Hybrid microcapsules

Abstract

The invention relates to a novel method for preparing mixed microcapsules. A hybrid microcapsule is also an object of the invention. Perfuming compositions and consumer products comprising said microcapsules, in particular perfumed consumer products in the form of home care or personal care products, are also part of the invention.

Description

Technical Field

[0001] The present invention relates to a new process for preparing hybrid microcapsules. Hybrid microcapsules are also an object of the present invention. Perfuming compositions and consumer products, in particular perfumed consumer products in the form of home care or personal care products, comprising said microcapsules are also part of the present invention. Background Art

[0002] One of the problems facing the perfume industry is that the olfactory benefits provided by odorous compounds are lost relatively quickly due to their volatility, especially the volatility of "top notes". In order to adjust the release rate of volatiles, a delivery system (such as microcapsules containing fragrances) is needed to protect and release the core payload when triggered. For these systems, a key requirement of the industry is to be able to remain suspended in a challenging base material without physical decomposition or degradation. This is called the stability of the delivery system. For example, aromatic personal and household cleaners containing high levels of aggressive surfactant detergents are very challenging for the stability of microcapsules.

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

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

[0005] The present invention proposes a solution to the above problems by providing novel hybrid microcapsules and a method for preparing the same. Summary of the invention

[0006] The first object of the present invention is a method for preparing a microcapsule slurry, comprising the following steps:

[0007] 1) suspending the coacervate particles in a solvent to form a dispersed phase;

[0008] 2) mixing at least one multifunctional monomer with a hydrophobic material to form an oil phase;

[0009] 3) The oil phase is added to the dispersed phase and they are mixed to form a two-phase Pickering emulsion under conditions that allow the formation of a microcapsule slurry by interfacial polymerization.

[0010] A second object of the present invention is a microcapsule slurry obtainable by the process according to any one of the preceding claims.

[0011] The present invention also relates to a perfumed consumer product and a flavoured (flavoured) edible product comprising the microcapsule slurry or microcapsules as defined above. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 : Schematic diagram of Pickering emulsion formation when coacervate particles are used to stabilize the oil phase.

[0013] Figure 2 : represents a micrograph of microcapsules prepared by the method of the present invention.

[0014] Figure 3 : indicates the preparation of coacervate particles using two polymer solutions (with opposite charges) using the transient nanoprecipitation process (FNP). DETAILED DESCRIPTION

[0015] Unless otherwise indicated, percentages (%) refer to weight percent of the composition.

[0016] By "active ingredient" is meant a single compound or a combination of ingredients.

[0017] By "flavor oil or flavoring (flavor) oil" it is meant a single flavoring or flavoring compound, or a mixture of several flavoring or flavoring compounds.

[0018] By “consumer product” or “final product,” we mean a finished product that is ready for distribution, sale, and use by consumers.

[0019] For the sake of clarity, the expression "dispersion" in the present invention refers to a system in which particles are dispersed in a continuous phase of different composition, and it specifically includes a suspension or an emulsion.

[0020] In the present invention, "microcapsule" or similar expressions refer to core-shell microcapsules having a particle size distribution in the micrometer range (e.g., an average diameter of about 1 to 3000 micrometers, preferably 1 to 500 micrometers, more preferably 5 to 50 micrometers), and comprising an outer solid polymer shell and an inner continuous oil phase surrounded by the outer shell.

[0021] By "microcapsule size" or "particle size" is meant the volume mean diameter (D[4,3]) of the relevant capsules / particles, capsule / particle suspension, obtained by laser light scattering of a diluted sample in a Malvern Mastersizer 3000.

[0022] Therefore, the microcapsules are defined as "hybrid" or "composite" depending on the nature of the shell, which consists of a polymer shell formed by interfacial polymerization in which the coacervate particles are embedded. The coacervate particles are used to stabilize the Pickering emulsion during the process.

[0023] By "microcapsule slurry" it is meant microcapsules dispersed in a liquid. According to one embodiment, the slurry is an aqueous slurry, ie the microcapsules are dispersed in an aqueous phase.

[0024] By "multifunctional monomer" is meant a molecule which, as a unit, chemically reacts or combines to form a polymer or supramolecular polymer. The multifunctional monomer of the present invention has at least two functional groups which are capable of reacting or combining with functional groups of another component and / or are capable of polymerizing to form a polymer shell.

[0025] It has been found that hybrid microcapsules can be obtained with overall good performance in challenging bases.

[0026] Method for preparing microcapsules

[0027] The first object of the present invention is a method for preparing a microcapsule slurry, comprising the following steps:

[0028] 1) suspending the coacervate particles in a solvent to form a dispersed phase;

[0029] 2) mixing at least one multifunctional monomer with a hydrophobic material to form an oil phase;

[0030] 3) The oil phase is added to the dispersed phase and they are mixed to form a two-phase Pickering emulsion under conditions that allow the formation of a microcapsule slurry by interfacial polymerization.

[0031] According to one embodiment, the method for preparing a microcapsule slurry comprises the following steps:

[0032] 1) suspending the coacervate particles in water to form an aqueous phase;

[0033] 2) mixing at least one multifunctional monomer with a hydrophobic material to form an oil phase;

[0034] 3) The oil phase is added to the water phase and they are mixed to form an oil-in-water Pickering emulsion under conditions that allow the formation of a microcapsule slurry by interfacial polymerization.

[0035] According to one embodiment, the solvent comprises water, preferably consists of water.

[0036] According to one embodiment, the dispersed phase is an aqueous phase.

[0037] According to one embodiment, the two-phase dispersion is an oil-in-water emulsion.

[0038] According to one embodiment, the solvent comprises water and an alcohol, such as glycerol, 1,4-butanediol, ethylene glycol, and mixtures thereof.

[0039] According to one embodiment, the second multifunctional monomer is added in the aqueous phase in step 1) and / or in the Pickering emulsion in step 3).

[0040] The second multifunctional monomer may be selected from melamine-based resins or urea-based resins.

[0041] According to one embodiment, the present invention combines two processes, namely the formation of coacervate particles prepared by a transient nanoprecipitation (FNP) process, and an interfacial polymerization (or interfacial reaction) process, to obtain microcapsules with excellent properties.

[0042] The method of the present invention comprises forming a Pickering emulsion, which is then further subjected to interfacial polymerization (or interfacial reaction).

[0043] Without being bound by theory, it is believed that the Pickering emulsion determines the morphology and surface properties (size, density, zeta potential, stiffness) of the membrane, while the interfacial reactions determine the permeability and stiffness of the capsule.

[0044] Figure 1 Represents the formation of a Pickering emulsion when coacervate particles are used as colloidal stabilizers to stabilize oil droplets.

[0045] According to one particular embodiment, a polymeric emulsifier is added to the aqueous phase in step 1).

[0046] By "polymer emulsifier" is meant an emulsifier that has both polar groups with affinity for water (hydrophilic) and non-polar groups with affinity for oil (lipophilic). The hydrophilic portion is soluble in the water phase and the hydrophobic portion is soluble in the oil phase, forming a film around the droplets. The coacervate particles used in the present invention are not polymer emulsifiers. Coacervate particles are colloidal stabilizers.

[0047] Such optional polymeric emulsifiers can help stabilize the oil droplets in the presence of coacervate particles. The polymeric emulsifier can be an ionic or nonionic surfactant. As non-limiting examples, nonionic polymers include polyvinyl alcohol, gum arabic, cellulose derivatives such as hydroxyethyl cellulose, polyethylene oxide, copolymers of polyethylene oxide with polyethylene oxide or polypropylene oxide, copolymers of alkyl acrylates and N-vinyl pyrrolidone, and nonionic polysaccharides. Ionic polymers include copolymers of acrylamide and acrylic acid, acidic anionic surfactants (e.g., sodium lauryl sulfate), acrylic acid copolymers with sulfonate groups, copolymers of vinyl ethers and maleic anhydride, and ionic polysaccharides.

[0048] According to one embodiment, no polymer emulsifier is added at any stage of the process.

[0049] In the first step of the process, the coacervate particles are dispersed in a solvent, preferably in an aqueous phase, preferably at a pH of 2 to 8. Typically, this is done under ultrasonic or high mechanical agitation conditions. In the second step, at least one multifunctional monomer is dissolved in a hydrophobic material (e.g., a fragrance oil or flavor oil) to form an oil phase, which is then added to a dispersed phase (typically an aqueous phase) to form a Pickering emulsion, preferably with an average droplet size of 1 to 3000 microns, more preferably 1 to 500 microns, and even more preferably 5 to 50 microns. For example, a high-speed mechanical disperser or an ultrasonic disperser is used at room temperature to prepare a two-phase Pickering dispersion (typically an oil-in-water Pickering emulsion).

[0050] Once the Pickering emulsion is formed, the pH is preferably adjusted to a value above 8.5, and preferably not above 11. However, this step may be omitted.

[0051] The interfacial polymerization is generally performed at a temperature of 50° C. to 80° C. for 2 to 40 hours under stirring to complete the reaction and form microcapsules in the form of a slurry.

[0052] The morphology of the microcapsules of the present invention can be either core-shell or matrix-type. According to one embodiment, they are core-shell. In this case, the microcapsules comprise a core based on a hydrophobic active ingredient (usually a fragrance oil or flavor oil) and a polymer shell comprising coacervate particles embedded in the polymer shell.

[0053] oil phase

[0054] According to the present invention, at least one multifunctional monomer is mixed with a hydrophobic material to form an oil phase.

[0055] According to one embodiment, the content of the multifunctional monomer used in the method of the present invention is 0.1 to 40 wt %, preferably 0.1 to 30 wt %, more preferably 0.2 to 20 wt %, based on the total amount of the oil phase.

[0056] According to one embodiment, the multifunctional monomer is selected from the group consisting of at least one isocyanate, anhydride or maleic anhydride, acid chloride, epoxide, (meth)acrylate monomer, alkoxysilane and mixtures thereof.

[0057] Suitable polyfunctional isocyanates for use in accordance with the present invention have at least two or three isocyanate functional groups and include aromatic isocyanates, aliphatic isocyanates, and mixtures thereof.

[0058] According to one particular embodiment, the polyfunctional isocyanate comprises at least 3 but may comprise up to 6, or even only 4 isocyanate functional groups, and the oil phase is substantially free of diisocyanates.

[0059] According to one particular embodiment, triisocyanates (3 isocyanate functional groups) are used.

[0060] According to one embodiment, the polyfunctional isocyanate is an aromatic polyfunctional isocyanate.

[0061] The term "aromatic polyfunctional isocyanate" is intended herein to encompass any polyfunctional isocyanate containing an aromatic moiety. Preferably, it contains a phenyl, toluoyl, xylyl, naphthyl or diphenyl moiety. More preferably, a toluoyl or xylyl moiety. Preferred aromatic polyfunctional isocyanates are biuret, polyisocyanurate and trimethylolpropane adducts of diisocyanates, more preferably containing one of the above-mentioned specific aromatic moieties. More preferably, the aromatic polyfunctional isocyanate is a polyisocyanurate of toluene diisocyanate (available from Bayer under the trade name RC), trimethylolpropane adduct of toluene diisocyanate (available from Bayer under the trade name L75), trimethylolpropane adduct of xylylene diisocyanate (available from Mitsui Chemicals under the trade name In a most preferred embodiment, the aromatic polyfunctional isocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

[0062] According to another embodiment, the polyfunctional isocyanate is an aliphatic polyfunctional isocyanate. The term "aliphatic polyfunctional isocyanate" is defined as a polyfunctional isocyanate that does not contain any aromatic moieties. Preferred aliphatic polyfunctional isocyanates are trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate (available from Mitsui Chemicals) or biuret of hexamethylene diisocyanate (available from Bayer under the trade name N 100 is commercially available), among which the biuret of hexamethylene diisocyanate is more preferred.

[0063] According to another embodiment, the at least one polyfunctional isocyanate is in the form of a mixture of at least one aliphatic functional polyisocyanate and at least one aromatic polyfunctional isocyanate, both containing at least two or three isocyanate functional groups, such as a mixture of a biuret of hexamethylene diisocyanate with a trimethylolpropane adduct of xylylene diisocyanate, a mixture of a biuret of hexamethylene diisocyanate with a polyisocyanurate of toluene diisocyanate, and a mixture of a biuret of hexamethylene diisocyanate with a trimethylolpropane adduct of toluene diisocyanate. Most preferably, it is a mixture of a biuret of hexamethylene diisocyanate with a trimethylolpropane adduct of xylylene diisocyanate.

