl chloride, azobenzene-4,4'-dicarbonyl dichloride, 2,5-furandicarbonyl dichloride, and mixtures thereof.

4. 2. Microcapsules according to claim 1, wherein the oligopeptide has an average molecular weight of less than 4000 g / mol, preferably up to 2000 g / mol, more preferably between 200 and 1000 g / mol.

5. The microcapsule of claim 1 , wherein the hydrophobic material comprises a fragrance.

6. 2. The microcapsule of claim 1, wherein the oligopeptide is selected from the group consisting of oligo-lysine, oligo-arginine, oligo-histidine, oligo-tryptophan, oligo-serine, oligo-glutamine, oligo-threonine, oligo-asparagine, oligo-ornithine.

7. 7. The microcapsule of claim 6, wherein the oligopeptide is oligo-lysine.

8. 2. The microcapsule of claim 1, wherein the polyamide shell comprises the reaction product between an oligo-lysine and terephthaloyl chloride, or the polyamide shell comprises the reaction product between an oligo-lysine and isophthaloyl chloride, or the polyamide shell comprises the reaction product between an oligo-lysine and phthaloyl chloride.

9. 2. Microcapsules according to claim 1, wherein the molar ratio of average amino groups from the oligopeptide to acyl chloride groups from the acyl chloride is from 0.05:1 to 65:1, preferably from 0.1:1 to 10:

1.

10. 1. A method for preparing a core-shell polyamide slurry, comprising the steps of: a) dispersing an oil phase comprising a hydrophobic material and at least one acyl chloride in a dispersed phase to form a two-phase dispersion; b) carrying out a hardening step to form microcapsules in the form of a slurry; Including, At least one stabilizer is added to the oil phase and / or the dispersed phase; A method wherein at least one oligopeptide is added to said dispersed phase and / or said oil phase and / or said two-phase dispersion.

11. 11. The method of claim 10, wherein at least one salt is added to the dispersed phase and / or the oil phase and / or the two-phase dispersion.

12. 11. The method of claim 10, wherein the stabilizer is selected from the group consisting of inorganic particles, polymeric emulsifiers such as polysaccharides, proteins, glycoproteins, and mixtures thereof.

13. 11. The method according to claim 10, wherein the acyl chloride is used at a concentration of 0.1% to 50% by weight, preferably 0.5 to 15% by weight, based on the oil phase.

14. 11. The method of claim 10, wherein an amino acid preferably selected in the group consisting of lysine, arginine, histidine, tryptophan, ornithine, glutamine, asparagine, citrulline and mixtures thereof is added to the dispersed phase and / or the two-phase dispersion.

15. A consumer product, preferably in the form of a home or personal or fabric care product, comprising microcapsules according to any one of claims 1 to 9.

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