[0064] According to one embodiment, the multifunctional monomer is an acid chloride.

[0065] According to a particular embodiment, the acid chloride conforms to the following formula (I),

[0066]

[0067] wherein n is an integer from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4, and

[0068] Where X is a (n+1) valent C2 to C 45 A hydrocarbon group, optionally comprising at least one group selected from (i) to (xi), in particular a group selected from (i) to (vi)

[0069]

[0070] wherein R is a hydrogen atom or an alkyl group, such as a methyl group or an ethyl group, preferably a hydrogen atom.

[0071] It is understood that by "...hydrocarbyl..." it is meant that the group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i.e. a straight or branched saturated hydrocarbon (e.g. an alkyl), a straight or branched unsaturated hydrocarbon (e.g. an alkenyl or alkynyl), a saturated cyclic hydrocarbon (e.g. a cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g. a cycloalkenyl or cycloalkynyl), or may be in the form of an aromatic hydrocarbon, i.e. an aryl, or may also be in the form of a mixture of the types of groups mentioned, e.g. unless specifically limited to only one type mentioned, a particular group may contain straight chain alkyl, branched alkenyl (e.g. with one or more carbon-carbon double bonds), (poly)cycloalkyl and aryl moieties. Similarly, in all embodiments of the present invention, when referring to a group in the form of more than one type of topology (e.g. straight chain, cyclic or branched) and / or saturation or unsaturation (e.g. alkyl, aromatic or alkenyl), it also means a group that may contain moieties having any of the topologies or saturation or unsaturation as explained above. Similarly, in all embodiments of the present invention, when referring to a group in one form (e.g., alkyl) of saturation or unsaturation, it is meant that the group can be of any type of topology (e.g., linear, cyclic, or branched) or have several moieties with various topologies.

[0072] It is to be understood that the term "...hydrocarbon group, optionally comprising..." means that the hydrocarbyl group optionally comprises heteroatoms to form ether, thioether, amine, nitrile or carboxylic acid groups and derivatives (including, for example, esters, acids, amides). These groups may replace hydrogen atoms of the hydrocarbyl group and thus be pendant to the hydrocarbon, or replace carbon atoms of the hydrocarbyl group (if chemically possible) and thus be inserted into the hydrocarbon chain or ring.

[0073] According to a specific embodiment, the acyl chloride is selected from the group consisting of benzene-1,3,5-triacyl trichloride (triformyl trichloride), benzene-1,2,4-triacyl trichloride, benzene-1,2,4,5-tetraacyl tetrachloride, cyclohexane-1,3,5-triacyl trichloride, isophthaloyl dichloride, diglycolyl oxide dichloride (diglycolyl dichloride), terephthaloyl chloride, fumaryl dichloride, adipoyl chloride, succinyl dichloride, propane-1,2,3-triyl trichloride, cyclohexane-1,2,4,5-tetrayl tetrachloride, 2,2'-disulfanediyl disuccinyl dichloride, 2-(2-chloro-2-oxoethyl)thiobutane dichloride, (4-chloro-4-oxobutyryl)-L-glutamyl dichloride, (S)-4-((1,5-dichloro-1,5-dioxopentan-2-yl)amino)-4-oxobutyric acid, 4-chloro-4-oxo-butyric acid 2,2-bis[(4-chloro-4-oxo-butyryl)oxymethyl]butyl ester, 4-chloro-4-oxo-butyric acid [2-[2,2-bis[(4-chloro-4-oxo 2-[(2-chlorocarbonylbenzoyl)oxymethyl]butyl] ester, 2-chlorocarbonylbenzoic acid 2,2-bis[(2-chlorocarbonylbenzoyl)oxymethyl]butyl ester, 2-chlorocarbonylbenzoic acid [2-[2,2-bis[(2-chlorocarbonylbenzoyl)oxymethyl]butoxymethyl]-2-[(2-chlorocarbonylbenzoyl)oxymethyl]butyl] ester, 2,4,5-trichlorocarbonyl-benzoic acid 4-(2,4,5-trichlorocarbonylbenzoyl)oxybutyl ester, tris(4-chloro-4-oxobutyric acid)propane-1,2,3-triyl ester, di(4-chloro-4-oxobutyric acid)propane-1,2-diyl ester and mixtures thereof.

[0074] According to a particular embodiment, the oil phase concentration is between 5% and 60%, preferably between 20% and 40% of the Pickering emulsion.

[0075] Hydrophobic materials

[0076] According to one embodiment, the core is an oil-based core.

[0077] The hydrophobic material according to the present invention may be an "inert" material, such as a solvent or an active ingredient.

[0078] When the hydrophobic materials are active ingredients, they are preferably selected from the group consisting of flavors, flavorings / edible flavors, flavor ingredients, fragrances (daily fragrances), fragrance ingredients, nutritional supplements, cosmetics, pest control agents, biocide active ingredients and mixtures thereof.

[0079] According to a specific embodiment, the hydrophobic material comprises a mixture of a fragrance and another ingredient selected from the group consisting of nutraceutical, cosmetic, pest control, and biocide active ingredients.

[0080] According to one embodiment, the hydrophobic material comprises a phase change material (PCM).

[0081] According to a specific embodiment, the hydrophobic material comprises a mixture of a biocide active ingredient and another ingredient selected from the group consisting of a fragrance, a nutraceutical, a cosmetic, a pest control agent.

[0082] According to a specific embodiment, the hydrophobic material comprises a mixture of a pest control agent and another ingredient selected from the group consisting of a fragrance, a nutraceutical, a cosmetic, a biocide active ingredient.

[0083] According to one particular embodiment, the hydrophobic material comprises a fragrance.

[0084] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0085] According to a particular embodiment, the hydrophobic material consists of a biocide active ingredient.

[0086] According to a specific embodiment, the hydrophobic material consists of a pest control agent.

[0087] By "fragrance" (or also referred to as "fragrance oil"), it is meant here an ingredient or composition that is liquid at about 20°C. According to any of the above embodiments, the fragrance oil may be a single fragrance ingredient or a mixture of multiple ingredients in the form of a fragrance composition. As a "fragrance ingredient", it is meant here a compound whose main purpose is to impart or adjust an odor. In other words, to be considered a fragrance ingredient, such an ingredient must be recognized by a person skilled in the art as being able to impart or modify the odor of a composition in at least an active or pleasant manner, rather than just having an odor. For the purposes of the present invention, fragrance oils also include combinations of fragrance ingredients with substances that together improve, enhance or modify the delivery of fragrance ingredients, such as fragrance precursors, emulsions or dispersions, as well as combinations that impart other benefits in addition to changing or imparting odor, such as persistence, burst, malodor counteracting, antibacterial effects, microbial stability, and pest control.

[0088] The nature and type of the perfuming ingredients present in the oil phase do not guarantee to be described in more detail here, and it is impossible to be exhaustive in any case, and the technician can select them based on their general knowledge and according to expected use or application and required sensory effect. Generally speaking, these perfuming ingredients belong to different chemical categories, such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds and essential oils, and the perfuming auxiliary ingredients can be natural or synthetic sources. In any case, many of these auxiliary ingredients are listed in references such as the work Perfume and Flavor Chemicals of S.Arctander, 1969, Montclair, New Jersey, USA or its updated version or other works of similar nature, and in the patent documentation abundant in the field of spices.

[0089] In particular, one may cite the perfuming ingredients commonly used in perfume formulations, for example:

[0090] - Aldehyde aroma components: decanal, dodecanal, 2-methylundecane, 10-undecenal, octanal, nonanal and / or nonenal;

[0091] - Aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0-2,7-]undec-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or α-pinene;

[0092] - balsamic ingredients: coumarin, ethyl vanillin and / or vanillin;

[0093] - Citrus aroma ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-menthenadiene;

[0094] -Floral fragrance ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethyl alcohol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone (β-violet ketone), methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1 -penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one, 2,5-dimethyl-2-indanemethanol, 2,6,6-trimethyl-3-cyclohexen-1-yl 1-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, tricyclodecenyl 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, methyl homocis-dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol , tricyclodecenyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-menthol, (S)-2-(1,1-dimethylpropoxy)propyl propionate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amylcinnamaldehyde, 8-decene-5-lactone, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, tricyclodecenyl isobutyrate, and / or a mixture of methylionone isomers;

[0095] - Fruity aroma components: γ-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiacyclopentane, 4-decanoic acid ethyl ester, hexyl acetate, 2-methylbutyric acid ethyl ester, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, [3-ethyl-2-oxiranyl]acetate 1-[3,3-dimethylcyclohexyl]ethyl ester and / or diethyl 1,4-cyclohexanedicarboxylate;

[0096] - Green fragrance ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styryl acetate, (2-methylbutoxy) allyl 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;

[0097] - Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecen-1-one, 1-oxa-12-cyclohexadecene-2-one, 1-oxa-13-cyclohexadecene-2-one, (9Z)-9-cycloheptadecene-1-one, 2-{1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3-methyl-5- Cyclopentadecen-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]isobenzopyran, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate, oxacyclohexadecane-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl propionate;

[0098] - Woody components: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[2,9'-tricyclo[6.2.1.0 2,7 ] undec[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate;

[0099] -Other ingredients (e.g. amber, powdery, spicy or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any of its stereoisomers, piperonal, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal.

[0100] It should also be understood that the ingredient may also be a compound known to release various types of perfuming compounds in a controlled manner, also known as a pro-fragrance or pro-fragrance. Non-limiting examples of suitable pro-fragrances may include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6-diene-1-oxo(phenyl)acetate, 2-phenylethyl ... ester, oxo(phenyl)acetate (Z)-hex-3-en-1-yl ester, hexadecanoic acid 3,7-dimethyl-2,6-octadien-1-yl ester, succinic acid bis(3,7-dimethyloct-2,6-dien-1-yl) ester, (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-(oct-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 2-(1-phenylethoxyprop-1-en-2-yl)naphthalene, (2-phenylethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)benzene benzene, 4-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or a mixture thereof.

[0101] The perfuming ingredients can be dissolved in solvents currently used in the perfume industry. The solvent is preferably not an alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, (rosin resin, available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes or isoparaffins. Preferably, the solvent is very hydrophobic and highly sterically hindered, e.g. or benzyl benzoate. Preferably, the fragrance contains less than 30% solvent. More preferably, the fragrance contains less than 20%, even more preferably less than 10% solvent, all of which percentages are by weight relative to the total weight of the fragrance. Most preferably, the fragrance is substantially free of solvent.

[0102] Preferred perfuming ingredients are those with high steric hindrance (bulky materials), in particular ingredients from one of the following groups:

[0103] - Group 1: perfuming ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted by at least one linear or branched C1-C4 alkyl or alkenyl substituent;

[0104] - Group 2: perfuming ingredients comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted by at least one linear or branched C4-C8 alkyl or alkenyl substituent;

[0105] - Group 3: perfuming ingredients comprising a benzene ring, or a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted by at least one linear or branched C5-C8 alkyl or alkenyl substituent, or substituted by at least one phenyl substituent and optionally substituted by one or more linear or branched C1-C3 alkyl or alkenyl substituents;

[0106] - Group 4: perfuming ingredients comprising at least two fused or linked C5 and / or C6 rings;

[0107] - Group 5: perfuming ingredients containing camphor-like ring structures;

[0108] - Group 6: contains at least one C7-C 20 Ring-structured fragrance ingredients;

[0109] - Group 7: perfuming ingredients having a logP value higher than 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent;

[0110] Examples of components from each of these groups are:

[0111] - Group 1: 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (source: Firmenich SA, Geneva, Switzerland), isocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (source: Firmenich SA, Geneva, Switzerland), nerol, terpineol, dihydroterpineol, terpene acetate, dihydroterpene acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1,8-p-menthadiene-7-ol (source: Firmenich SA, Geneva, Switzerland), l-p-menthen-4-ol, (1RS, 3RS, 4SR)-3-p-menthyl acetate, (1R, 2S, 4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (Source: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, trimethylcyclohexyl acetate (cyclanol), 1,4-cyclohexane diethyl dicarboxylate (Source: Firmenich SA, Geneva, Switzerland), (3ARS, 6SR, 7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (Source: Firmenich SA, Geneva, Switzerland), (6R)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (Source: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde;

[0112] - Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (Source: Givaudan SA, Vergne, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (Source: Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol (Source: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentane acetate (Source: Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (Source: Firmenich SA, Geneva, Switzerland), SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (Source: Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (Source: Givaudan SA, Vergne, Switzerland);

[0113] - Group 3: damascenone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (source: Firmenich SA, Geneva, Switzerland), (1'R)-2-[2-(4'-methyl-3'-cyclohexen-1'-yl)propyl]cyclopentanone, α-ionone, β-ionone, damascenone, a mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (source: Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (source: Firmenich SA, Geneva, Switzerland), propionic acid (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl ester (Source: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (Source: International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethyl-cyclohexyl)-3-hexanol (Source: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (Source: Firmenich SA, Geneva, Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpene isobutyrate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate (Source: Firmenich SA, Geneva, Switzerland), 8-methoxy-1-menthene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate (Source: Firmenich SA, Geneva, Switzerland), p-tert-butylcyclohexanone, menthyl mercaptan, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allyl cyclohexylpropionate, cyclohexyl salicylate, 2-methoxy-4-methylphenyl methyl carbonate, 2-methoxy-4-methylphenyl ethyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate;

[0114] - Group 4: Methyl cedryl ketone (source: International Flavors and Fragrances, USA), 2-methylpropanoic acid (1RS, 2SR, 6RS, 7RS, 8SR)-tricyclic [5.2.1.0 2,6 ]dec-3-en-8-yl ester and 2-methylpropionic acid (1RS, 2SR, 6RS, 7RS, 8SR)-tricyclo[5.2.1.0 2,6] mixture of dec-4-en-8-yl esters, vetyverol, vetyverone, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone (source: International Flavors and Fragrances, USA), (5RS,9RS,10SR)-2,6,9,10-tetramethyl-1-oxaspiro[4.5]dec-3,6-diene and (5RS,9SR,10RS) isomers, 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]dec-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indanone (source: International Flavors and Fragrances, USA) and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal (Source: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undec-4-ene-9-spiro-2'-oxirane (Source: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (acetic acid perhydro-5,5,8A-trimethyl-2-naphthyl ester (Source: Firmenich SA, Geneva, Switzerland), 1-naphthol (octalynol), (dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan (Source: Firmenich SA, Geneva, Switzerland) SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl propionate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl propionate, (+)-(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1]heptane-3-spiro-2′-cyclohexen-4′-one;

[0115] - Group 5: Camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedrane, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane (source: Firmenich SA, Geneva, Switzerland), cedrene, cedrene alcohol, cedrol, 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecan-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-5-one. 2,7] mixture of undec-4-one (source: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (source: Firmenich SA, Geneva, Switzerland);

[0116] - Group 6: (trimethyl-13-oxabicyclo-[10.1.0]-tridec-4,8-diene (source: Firmenich SA, Geneva, Switzerland), 9-hexadecene-16-lactone (source: Firmenich SA, Geneva, Switzerland), cyclopentadecenolactone (source: Firmenich SA, Geneva, Switzerland), 3-methyl(4 / 5)-cyclopentadecenone (source: Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (source: Firmenich SA, Geneva, Switzerland), pentadecalactone (source: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (source: Firmenich SA, Geneva, Switzerland), (1-ethoxyethoxy)cyclododecane (source: Firmenich SA, Geneva, Switzerland), 1,4-dioxacycloheptadecan-5,17-dione, 4,8-cyclododecadien-1-one;

[0117] - Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propyl)phenyl]propanal (source: Givaudan SA, Vergne, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0118] Preferably, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients selected from Groups 1 to 7 as defined above. More preferably, the perfume comprises at least 30%, preferably at least 50% of ingredients selected from Groups 3 to 7 as defined above. Most preferably, the perfume comprises at least 30%, preferably at least 50% of ingredients selected from Groups 3, 4, 6 or 7 as defined above.

[0119] According to another preferred embodiment, the fragrance comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients having a logP above 3, preferably above 3.5, even more preferably above 3.75.

[0120] According to a specific embodiment, the perfume used in the present invention contains less than 10% of its own weight of primary alcohol, less than 15% of its own weight of secondary alcohol and less than 20% of its own weight of tertiary alcohol. Advantageously, the perfume used in the present invention does not contain any primary alcohol, but contains less than 15% of secondary and tertiary alcohols.

[0121] According to one embodiment, the oil phase (or oil-based core) comprises:

[0122] - 25 to 100 wt%, preferably 25 to 98 wt%, of a fragrance oil comprising at least 15 wt% of a high impact fragrance raw material having a Log T < -4, and

[0123] - 0 to 75% by weight, preferably 2 to 75% by weight, with a density greater than 1.07 g / cm 3 Density balanced material.

[0124] "High impact fragrance raw materials" are understood to be fragrance raw materials with Log T < -4. The odor threshold concentration of a chemical compound is determined in part by its shape, polarity, partial charge and molecular weight. For convenience, the odor threshold concentration is expressed as the common logarithm of the threshold concentration, i.e. Log [threshold] ("LogT").

[0125] "Density balanced material" should be understood as having a density greater than 1.07 g / cm 3 And materials with low odor or no odor are preferred.

[0126] The odor threshold concentration of the flavoring compounds is determined by using a gas chromatograph ("GC"). Specifically, the gas chromatograph is calibrated to determine the exact volume of the fragrance oil component injected by the syringe, the exact split ratio and the hydrocarbon response using hydrocarbon standards of known concentration and chain length distribution. The air flow rate is accurately measured and the sampling volume is calculated assuming that the duration of human inhalation lasts 12 seconds. Since the exact concentration at the detector at any point in time is known, the mass per volume inhaled is known, so the concentration of the flavoring compound is known. To determine the threshold concentration, the solution is delivered to the sniffing port with the back-calculated concentration. The panelist sniffs the GC effluent and determines the retention time when the odor is perceived. The average of all panelists determines the odor threshold concentration of the flavoring compound. The determination of odor thresholds is described in more detail in C. Vuilleumier et al., Multidimensional Visualization of Physical and Perceptual Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, Vol. 33, September,, 2008, pages 54-61.

[0127] WO2018115250 describes high impact fragrance raw materials with Log T < -4 and with a density greater than 1.07 g / cm 3 The density of the density balance material properties, the contents of which are incorporated by reference.

[0128] According to one embodiment, the high impact fragrance raw material with Log T<-4 is selected from the group consisting of: (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1-phenyl acetate, pyrazole butyl ether, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl)pyridine, 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, -1-one, a mixture comprising (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one and (3SR,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one, (+-)-1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1-one, (1'S,3'R)-1-methyl-2-[(1',2',2'-trimethylbicyclo[3.1.0]hex-3'-yl)methyl]cyclopropyl}methanol , (+-)-3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, H-methyl-2h-1,5-benzodioxepin-3(4H)-one, (2E,6Z)-2,6-nonadien-1-ol, (4Z)-4-dodecenal, (+-)-4-hydroxy-2,5-dimethyl-3(2H)-furanone, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-perhydro-4α,8Aβ-dimethyl -4a-naphthol, patchouli alcohol, 2-methoxy-4-(1-propenyl)phenol, a mixture comprising (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylidene-2-phenyl-2H-pyran, a mixture comprising 4-methylidene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,6-dihydro-2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonenal, 2-methoxy-4-propylphenol, 3-methyl-5-phenyl-2-pentenenitrile, 1-(spiro[4.5]dec-6 / 7-en-7-yl)-4-penten-1-one (, 2-methoxynaphthalene, (-)-(3aR,5AS,9AS,9BR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 5-nonalactone, (3aR,5AS,9AS,9BR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 7-isopropyl-2H,4H-1,5-benzodioxepin-3-one, coumarin, 4-methylphenyl isobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, β,2,2,3-tetramethyl-δ-methylidene-3 -cyclopentene-1-butanol, δ-damascenone ((2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one), (+-)-3,6-dihydro-4,6-dimethyl-2-phenyl-2h-pyran, anisaldehyde, p-cresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2-aminobenzoate, ethyl methylphenyl glycidate, γ-octalactone, ethyl 3-phenyl-2-acrylate, (-)-(2E)-2-ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, p-cresol acetate, dodecalactone, dimethyl tricyclo[7.1.1.0. 2,7] Undec-2-en-4-one (tricyclone), (+)-(3R,5Z)-3-cyclopentadecen-1-one, undecanolide, (1R,4R)-8-mercapto-3-menthone, (3S,3AS,6R,7AR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, β-ionone, (+-)-6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1,3,5-undecadiene, 10-undecenal, (9E)-9-undecanoic acid aldehyde, (9Z)-9-undecenal, (Z)-4-decenal, 2-methylpentanoic acid (+-)-ethyl ester, 1,2-diallyl disulfane, 2-tridecenenitrile, 3-tridecenenitrile, (+-)-2-ethyl-4,4-dimethyl-1,3-oxathiacyclohexane, (+)-(3R,5Z)-3-methyl-5-cyclopentadecen-1-one, 3-(4-tert-butylphenyl)propanal, (cyclohexyloxy)acetate, methyl naphthyl ketone, (+-)-(4E)-3-methyl-4-cyclopentadecen-1-one ketone, (+-)-5E3-methyl-5-cyclopentadecen-1-one, 3-hexenoic acid cyclopropyl methyl ester, (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-butene-2-one, (3aRS,5aSR,9aSR,9bRS)-3a,6, 6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan, (2S,5R)-5-methyl-2-(2-propyl)cyclohexanone oxime, 6-hexyltetrahydro-2H-pyran-2-one, (+-)-3-(3-isopropyl-1-phenyl)butyraldehyde, 2-(3-oxo-2-pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohex-2-enyl)pent-1-en-3-one, indole, 7-propyl-2H,4H-1,5-benzodioxepin-3-one, ethyl maltol (ethyl praline), (4-methylphenoxy)acetaldehyde, tricyclo[5.2.1.0.(2,6)]decane-2-carboxylic acid ethyl ester, (+)-(1'S,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol, (4E)-3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-isopropyl-6-methyl-bicyclo[2.2.2] oct-5-ene-2-carboxaldehyde, methylnonyl acetaldehyde, 2-methylpropionic acid 4-formyl-2-methoxyphenyl ester, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-butene-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-acrylonitrile, 4-methoxybenzyl acetate, (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, (2 / 3-methylbutoxy) allyl acetate, (+-)-(2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1-penten-3-one, and mixtures thereof.

[0129] According to one embodiment, the fragrance raw material with Log T<-4 is selected from the group consisting of aldehydes, ketones, alcohols, phenols, esters, lactones, ethers, epoxides, nitriles and mixtures thereof.

[0130] According to one embodiment, the fragrance raw material with Log T <-4 comprises at least one compound selected from the group consisting of alcohols, phenols, esters, lactones, ethers, epoxides, nitriles and mixtures thereof, preferably in an amount of 20 to 70% by weight, based on the total weight of the fragrance raw materials with Log T <-4.

[0131] According to one embodiment, the fragrance raw materials with Log T <-4 comprise 20 to 70 wt. % of aldehydes, ketones and mixtures thereof, based on the total weight of the fragrance raw materials with Log T <-4.

[0132] Therefore, the remaining perfume raw materials contained in the oil-based core may have a Log T>-4.

[0133] According to one embodiment, the fragrance raw material with Log T>-4 is selected from the group consisting of: ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6 / 8-sec-butylquinoline, (+-)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal, tricyclodecenyl propionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone, methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl) acetate, (+-)-(E)-4-methyl-3-decen-5-ol, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 1,3,3-trimethyl-2-oxadiazine Cyclo[2.2.2]octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa-12-cyclohexadecene-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, C11 aldehyde, (+-)-2,6-dimethyl-7-octen-2-ol, allyl 3-cyclohexylpropionate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-n-propyl)cyclohexanone, allyl heptanoate, 2-(2-methyl-2-n-propyl)cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl butyrate, geranyl acetate, neryl acetate, (+-)-1-phenylethyl acetate ester, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, ethyl 3-oxobutyrate, 3-hydroxy-2-butenoic acid (2Z)-ethyl ester, 8-p-menthol, 8-p-menthyl acetate, 1-p-menthyl acetate, (+-)-2-(4-methyl-3-cyclohexen-1-yl)-2-propyl acetate, (+-)-2-methylbutyl butyrate, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3,5,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 2-cyclohexylethyl acetate esters, octanal, ethyl butyrate, (+-)-(3E)-4-(2,6,6-trimethyl-1 / 2-cyclohexen-1-yl)-3-buten-2-one, 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, ethyl hexanoate, undecanal, decanal, 2-phenylethyl acetate, (1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1] heptane-2-ol), (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2-propylidene)cyclohexene, (+)-(R)-4-(2-methoxyprop-2-yl)-1-methylcyclohex-1-ene, tricyclodecenyl acetate, (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3R)-1-[(1S,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (+)-(1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate, and mixtures thereof.

[0134] According to one embodiment, the fragrance formulation comprises:

[0135] - 0 to 60% by weight of a hydrophobic solvent (based on the total weight of the fragrance formulation),

[0136] - 40 to 100 wt. % of a fragrance oil (based on the total weight of the fragrance formulation), wherein the fragrance oil has at least two, preferably all, of the following properties:

[0137] o at least 35%, preferably 40%, preferably at least 50%, more preferably at least 60% of the perfuming ingredients have a log P greater than 3, preferably greater than 3.5,

[0138] o at least 20%, preferably 25%, preferably at least 30%, more preferably at least 40% of bulky materials of Groups 1 to 6, preferably Groups 3 to 6, as defined above, and

[0139] o at least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least 30% of the high impact fragrance material as defined above having a Log T < -4,

[0140] - Optionally, additional hydrophobic active ingredients.

[0141] According to a particular embodiment, the fragrance comprises from 0 to 60% by weight of a hydrophobic solvent.

[0142] According to a particular embodiment, the hydrophobic solvent is a density balancing material, preferably selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylate, benzyl cinnamate and mixtures thereof.

[0143] In a particular embodiment, the hydrophobic solvent has a Hansen Solubility Parameter that is compatible with the entrapped fragrance oil.

[0144] The term "Hansen solubility parameters" is understood to refer to the solubility parameter method proposed by Charles Hansen for predicting the solubility of polymers and developed on the basis that the total vaporization energy of a liquid consists of several individual components. To calculate the "weighted Hansen solubility parameters", the effects of (atomic) dispersion forces, (molecular) permanent dipole-permanent dipole forces and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen solubility parameter" is calculated as (δD 2 +δP 2 +δH 2 ) 0.5 , where δD is the Hansen dispersion value (hereinafter also referred to as atomic dispersion force), δP is the Hansen polarizability value (hereinafter also referred to as dipole moment), and δH is the Hansen hydrogen bond ("h-bond") value (hereinafter also referred to as hydrogen bond). For a more detailed description of this parameter and this value, please refer to The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient by Charles Hansen, Danish Technical Press (Copenhagen, 1967).

[0145] The Euclidean difference of the solubility parameters of the fragrance and the solvent was calculated as (4*(δD solvent -δD fragrance ) 2 +(δP solvent -δP fragrance ) 2 +(δH solvent -δH fragrance ) 2 ) 0.5 , where δD solvent ,δP solvent and δH solvent are the Hansen dispersion value, Hansen polarizability value and Hansen hydrogen bond value of the solvent respectively; and δD fragrance ,δ fragrance and δH fragrance They are the Hansen dispersion value, Hansen polarizability value and Hansen hydrogen bonding value of the fragrances, respectively.

[0146] In a particular embodiment, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the first group consisting of: atomic dispersion force (δD) of 12 to 20, dipole moment (δP) of 1 to 8, and hydrogen bonding (δH) of 2.5 to 11.

[0147] In a particular embodiment, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the second group consisting of: atomic dispersion forces (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δP) of 1 to 8, preferably 1 to 7, and hydrogen bonds (δH) of 2.5 to 11, preferably 4 to 11.

[0148] In a particular embodiment, at least 90% of the fragrance oils, preferably at least 95% of the fragrance oils, and most preferably at least 98% of the fragrance oils have at least two Hansen solubility parameters selected from the first group consisting of: atomic dispersion forces (δD) of 12 to 20, dipole moments (δP) of 1 to 8, and hydrogen bonds (δH) of 2.5 to 11.

[0149] In a particular embodiment, the fragrance oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from the second group consisting of: atomic dispersion forces (δD) of 12 to 20, preferably 14 to 20, a dipole moment (δP) of 1 to 8, preferably 1 to 7, and hydrogen bonds (δH) of 2.5 to 11, preferably 4 to 11.

[0150] According to one embodiment, the perfuming formulation comprises a fragrance modulator (which may be used together with the hydrophobic solvent when the hydrophobic solvent is present, or as a substitute for the hydrophobic solvent when the hydrophobic solvent is absent).

[0151] Preferably, a fragrance modulator is defined as a fragrance material having:

[0152] i. Vapor pressure less than 0.0008 Torr at 22°C;

[0153] ii. clogP of 3.5 or more, preferably 4.0 or more, more preferably 4.5;

[0154] iii. at least two Hansen solubility parameters selected from the first group consisting of: atomic dispersion forces of 12 to 20, dipole moments of 1 to 7, and hydrogen bonding of 2.5 to 11,

[0155] iv. at least two Hansen solubility parameters selected from the second group consisting of: atomic dispersion forces of 14 to 20, dipole moments of 1 to 8, hydrogen bonds of 4 to 11, when in solution with a compound having a vapor pressure range of 0.0008 to 0.08 Torr at 22°C.

[0156] Preferably, as examples, the following ingredients can be listed as regulators, but the list is not limited to the following substances: alcohol C12, oxahedral, 3-[(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecan-1-one, cyclopentadecanone, (8Z)-oxahedral, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furanyl)-tetrahydro-5-methyl-2-furanyl]-2-propanol, lily 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-hexa Hydrocyclopenta[g]isobenzopyran, (+)-(1S,2S,3S,5R)-2,6,6-trimethylspiro[bicyclo[3.1.1]heptane-3,1'-cyclohexane]-2'-en-4'-one, oxahertzan-2-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, (+)-(4 R,4aS,6R)-4,4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amyl cinnamaldehyde, hexyl cinnamaldehyde, hexyl salicylate, (1E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,6-heptadien-3-one, (9Z)-9-cycloheptadecene-1-one.

[0157] According to a particular embodiment, the hydrophobic material does not contain any active ingredients (e.g. fragrances). According to this particular embodiment, it comprises, preferably consists of, a hydrophobic solvent, preferably selected from isopropyl myristate, triglycerides (e.g. MCT oil, vegetable oil), D-limonene, silicone oil, mineral oil and mixtures thereof, and optionally a hydrophilic solvent preferably selected from the following: 1,4-butylene glycol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propylene glycol), 1,3-propylene glycol, dipropylene glycol, glycerol, glycol ethers and mixtures thereof.

[0158] The term "biocide" refers to a chemical substance that can kill living organisms (e.g., microorganisms) or reduce or prevent their growth and / or accumulation. Biocides are commonly used in medicine, agriculture, forestry, and in industries such as preventing scaling of water, agricultural products (including seeds), and oil pipelines. Biocides can be pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, miticides, and rodenticides; and / or antimicrobial agents, such as bactericides, antibiotics, antibacterial agents, antiviral agents, antifungal agents, antiprotozoal and / or antiparasitic agents.

[0159] As used herein, "pest control agent" refers to a substance used to repel or attract pests to reduce, inhibit or promote their growth, development or activity. Pests are any organisms that are invasive or troublesome to plants or animals, whether animals, plants or fungi, including insects, especially arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0160] By "flavor oil", it is meant here a flavoring ingredient, or a mixture of flavoring ingredients, solvents or adjuvants currently used to prepare flavoring formulations, i.e. a specific mixture of ingredients intended to be added to an edible composition or chewing product to impart, improve or modify its organoleptic properties, in particular its flavor and / or taste. Flavoring ingredients are well known to those skilled in the art, and their properties do not warrant a more detailed description here, which is in any case not exhaustive, and a skilled flavorist can select them according to his general knowledge and according to the intended use or application and the organoleptic effect he wishes to achieve. Many of these flavoring ingredients are listed in the references, such as S. Arctander's book Perfume and Flavor Chemicals, 1969, Montclair, NJ, USA or its latest version, or other works of similar nature, such as Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press or MB Jacobs' Synthetic Food Adjuncts, 1947, van Nostrand Co., Inc. The solvents and adjuvants currently used to prepare flavoring formulations are also well known in the art.

[0161] In a specific embodiment, the flavor is a mint flavor. In a more specific embodiment, the mint is selected from the group consisting of peppermint and spearmint.

[0162] In a further embodiment, the flavoring agent is a cooling agent or a mixture thereof.

[0163] In another embodiment, the flavor is a menthol flavor.

[0164] Flavors derived from or based on fruits (citric acid is the main naturally occurring acid in the fruit) include, but are not limited to, for example, citrus fruits (e.g., lemons, limes), limonene, strawberries, oranges, and pineapples. In one embodiment, the flavored food is lemon juice, lime juice, or orange juice extracted directly from the fruit. Other embodiments of flavors include juices or liquids extracted from oranges, lemons, grapefruits, limes, citrons, clementines, mandarins, tangerines, and any other citrus fruits or their variants or hybrids. In a specific embodiment, flavors include liquids extracted or distilled from oranges, lemons, grapefruits, limes, citrons, clementines, tangerines, any other citrus fruits or their variants or hybrids, pomegranates, kiwis, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruit, mangoes, pears, tomatoes, and strawberries.

[0165] In a specific embodiment, the flavor comprises a limonene-containing composition. In a specific embodiment, the composition is citrus further comprising limonene.

[0166] In another specific embodiment, the flavor comprises a flavor selected from the group consisting of strawberry, orange, lime, tropical fruit, berry blend, and pineapple.

[0167] The phrase flavoring agent includes not only flavoring agents that impart or modify food smell, but also ingredients that impart or modify taste. The latter does not necessarily have taste or smell itself, but can improve the taste provided by other ingredients such as salt enhancement ingredients, sweet enhancement ingredients, umami enhancement ingredients, bitterness blocking ingredients, etc.

[0168] In further embodiments, suitable sweetening components may be included in the particles described herein. In a specific embodiment, the sweetening component is selected from the group consisting of sugar (such as but not limited to sucrose), stevia components (such as but not limited to stevioside or rebaudioside A), sodium cyclamate (cyclamate), aspartame, sucralose, saccharin sodium and acesulfame potassium or mixtures thereof.

[0169] Specific embodiments of the aqueous phase

[0170] According to a particular embodiment, the method of the invention comprises a step of adding a reactant to the aqueous phase during the reaction. This optionally used reactant may participate in the formation of the shell of the microcapsules.

[0171] The reactants may be water soluble or water suspendable. Examples of suitable reactants include alcohols, amines, phenols, thiols and mixtures thereof.

[0172] According to a particular embodiment, when the polyfunctional monomer is a polyfunctional isocyanate, no significant amount of amines or other water-soluble reactants that readily polymerize with the polyfunctional isocyanate, such as alcohols, thiols, ureas, urethanes, and mixtures thereof, are added at any stage of the process.

[0173] According to one embodiment, the weight ratio of the oil phase to the water phase is from 1:99 to 50:50, preferably from 10:90 to 40:60.

[0174] Coacervate particles

[0175] Coacervate particles can be "simple" coacervate particles (i.e., made by "simple" coacervation) or "complex" coacervates (i.e., made by "complex" coacervation) or mixtures thereof. By simple coacervate, it is meant that one polymer (or copolymer) is prepared alone to phase separate and then precipitated from a homogeneous solution in the presence of an antisolvent to form coacervate particles. By complex coacervate, it is meant a process where at least two oppositely charged polymers (or polyelectrolytes) are brought together (at a particular pH) to form coacervate particles. Complex coacervate also encompasses coacervates formed from charged polyions (polyions) and oppositely charged polymers.

[0176] Complex coacervate particles

[0177] According to one specific embodiment, the coacervate is a complex coacervate particle. In other words, according to this embodiment, the coacervate particle comprises at least a first polymer and a second polymer. According to one embodiment, the first polymer and the second polymer are water soluble.

[0178] The first polymer and the second polymer may also be referred to as a first polyelectrolyte and a second polyelectrolyte, respectively.

[0179] According to one embodiment, the first and / or second polymer is a biopolymer.

[0180] According to one embodiment, the first polymer contains at least one cationic group, such as an amino group, an azole group, an amide group, a quaternary ammonium cation or a guanidine cation.

[0181] The first polymer is preferably selected from the group consisting of proteins (e.g. gelatin, whey protein, albumin), chitosan and its derivatives, cationically modified polysaccharides, polyethyleneimines, poly(amidoamines), poly(amino-co-esters), cationic polyacrylates or mixtures thereof.

[0182] According to one embodiment, the protein is a vegetable protein, preferably selected from the group consisting of potato protein, chickpea protein, pea protein, bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, canola protein, rice protein, sunflower protein and mixtures thereof.

[0183] The second polymer is selected from the group consisting of modified starch, gum arabic, chitosan, alginates, cellulose derivatives, guar gum, pectinates, pectin, carrageenan, sodium caseinate, hyaluronic acid, polyacrylic acid and methacrylic acid, xanthan gum or a polyanion preferably selected from sodium triphosphate, trisodium trimetaphosphate, sodium pyrophosphate, dextran sulfate sodium salt and mixtures thereof.

[0184] The weight ratio between the first polymer and the second polymer is preferably from 1:9 to 9:1, more preferably from 3:7 to 7:3.

[0185] According to one embodiment, the coacervate particles comprise chitosan (as the first polymer) and sodium caseinate (as the second polymer).

[0186] According to one embodiment, the coacervate particles comprise whey protein (as the first polymer) and gum arabic (as the second polymer).

[0187] According to one embodiment, the coacervate particles comprise whey protein (as the first polymer) and chitosan (as the second polymer).

[0188] According to one embodiment, the coacervate particles comprise chitosan (as the first polymer) and sodium alginate (as the second polymer).

[0189] According to one embodiment, the coacervate particles comprise chitosan (as the first polymer) and pectin (as the second polymer).

[0190] According to one embodiment, the coacervate particles comprise a polymer and a polyion (e.g., an anion and a cation) having an opposite charge to the polymer. Examples of anions are multivalent anions, such as sodium triphosphate, trisodium trimetaphosphate, sodium pyrophosphate, dextran sulfate sodium salt. Examples of cations are multivalent metal cations, such as Sn. 4+ 、Al 3+ , Fe 3+ , Sb 3+ , Ga 3+ , Ca 2+ Mg 2+ 、Zn 2+ , Ba 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and mixtures thereof.

[0191] According to a specific embodiment, the coacervate particles are prepared by transient nanoprecipitation (FNP).The coacervate particles can be prepared using a MIVM (Multi-Inlet Vortex Mixer) device, which typically comprises 2 to 4 inlets.

[0192] It has been found that the preparation of coacervate particles using transient nanoprecipitation (FNP) has several advantages. In fact, coacervate particles with controlled size and narrow size distribution can be obtained when prepared by FNP, which is one of the key factors for the surface activity of these coacervate particles at the water-in-oil interface to prepare stable Pickering emulsions.

[0193] Furthermore, when biopolymers are used as polyelectrolytes, FNPs can provide coacervate particle suspensions with higher biopolymer content, which means that more biopolymers can be embedded into the shell during the shell formation process.

[0194] Finally, active ingredients can be incorporated into the coacervate particles during the FNP process, providing additional benefits to microencapsulation.

[0195] According to one embodiment, when the coacervate particles are complex coacervate particles (i.e., comprising at least two polymers), the coacervate particles are prepared by a transient nanoprecipitation (FNP) process comprising the following steps:

[0196] (i) injecting a first polymer solution into a first stream of a multi-inlet vortex mixer,

[0197] (ii) Injecting the second polymer solution into the second stream of the multi-inlet vortex mixer

[0198] (iii) optionally, injecting the third solution and / or the fourth solution into the third and / or fourth stream of the multi-inlet vortex mixer,

[0199] (iv) Mixing of solutions injected from different streams to form a complex coacervate particle suspension.

[0200] The first polymer and the second polymer are as defined above.

[0201] The third solution and / or the fourth solution typically comprises water of a buffer solution.

[0202] A buffer solution may be added in step (iii) to adjust the pH, typically between 2.0 and 8.0.

[0203] The fourth solution and / or the third solution may comprise an active ingredient.The third solution and / or the fourth solution is preferably miscible with water.

[0204] The skilled person will be able to select suitable process parameters.Injection is typically performed using a pump (eg PHD ULTRA, Harvard) at a rate of 10 mL / min to 120 mL / min, preferably 20 mL / min to 80 mL / min.

[0205] Figure 2 A typical process is shown.

[0206] Simple coacervate particles

[0207] According to a specific embodiment, the coacervate is a simple coacervate particle. In other words, according to this embodiment, the coacervate particle only comprises:

[0208] (a) Water-soluble polymer (or copolymer): coacervate particles formed by precipitation of a water-soluble polymer solution in the presence of an antisolvent, or

[0209] (b) Water-insoluble polymer (or copolymer): coacervate particles formed by precipitation of a water-insoluble polymer solution in the presence of water or an aqueous solution (aqueous solution).

[0210] Simple coacervate particles can be obtained by an instantaneous nanoprecipitation process, which includes the following steps:

[0211] (i) injecting the polymer solution into the first stream of the multi-inlet vortex mixer,

[0212] (ii) injecting the antisolvent into the second stream of the multi-inlet vortex mixer,

[0213] (iii) optionally, injecting the third solution and / or the fourth solution into the third and / or fourth stream of the multi-inlet vortex mixer,

[0214] (iv) Mixing of solutions injected from different streams to form a simple coacervate particle suspension.

[0215] Depending on the nature of the polymer used in step i) (water-soluble or water-insoluble), a person skilled in the art will be able to select a suitable anti-solvent in step ii).

[0216] (a) Water-soluble polymer (or copolymer)

[0217] For the purposes of the present invention, "water-soluble polymer" means any polymer that forms a single-phase solution in water. Preferably, it forms a single-phase solution when dissolved in water at a concentration of up to 20% by weight, more preferably even up to 50% by weight. Most preferably, it forms a single-phase solution when dissolved in water at any concentration.

[0218] The water-soluble polymer may be selected from the group consisting of proteins (e.g., gelatin, sodium caseinate, whey protein, albumin), chitosan and its derivatives, cationically modified polysaccharides, polyethylene imine, poly(amidoamine), poly(amino-co-esters), cationic polyacrylates, modified starches, gum arabic, chitosan, alginates, zein, cellulose derivatives, guar gum, pectinates, pectin, carrageenan, hyaluronic acid, polyacrylic and methacrylic acids, xanthan gum or polyanions composed of sodium triphosphate, trisodium trimetaphosphate, sodium pyrophosphate, sodium dextran sulfate, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polyhydroxyethyl methacrylate and other hydrophilic polyacrylates, poly(N-isopropylacrylamide), polyols, polyoxazolines, polyphosphates, polyphosphazenes, polyvinyl methyl ethers, locust bean gum, xyloglucan, hydroxypropyl guar gum, hydroxypropyl cellulose and hydroxypropyl methylcellulose. According to one embodiment, the water-soluble copolymer contains a hydrophilic block, which can be selected from polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyacrylate, polyacrylamide, polyol, polyvinyl pyrrolidone or other polyelectrolytes.

[0219] As anti-solvent, for example, organic solvents miscible with water, acid solutions, alkaline solutions or salt solutions may be mentioned. Optionally, a further step of removing the organic solvent from the particle suspension may be included.

[0220] (b) Water-insoluble polymer (or copolymer)

[0221] The polymer (or copolymer) may include proteins, polycaprolactone polyols, polylactic acid-glycolic acid copolymers, polylactic acid, polyepoxides, polyanhydrides, poly(meth)acrylates, and copolymers containing polylactic acid-glycolic acid, polylactic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyacrylates, polyacrylamides, polyols, and polyvinyl pyrrolidone.

[0222] In step i), the water-insoluble polymer or copolymer should be dissolved in a water-soluble organic solvent. Water-soluble solvents include methanol, ethanol, ethylene glycol, propylene glycol, glycerol, acetone, ethyl acetate, tetrahydrofuran, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, pyridine, acetic acid, 2-methoxyethanol, 2-ethoxyethanol, morpholine, N-methyl-2-pyrrolidone, formamide, acetamide. The polymer or copolymer can be dissolved in these solvents and precipitated from the solution in the presence of water or an aqueous solution as an anti-solvent in step ii).

[0223] Water or an aqueous solution acts as an antisolvent. For example, an acid solution, an alkaline solution or a salt solution can also be mentioned.

[0224] Optionally, the process may comprise the further step of removing the organic solvent from the particle suspension.

[0225] According to one embodiment, the coacervate particles have a particle size of 100 nm to 10 μm, preferably 200 nm to 5 μm.

[0226] By "particle size" is meant the mean diameter of the particles of a size distribution measured by dynamic light scattering (DLS) using a Zetasizer Nano ZS device from Malvern Instruments Ltd., UK, when the particles are dispersed in an aqueous phase.

[0227] Preferably, the total amount of coacervate particles present in the aqueous phase is from 0.1 to 20 wt%, preferably from 0.2 to 10 wt%.

[0228] According to one embodiment, the coacervate particles comprise an active ingredient, preferably selected from the group consisting of a cosmetic ingredient, a skin care ingredient, a perfume ingredient, a flavor ingredient, a malodor counteracting ingredient, an antimicrobial ingredient, a pharmaceutical or agrochemical ingredient, a disinfectant ingredient, an insect repellent or attractant, and mixtures thereof.

[0229] According to one embodiment, the active ingredient is an antimicrobial ingredient. The antimicrobial ingredient may be an antibacterial ingredient, an antifungal ingredient and / or an antiparasitic ingredient. Non-exhaustive examples of such ingredients include quaternary ammonium salts and polymers containing quaternary ammonium salt groups, cathelicidins, chitosan and its derivatives, polyphenols, and inorganic particles, such as silver particles, titanium dioxide particles, and zinc oxide particles.

[0230] When prepared by FNPs, the active ingredient can be added by mixing the active ingredient (or active ingredient solution) into the polymer solution or by injecting the active ingredient into one stream of a multi-inlet vortex mixer during the process.

[0231] Optional step: outer coating layer

[0232] According to a specific embodiment, the surface of the microcapsules obtained by the method of the present invention can be modified by an additional step, and the monomers or polymers suitable for surface modification are selected from compounds that can form chemical bonds with the microcapsules and can improve the compatibility between the microcapsules and the target matrix.

[0233] Therefore, according to a specific embodiment of the present invention, at the end of step 3) of the method, a coating material selected from the group consisting of non-ionic polysaccharides, cationic polymers, polysuccinimide derivatives (such as those described in WO2021185724) and mixtures thereof can also be added to the slurry of the present invention to form an outer coating layer (coating) of the microcapsules.

[0234] Nonionic polysaccharide polymers are well known to those skilled in the art. Preferred nonionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar gum, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

[0235] Cationic polymers are well known to those skilled in the art. The cationic charge density of the preferred cationic polymer is at least 0.5 meq / g, more preferably at least about 1.5 meq / g, but also preferably less than about 7 meq / g, more preferably less than about 6.2 meq / g. The cationic charge density of the cationic polymer can be determined by the Kjeldahl method, as described in the chemical test for nitrogen determination by the US Pharmacopoeia. Preferred cationic polymers are selected from those containing primary amine, secondary amine, tertiary amine and / or quaternary amine groups, which units can form part of the main polymer chain or can be carried by side substituents directly connected thereto. The weight average molecular weight (Mw) of the cationic polymer is preferably 10,000 to 3.5 M Daltons, more preferably 50,000 to 1.5 M Daltons.

[0236] According to a particular embodiment, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylaminomethacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-imidazol-3-ium chloride), vinylpyrrolidone, acrylamidopropyltrimethylammonium chloride, cassia hydroxypropyltrimethylammonium chloride, guar hydroxypropyltrimethylammonium chloride or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimethylammonium chloride and cellulose hydroxypropyltrimethylammonium chloride will be used. Preferably, the copolymer should be selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride.

[0237] Specific examples of commercially available products include SC60 (cationic copolymer of acrylamidopropyltrimethylammonium chloride and acrylamide, source: BASF) or For example, PQ 11N, FC 550 or Style (polyquaternium-11-68 or vinyl pyrrolidone quaternized copolymer, source: BASF), or (C13S or C17, source: Rhodia).

[0238] According to any of the above embodiments of the present invention, the amount of the above polymer added is about 0% to 5% w / w, or even about 0.1% to 2% w / w, the percentage being expressed on a w / w basis relative to the total weight of the slurry obtained after step 3). It is clearly understood by those skilled in the art that only a portion of the added polymer will be incorporated into / deposited on the microcapsule shell.

[0239] Another object of the present invention is a method for preparing microcapsule powders, comprising the following steps:

[0240] 1) suspending the coacervate particles in water to form an aqueous phase;

[0241] 2) mixing at least one multifunctional monomer with a hydrophobic material to form an oil phase;

[0242] 3) The oil phase is added to the water phase and they are mixed to form an oil-in-water Pickering emulsion under conditions that allow the formation of a microcapsule slurry by interfacial polymerization.

[0243] 4) Drying the microcapsule slurry to obtain microcapsule powder.

[0244] Any drying method known to those skilled in the art can be used; in particular, the slurry can be spray-dried, preferably in the presence of a polymeric carrier material (e.g., polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gum, pectin, xanthan gum, alginates, carrageenan or cellulose derivatives), to provide microcapsules in powder form.

[0245] The microencapsulated powder may also contain free fragrance.

[0246] Microcapsules

[0247] The object of the present invention is to provide a microcapsule slurry or microcapsule powder obtained by the above method.

[0248] Another object of the present invention is a microcapsule or a microcapsule slurry comprising at least one microcapsule comprising:

[0249] - a core, preferably an oil-based core, comprising a hydrophobic material, preferably a perfume oil,

[0250] - A composite shell comprising a first material and a second material, wherein:

[0251] the first material is different from the second material,

[0252] the first material is coacervate particles,

[0253] • The second material is a polymeric material.

[0254] The previous embodiments and definitions, especially those for hydrophobic materials, coacervate particles (as described above), apply mutatis mutandis.

[0255] The polymeric material is preferably selected from the group consisting of polyureas, polyesters, polyurethanes, polyamides, polyacrylates, polysiloxanes, polycarbonates, polysulfonamides, polymers of urea and formaldehyde, polymers of melamine and formaldehyde, polymers of melamine and urea, or polymers of melamine and glyoxal, and mixtures thereof.

[0256] Preferably, the weight ratio of the first material to the second material in the slurry is 1:99 to 99:1, preferably 10:90 to 99:1.

[0257] Preferably, the second material is present in an amount less than 5 wt % based on the total weight of the microcapsule slurry.

[0258] In a particular embodiment, the shell material is a biodegradable material.

[0259] In a particular embodiment, the shell has a biodegradability within 60 days according to OECD 301 F of at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%.

[0260] In a particular embodiment, the core-shell microcapsules have a biodegradability within 60 days according to OECD 301 F of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%.

[0261] It will thus be appreciated that the core-shell microcapsules including all components, e.g. core, shell and optional coating, may have a biodegradability within 60 days according to OECD 301F of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%.

[0262] In a particular embodiment, the oil core, preferably a fragrance oil, has a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD 301F.

[0263] OECD301F is the standard test method for biodegradability of the Organization for Economic Co-operation and Development.

[0264] A typical method for extracting shells to measure biodegradability is disclosed in Gasparini et al. in Molecules 2020, 25, 718.

[0265] According to one embodiment, the coacervate particles have a particle size of 100 nm to 10 μm, preferably 200 nm to 5 μm.

[0266] Optional Ingredients

[0267] When the microcapsules are in the form of a slurry, the microcapsule slurry may contain auxiliary ingredients selected from the group consisting of thickeners / rheology modifiers, antimicrobial agents, opacity enhancers, mica particles, salts, pH stabilizers / buffering components, preferably in an amount of 0 to 15 wt %, based on the total weight of the slurry.

[0268] According to another embodiment, the microcapsule slurry of the present invention comprises additional free (ie unencapsulated) fragrance in an amount preferably ranging from 5 to 50% by weight based on the total weight of the slurry.

[0269] Multiple microcapsule system

[0270] According to one embodiment, the microcapsules of the present invention (microcapsules of the first type) can be used in combination with microcapsules of the second type.

[0271] Another object of the present invention is a microcapsule delivery system comprising:

[0272] - microcapsules of the invention as first type of microcapsules, and

[0273] - microcapsules of a second type, wherein the microcapsules of the first type differ from the microcapsules of the second type in their hydrophobic material and / or their wall material and / or their coacervate particles and / or their coating material.

[0274] According to a specific embodiment, the microcapsule delivery system is in the form of a slurry.

[0275] The wall of the second type of microcapsules can vary. As non-limiting examples, the polymer shell of the second type of microcapsules comprises a material selected from the group consisting of polyureas, polyurethanes, polyamides, polyhydroxyalkanoates, polyacrylates, polyesters, polyurethanes, polyepoxides, silicones, polycarbonates, polysulfonamides, urea-formaldehydes, melamine-formaldehyde resins, melamine-formaldehyde resins crosslinked with polyisocyanates or aromatic polyols, melamine-urea resins, melamine-glyoxal resins, gelatin / gum arabic shell walls, and mixtures thereof.

[0276] The second type of microcapsule may comprise an oil-based core comprising a hydrophobic active substance, preferably a fragrance, and a composite shell comprising a first material and a second material, wherein the first material and the second material are different, the first material is a coacervate, and the second material is a polymeric material. In a specific embodiment, the weight ratio between the first material and the second material is 50:50 to 99.9:0.1. In a specific embodiment, the coacervate comprises a first polyelectrolyte and a second polyelectrolyte, the first polyelectrolyte is preferably selected from proteins (e.g. gelatin), polypeptides or polysaccharides (e.g. chitosan), most preferably gelatin, and the second polyelectrolyte is preferably alginate, cellulose derivatives, guar gum, pectinate, carrageenan, polyacrylic acid and methacrylic acid or xanthan gum, or a vegetable gum such as acacia gum (gum arabic), most preferably gum arabic. The coacervate first material may be chemically hardened using a suitable crosslinking agent such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin, or may be enzymatically hardened using an enzyme such as transglutaminase. The second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, silicone, polycarbonate, polysulfonamide, polymer of urea and formaldehyde, polymer of melamine and formaldehyde, polymer of melamine and urea, or polymer of melamine and glyoxal, and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount of less than 3 wt%, preferably less than 1 wt%, based on the total weight of the second type of microcapsule slurry.

[0277] As non-limiting examples, the shell of the second type of microcapsules may be polyurea-based or polyurethane-based. The shell of the second type of microcapsules may also be composite, i.e., organic-inorganic, such as a composite shell composed of at least two types of crosslinked inorganic particles, or a shell produced by hydrolysis and condensation of a polyalkoxysilane macromer composition.

[0278] According to one form, the shell of the second type of microcapsules comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine-formaldehyde or melamine-glyoxal.

[0279] According to another embodiment, the shell of the second type of microcapsules is polyurea-based, made of, for example, but not limited to, isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules comprise a polyurea wall, which is a polymerization reaction product between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reactant selected from 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 specific embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol, 0.6% to 1% of a cationic copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (all percentages are defined by the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is an anionic or amphiphilic biopolymer, which can be selected, for example, from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0280] According to another embodiment, the microcapsule wall material of the second type of microcapsules may include any suitable resin, especially including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include reaction products of aldehydes and amines, and suitable aldehydes include formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril and mixtures thereof. Suitable melamines include methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof. Suitable ureas include dimethylol urea, methylated dimethylol urea, urea-resorcinol and mixtures thereof. Suitable materials for manufacture can be obtained from one or more of the following companies: Solutia Inc. (St Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), Sigma-Aldrich (St.Louis, Missouri USA).

[0281] According to another embodiment, the second type of microcapsules are single-shell aminoplast core-shell microcapsules obtainable by a process comprising the following steps:

[0282] 1) mixing a fragrance oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase;

[0283] 2) dispersing or dissolving an aminoplast resin and an optional stabilizer in water to form an aqueous phase;

[0284] 3) preparing an oil-in-water dispersion by mixing an oil phase and an aqueous phase, wherein the average droplet size is 1 to 100 microns;

[0285] 4) performing a curing step to form the wall of the microcapsule; and

[0286] 5) Optionally, the final dispersion is dried to obtain dry core-shell microcapsules.

[0287] According to one embodiment, the second type of microcapsules are formaldehyde-free capsules. A typical method for preparing a slurry of aminoplast formaldehyde-free microcapsules comprises the following steps:

[0288] 1) preparing an oligomeric composition comprising the reaction product of, or an oligomeric composition obtained by reacting together:

[0289] a. a polyamine component in the form of melamine or a mixture of melamine and at least one C1-C4 compound comprising two NH2 functional groups;

[0290] b. Glyoxal, C 4-6 The aldehyde component is in the form of a mixture of 2,2-dialkoxyacetaldehyde and optionally glyoxylate, the glyoxal / C 4-6 The molar ratio of 2,2-dialkoxyethanol is 1 / 1 to 10 / 1; and

[0291] c. Protonic acid catalyst;

[0292] 2) preparing an oil-in-water dispersion wherein the droplet size is from 1 to 600 microns and comprising:

[0293] a.Oil;

[0294] b. Water medium

[0295] c. at least one oligomeric composition as obtained in step 1;

[0296] d. at least one cross-linking agent selected from the group consisting of:

[0297] i.C4-C 12 Aromatic or aliphatic di- or triisocyanates and their biuret, triuret, trimer, trimethylolpropane adducts and mixtures thereof; and / or

[0298] ii. a di- or tri-oxirane compound of the formula

[0299] A-(Oxiran-2-ylmethyl) n

[0300] wherein n represents 2 or 3, A represents a C2-C6 group optionally containing 2 to 6 nitrogen and / or oxygen atoms;

[0301] e. Optionally, a C1-C4 compound comprising two NH2 functional groups;

[0302] 3) heating the dispersion;

[0303] 4) Cool the dispersion.

[0304] In another specific embodiment, the second type of microcapsules comprises:

[0305] - an oil-based core comprising a hydrophobic active substance, preferably a perfume,

[0306] - Optionally, an inner shell made from polymerized multifunctional monomers;

[0307] - A biopolymer shell comprising proteins, wherein at least one of the proteins is cross-linked.

[0308] According to a specific embodiment, the protein is selected from the group consisting of milk protein, caseinates such as sodium caseinate or calcium caseinate, casein, whey protein, hydrolyzed protein, gelatin, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate, most preferably sodium caseinate.

[0309] According to a specific embodiment, the protein comprises sodium caseinate and globular proteins, preferably selected from the group consisting of whey protein, beta-lactoglobulin, ovalbumin, bovine serum albumin, vegetable proteins and mixtures thereof.

[0310] The protein is preferably a mixture of sodium caseinate and whey protein.

[0311] According to a specific embodiment, the biopolymer shell comprises cross-linked proteins selected from the group consisting of sodium caseinate and / or whey proteins.

[0312] According to a particular embodiment, the second type of microcapsule slurry comprises at least one microcapsule made of:

[0313] - an oil-based core comprising a hydrophobic active substance, preferably a fragrance;

[0314] - an inner shell made from polymerized polyfunctional monomers; preferably a polyisocyanate having at least two isocyanate functional groups;

[0315] - a biopolymer shell comprising proteins, wherein at least one of the proteins is cross-linked; wherein the proteins preferably comprise a mixture comprising sodium caseinate and globular proteins, preferably whey proteins;

[0316] - Optionally, at least one outer mineral layer.

[0317] According to one embodiment, the sodium caseinate and / or whey protein are cross-linked proteins.

[0318] The weight ratio between sodium caseinate and whey protein is preferably from 0.01 to 100, preferably from 0.1 to 10, more preferably from 0.2 to 5.

[0319] In another specific embodiment, the second type of microcapsules are polyamide core-shell polyamide microcapsules comprising:

[0320] - an oil-based core comprising a hydrophobic active substance, preferably a perfume, and

[0321] - a polyamide shell comprising or obtainable from:

[0322] ·Acid chloride,

[0323] The first amino compound,

[0324] The second amino compound,

[0325] Optionally, carbohydrates.

[0326] According to a particular embodiment, the second type of microcapsules comprises:

[0327] - an oil-based core comprising a hydrophobic active substance, preferably a perfume, and

[0328] - a polyamide shell comprising or obtainable from:

[0329] Acid chloride, preferably in an amount of 5 to 98%, preferably 20 to 98%, more preferably 30 to 85% w / w;

[0330] a first amino compound, preferably in an amount of 1% to 50% w / w, preferably 7 to 40% w / w;

[0331] a second amino compound, preferably in an amount of 1% to 50% w / w, preferably 2 to 25% w / w;

[0332] Optionally, a stabilizer, preferably a biopolymer, preferably in an amount of 0 to 90%, preferably 0.1 to 75%, more preferably 1 to 70%,

[0333] Optionally, carbohydrates.

[0334] According to a particular embodiment, the second type of microcapsules comprises:

[0335] - an oil-based core comprising a hydrophobic active substance, preferably a perfume, and

[0336] - a polyamide shell comprising or obtainable from:

[0337] ·Acid chloride,

[0338] a first amino compound, which is an amino acid, preferably selected from the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and / or mixtures thereof,

[0339] a second amino compound selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine and / or mixtures thereof, and

[0340] a biopolymer, preferably selected from the group consisting of potato protein, chickpea protein, pea protein, algae protein, bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, soy protein, rice protein, whey protein, egg white protein, casein, sodium caseinate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin, and mixtures thereof,

[0341] Optionally, a carbohydrate, preferably selected from the group consisting of anionic alginates, preferably sodium alginate, pectin, lignin, anionic modified starch, carboxymethylcellulose, carrageenan, and mixtures thereof.

[0342] According to another form, the shell of the second type of microcapsules is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea-based and polyurethane-based microcapsule slurries are described, for example, in International Patent Application Publication No. WO2007 / 004166, European Patent Application Publication No. EP 2300146 and European Patent Application Publication No. EP25799. Generally, the method for preparing polyurea-based or polyurethane-based microcapsule slurries comprises the following steps:

[0343] a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase;

[0344] b) preparing an aqueous solution of an emulsifier or a colloid stabilizer to form a dispersed phase;

[0345] c) adding the oil phase to the water phase to form an oil-in-water dispersion wherein the average droplet size is from 1 to 500 μm, preferably from 5 to 50 μm; and

[0346] d) applying conditions sufficient to initiate interfacial polymerization and form microcapsules in the form of a slurry.

[0347] Perfuming composition and consumer product

[0348] The microcapsules of the present invention can be used in combination with active ingredients. Therefore, an object of the present invention is a composition comprising:

[0349] (i) microcapsules or microcapsule slurries as defined above;

[0350] (ii) an active ingredient, preferably selected from the group consisting of a cosmetic ingredient, a skin care ingredient, a perfume ingredient, a flavoring ingredient, a malodor counteracting ingredient, a bactericide ingredient, a fungicide ingredient, a pharmaceutical or agrochemical ingredient, a disinfectant ingredient, an insect repellent or attractant, and mixtures thereof.

[0351] The capsules of the present invention show good performance in terms of stability in challenging media.

[0352] Another object of the present invention is a perfuming composition comprising:

[0353] (i) microcapsules or microcapsule slurries as defined above, wherein the oil comprises fragrance;

[0354] (ii) at least one ingredient selected from the group consisting of a perfume carrier, a perfume co-ingredient, and mixtures thereof;

[0355] (iii) optionally, at least one flavor adjuvant.

[0356] As liquid perfume carriers, there may be mentioned, as non-limiting examples, emulsifying systems, i.e. solvents and surfactant systems, or solvents commonly used in the perfume industry. A detailed description of the properties and types of solvents commonly used in the perfume industry is not exhaustive. However, there may be mentioned, as non-limiting examples, solvents such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate, which are the most commonly used. For compositions comprising both perfume carriers and perfume co-ingredients, in addition to those previously specified, other suitable perfume carriers may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, for example those sold under the trademark PANDEFLOR. (Source: Exxon Chemical) Those known as glycol ethers and glycol ether esters, such as those sold under the trademark (Source: Dow Chemical Company) are known to those skilled in the art. By "fragrance co-ingredient" it is meant herein a compound which is used in a perfuming preparation or composition to impart a hedonic effect and which is not a microcapsule as defined above. In other words, to be considered a perfuming co-ingredient it must be recognized by those skilled in the art as being capable of imparting or modifying the odor of a composition in an active or pleasant manner, rather than merely possessing an odor.

[0357] The nature and type of the perfuming co-ingredients present in the perfuming composition do not guarantee a more detailed description here, which is in any case impossible to be exhaustive, and the technician can select them according to his common sense and according to the intended use or application and the required sensory effect. Generally speaking, these perfuming co-ingredients belong to different chemical classifications, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds and essential oils, and the perfuming co-ingredients can be natural or synthetic in origin. In any case, many of these co-ingredients are listed in references such as S. Arctander's work Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA or its updated version or other works of similar nature, and in the rich patent literature in the field of spices. It is also understandable that the co-ingredients can also be known compounds that release various types of perfuming compounds in a controlled manner.The auxiliary component can be selected from the group consisting of: 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyl oxy(phenyl)acetate, 3,7-dimethylocta-2,6-diene-1-yl oxy(phenyl)acetate. -yl ester, oxo(phenyl)acetate (Z)-hex-3-en-1-yl ester, hexadecanoic acid 3,7-dimethyl-2,6-octadien-1-yl ester, succinic acid bis(3,7-dimethyloct-2,6-dien-1-yl) ester, (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-en-1-yl , (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(oct-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenylethoxyprop-1-en-2-yl)benzene, 2-(1-phenylethoxyprop-1-en-2-yl)naphthalene, (2-phenylethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)benzene benzene, 4-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or a mixture thereof.

[0358] By "perfume adjuvants" it is meant here ingredients capable of imparting additional added benefits such as colour, specific lightfastness, chemical stability, etc. A detailed description of the nature and types of adjuvants commonly used in perfuming bases is not exhaustive, but it must be mentioned that said ingredients are well known to those skilled in the art.

[0359] Preferably, the perfuming composition according to the invention comprises from 0.01 to 30% by weight of microcapsules as defined above.

[0360] The microcapsules of the present invention can be advantageously used in many fields of application and in consumer products. The microcapsules can be used in liquid form for liquid consumer products or in powder form for powder consumer products.

[0361] According to a particular embodiment, the consumer product as defined above is a liquid and comprises:

[0362] a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product;

[0363] b) water or a water-miscible hydrophilic organic solvent; and

[0364] c) a microcapsule slurry or microcapsules as defined above,

[0365] d) Alternatively, non-encapsulated flavorants.

[0366] According to a particular embodiment, the consumer product as defined above is in powder form and comprises:

[0367] a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product;

[0368] b) Microcapsule powders as defined above.

[0369] c) Optionally, a flavor powder, which is different from the microcapsules as defined above.

[0370] In the case of microcapsules comprising a perfume oil-based core, the product of the invention is particularly useful for perfumed consumer products, such as products belonging to high-quality fragrances (fine fragrance) or "functional" fragrances. Functional fragrances include in particular personal care products, including hair care, body cleaning, skin care, hygiene care and home care products, including clothing care, surface care and air care. Therefore, another object of the present invention is a perfumed consumer product, which comprises as a perfume ingredient a microcapsule as defined above or a perfume composition as defined above. The perfume ingredient of the consumer product can be a combination of perfume microcapsules as defined above and free or non-encapsulated perfumes, as well as other types of perfume microcapsules than those disclosed here.

[0371] In particular, the following liquid consumer product is another object of the present invention, comprising:

[0372] a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product;

[0373] b) water or a water-miscible hydrophilic organic solvent; and

[0374] c) A perfuming composition as defined above.

[0375] Likewise, the following powdered consumer product is also part of the present invention, comprising:

[0376] (a) 2 to 65% by weight of at least one surfactant relative to the total weight of the consumer product; and

[0377] (b) A perfuming composition as defined above.

[0378] Thus, the microcapsules of the invention can be added as such or as part of a perfuming composition of the invention to an already perfumed consumer product.

[0379] For the sake of clarity, it has to be mentioned that a "perfumed consumer product" refers to a consumer product intended to deliver a perfuming effect among different benefits to the surface to which it is applied (e.g. skin, hair, fabric, paper or household surfaces) or to the air (air fresheners, deodorants / deodorants, etc.). In other words, a perfumed consumer product according to the present invention is a processed product comprising a functional formula (also called "base") and benefit agents, wherein an effective amount of microcapsules according to the present invention are present.

[0380] The nature and type of the other ingredients of the perfumed consumer product do not warrant a more detailed description here, which in any case cannot be exhaustive, and the skilled person is able to select them according to his general knowledge and according to the nature and the desired effect of the product in question. The formulations of the bases of the consumer product in which the microcapsules according to the invention can be incorporated can be found in the extensive literature relating to such products. These formulations do not warrant a detailed description here, which in any case cannot be exhaustive. The skilled person in the field of formulating such consumer products is fully able to select suitable components according to his general knowledge and the available literature.

[0381] Non-limiting examples of suitable perfumed consumer products may be perfumes, such as high-quality perfumes, colognes, aftershaves, body-splashes; fabric care products, such as liquid or solid detergents, tablets and capsules (single or multi-chamber), fabric softeners, dryer sheets, fabric refreshers, ironing water, or bleaching agents; personal care products, such as hair care products (e.g. shampoo, hair conditioning agents, coloring preparations or hair sprays), cosmetic preparations (e.g. vanishing creams, body lotions, or deodorants or antiperspirants), or skin care products (e.g. soaps, bath or shower mousses, body washes, etc.). wash), bath oil or shower gel, bath salts, or hygiene products); air care products, such as air fresheners or "ready-to-use" powdered air fresheners; or household care products, such as all-purpose cleaners, liquid or powdered or tablet dishwashing products, toilet bowl cleaners or products for cleaning various surfaces, such as sprays and wipes for treating / renovating textiles or hard surfaces (floors, tiles, stone floors, etc.); hygiene products, such as sanitary napkins, diapers, toilet paper.

[0382] Another object of the present invention is a consumer product comprising:

[0383] - personal care active bases, and

[0384] - a microcapsule or a microcapsule slurry as defined above or a perfuming composition as defined above,

[0385] Wherein the consumer product is in the form of a personal care composition.

[0386] The personal care active bases into which the microcapsules of the present invention can be incorporated can be found in the extensive literature relating to such products. These formulations do not warrant a detailed description here, which is by no means exhaustive. A person skilled in the art of formulating such consumer products is fully capable of selecting suitable components based on his general knowledge and the available literature.

[0387] The personal care composition is preferably selected from the group consisting of a hair care product (e.g. a shampoo, a hair conditioner, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream, a body lotion, or a deodorant or an antiperspirant), or a skin care product (e.g. a soap, a bath or shower mousse, a body wash, a bath oil or a shower gel, a bath salt, or a hygiene product).

[0388] Another object of the present invention is a consumer product comprising:

[0389] - home care or fabric care active bases, and

[0390] - a microcapsule or a microcapsule slurry as defined above or a perfuming composition as defined above,

[0391] Wherein the consumer product is in the form of a home care or fabric care composition.

[0392] Home care or fabric care bases into which the microcapsules of the invention can be incorporated can be found in the extensive literature relating to such products. These formulations do not warrant a detailed description here, which is in no way exhaustive. A person skilled in the art of formulating such consumer products is fully capable of selecting suitable components on the basis of his general knowledge and the available literature.

[0393] Preferably, the consumer product comprises 0.1 to 15 wt%, more preferably 0.2 to 5 wt% of the microcapsules of the invention, these percentages being defined by weight relative to the total weight of the consumer product. Of course, the above concentrations can be adjusted according to the desired beneficial effects of each product.

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

[0395] An object of the present invention is a consumer product, preferably a home care or fabric care consumer product, comprising the microcapsules or microcapsule slurry as defined above, wherein the pH of the consumer product is equal to or greater than 7.

[0396] For the liquid consumer products mentioned below, "active base" is understood to mean an active base comprising active materials (usually including surfactants) and water.

[0397] For solid consumer products referred to hereinafter, "active base" is understood to mean the active base comprising active materials (usually including surfactants) and adjuvants (e.g. bleaches, buffers; builders; soil removers or soil suspension polymers; granular enzyme particles, corrosion inhibitors, defoamers, foam suppressors; dyes, fillers and mixtures thereof).

[0398] Fabric softener

[0399] An object of the present invention is a consumer product in the form of a fabric softener composition comprising:

[0400] - a fabric softener active base; preferably comprising at least one active material selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (esterquats), Hamburg ester quaternary ammonium salts (HEQ), TEAQ (triethanolamine quaternary ammonium salts), silicones and mixtures thereof, the active base being preferably used in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0401] - microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition;

[0402] -Optionally, free fragrance oil.

[0403] Liquid detergent

[0404] An object of the present invention is a consumer product in the form of a liquid detergent composition comprising:

[0405] - a liquid detergent active base; preferably comprising at least one active material selected from the group consisting of anionic surfactants, such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants, such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucamides, the active base preferably being used in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0406] - microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition;

[0407] -Optionally, free fragrance oil.

[0408] Solid detergent

[0409] An object of the present invention is a consumer product in the form of a solid detergent composition comprising:

[0410] - a solid detergent active base; preferably comprising at least one active material selected from the group consisting of anionic surfactants such as alkylbenzene sulfonates (ABS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and nonionic surfactants such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucamides, the active base preferably being used in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0411] - microcapsule powder or microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition;

[0412] -Optionally, free fragrance oil.

[0413] Shampoo / shower gel

[0414] An object of the present invention is a consumer product in the form of a shampoo or shower gel composition comprising:

[0415] - a shampoo or shower gel active base; preferably comprising at least one active material selected from the group consisting of sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glucoside and amino acid-based surfactants and mixtures thereof, the active base preferably being used in an amount of 85 to 99.95% by weight based on the total weight of the composition,

[0416] - microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition;

[0417] -Optionally, free fragrance oil.

[0418] Rinse-off conditioner

[0419] An object of the present invention is a consumer product in the form of a rinse-off conditioner composition comprising:

[0420] - a rinse-off conditioner active base; preferably comprising at least one active material selected from the group consisting of cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, benzalkonium chloride, behenyltrimethylammonium chloride and mixtures thereof, the active base preferably being used in an amount of 85 to 99.95% by weight based on the total weight of the composition,

[0421] - microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition;

[0422] -Optionally, free fragrance oil.

[0423] Solid flavor enhancer

[0424] An object of the present invention is a consumer product in the form of a solid scent booster comprising:

[0425] - a solid carrier, preferably selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, sugars such as sucrose, mono-, disaccharides and polysaccharides and derivatives such as starch, cellulose, methylcellulose, ethylcellulose, propylcellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol and isomalt, PEG, PVP, citric acid or any water-soluble solid acid, fatty alcohols or fatty acids and mixtures thereof,

[0426] - Microcapsule slurry or microcapsules as defined above, in powder form, preferably in an amount of 0.05 to 15 wt%, more preferably 0.1 to 5 wt%, based on the total weight of the composition.

[0427] -Optionally, free fragrance oil.

[0428] Liquid Fragrance Enhancers

[0429] An object of the present invention is a consumer product in the form of a liquid flavor enhancer comprising:

[0430] - aqueous phase,

[0431] - a surfactant system consisting essentially of one or more than one nonionic surfactant, wherein the surfactant system has an average HLB of 10 to 14, preferably selected from the group consisting of ethoxylated aliphatic alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono- and polyglycerol esters, sucrose ester compounds, polyoxyethylene hydroxy esters, alkyl polyglucosides, amine oxides and combinations thereof;

[0432] - a linker selected from the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxycarboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactants with an HLB of less than 10, and mixtures thereof, and

[0433] - Microcapsule slurry or microcapsules as defined above, in the form of a slurry, preferably in an amount of 0.05 to 15 wt%, more preferably 0.1 to 5 wt%, based on the total weight of the composition.

[0434] -Optionally, free fragrance oil.

[0435] Hair dye

[0436] An object of the present invention is a consumer product in the form of an oxidative hair dyeing composition comprising:

[0437] - an oxidizing phase comprising an oxidizing agent and a basic phase comprising an alkaline agent, a dye precursor and a coupling compound; wherein the dye precursor and the coupling compound form an oxidative hair dye in the presence of the oxidizing agent, preferably in an amount of 85 to 99.95% by weight, based on the total weight of the composition,

[0438] - microcapsule slurry or microcapsules as defined above, preferably in an amount of 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition;

[0439] -Optionally, free fragrance oil.

[0440] Perfuming composition

[0441] According to a particular embodiment, the consumer product is in the form of a perfuming composition comprising, based on the total weight of the perfuming composition:

[0442] - 0.1 to 30% by weight, preferably 0.1 to 20% by weight, of microcapsules or microcapsule slurries as defined above,

[0443] - 0 to 40% by weight, preferably 3 to 40% by weight, of fragrance, and

[0444] - 20 to 90% by weight, preferably 40 to 90% by weight, of ethanol.

[0445] The present invention will now be further described by way of examples. It should be understood that the invention as claimed is not intended to be limited in any way by these examples.

[0446] Example

[0447] Example 1

[0448] Preparation of microcapsules according to the invention

[0449] Table 1: Fragrance Oil A

[0450] Element % in oil Ethyl 2-methylvalerate 3.20％ Eucalyptol 7.80％ 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde 0.75％ Aldehyde C10 0.75％ Citronella nitrile 4.30％ Isobornyl acetate 3.00％ 2-tert-Butyl-1-cyclohexyl acetate 9.80％ Citronellyl acetate 1.30％ 2-Methylundecanal 3.00％ Diphenyl ether 0.80％ Aldehyde C12 1.30％ Dicyclopentadienyl acetate 9.85％ β-Ionone 3.30％ γ-Undecalactone 18.75％ Hexyl Salicylate 15.90％ Benzyl salicylate 16.20％

[0451] Microcapsule A

[0452] Preparation of sodium caseinate / chitosan composite particle suspension

[0453] 2.0% sodium caseinate solution (sodium caseinate dissolved in deionized water) and 0.4% chitosan solution (chitosan dissolved in 1% acetic acid solution) were injected into two different streams of the four-stream multi-inlet vortex. The other two streams were injected with water with a pH value of 5.0. A pump (PHD ULTRA, Harvard) was used to inject at a speed of 40 mL / min.

[0454] The obtained complex coagulation suspension contained 0.5% sodium caseinate and 0.1% chitosan (average particle size: 347 nm) and had a pH value of 4.8-5.0.

[0455] Microcapsule preparation

[0456] Will contain fragrance oils (see Table 1) and The oil phase of (phenylenediisocyanate adduct polymer) was added to the complex coacervation suspension with an oil-water ratio of 3:7, and a stable Pickering emulsion was formed using a homogenizer.

[0457] The Pickering emulsion was transferred to a reactor and the interfacial reaction was carried out at 70 °C for 3 h.

[0458] Table 2: Composition of microcapsule A

[0459]

[0460] 1) D-110N (75% active solution of trimethylolpropane adduct of xylylene diisocyanate in ethyl acetate), source: Mitsui Chemicals, Inc., Japan

[0461] Microcapsule B

[0462] Preparation of sodium caseinate / chitosan composite particle suspension

[0463] 2.0% sodium caseinate solution (sodium caseinate dissolved in deionized water) and 0.4% chitosan solution (chitosan dissolved in 1% acetic acid solution) were injected into the dual-flow inlet vortex. The injection was performed at a rate of 40 mL / min using a pump (PHD ULTRA, Harvard).

[0464] The obtained complex coacervation suspension contained 1.0% sodium caseinate and 0.2% chitosan (average particle size: 764 nm), and the pH value of the suspension was adjusted to 4.8-5.0.

[0465] Microcapsule preparation

[0466] Will contain fragrance oils (see Table 1) and The oil phase of (phenylenediisocyanate adduct polymer) was added to the complex coacervation suspension with an oil-water ratio of 3:7, and a stable Pickering emulsion was formed using a homogenizer.

[0467] The Pickering emulsion was transferred to a reactor and the interfacial reaction was carried out at 70 °C for 3 h.

[0468] Table 3: Composition of microcapsule B

[0469] Element <![CDATA[Effective amount of ingredient (% by weight) a) > water 69.16 Sodium Caseinate 0.7 Chitosan 0.14 Fragrance Oil 29.4 <![CDATA[Benzene dimethyl diisocyanate adduct polymer 1) > 0.6

[0470] 1) D-110N (trimethylolpropane adduct of benzyl diisocyanate), source:

[0471] Japan Mitsui Chemicals, Inc.

[0472] Figure 2 A micrograph of microcapsule B is shown.

[0473] Microcapsule C

[0474] Preparation of whey protein / gum arabic composite particle suspension

[0475] 0.6% whey protein solution (whey protein dissolved in deionized water) and 1.2% gum arabic solution (gum arabic dissolved in deionized water) were injected into the dual-flow inlet vortex at a rate of 40 mL / min using a pump (PHD ULTRA, Harvard).

[0476] The obtained complex coacervation suspension contained 0.3% whey protein and 0.6% gum arabic (average particle size: 1.2 μm), and the pH value was adjusted to 4.3-4.6.

[0477] Will contain fragrance oils (see Table 1) and The oil phase of (phenylenediisocyanate adduct polymer) was added to the complex coacervation suspension with an oil-water ratio of 3:7, and a stable Pickering emulsion was formed using a homogenizer.

[0478] The Pickering emulsion was transferred to a reactor and the interfacial reaction was carried out at 70 °C for 3 h.

[0479] Table 4: Composition of microcapsule C

[0480] Element <![CDATA[Effective amount of ingredient (% by weight) a) > water 69.37 Whey protein 0.21 Gum Arabic 0.42 Fragrance Oil 29.4 <![CDATA[Benzene dimethyl diisocyanate adduct polymer 1) > 0.6

[0481] 1) D-110N (trimethylolpropane adduct of benzyl diisocyanate), source:

[0482] Japan Mitsui Chemicals, Inc.

[0483] Microcapsule D

[0484] Preparation of whey protein / chitosan composite particle suspension

[0485] 4.0% whey protein solution (whey protein dissolved in deionized water) and 0.8% chitosan solution (chitosan dissolved in 1% acetic acid solution) were injected into two streams of the four-stream multi-inlet vortex, and the other two streams were injected with water with a pH of 5.5. A pump (PHD ULTRA, Harvard) was used for injection at a speed of 40 mL / min.

[0486] The obtained complex coacervate suspension contained 1.0% whey protein and 0.2% chitosan (average particle size: 5.0 μm) and had a pH of about 5.5.

[0487] Will contain fragrance oils (see Table 1) and The oil phase of (phenylenediisocyanate adduct polymer) was added to the complex coacervation suspension with an oil-water ratio of 3:7, and a stable Pickering emulsion was formed using a homogenizer.

[0488] The Pickering emulsion was transferred to a reactor and the interfacial reaction was carried out at 70 °C for 3 h.

[0489] Table 5: Composition of microcapsule D

[0490] Element <![CDATA[Effective amount of ingredient (% by weight) a) > water 69.16 Whey protein 0.7 Chitosan 0.14 Fragrance Oil 29.4 <![CDATA[Benzene dimethyl diisocyanate adduct polymer 1) > 0.6

[0491] 1) D-110N (trimethylolpropane adduct of benzyl diisocyanate), source:

[0492] Japan Mitsui Chemicals, Inc.

[0493] Microcapsule E:

[0494] Preparation of potato protein / gum arabic composite particle suspension

[0495] A 2.0% potato protein solution (adjusted to pH 2 with a 5.0% hydrochloric acid solution and a 5.0% sodium hydroxide solution) and a 2.0% gum arabic solution (adjusted to pH 2 with a 5.0% hydrochloric acid solution and a 5.0% sodium hydroxide solution) were respectively injected into two different flow paths of a dual-flow multi-inlet vortex, and the injection was performed at a rate of 40 mL / min using a pump (PHD ULTRA, Harvard).

[0496] The obtained complex coacervate suspension contained 1.0% potato protein and 1.0% gum arabic (average particle size: 814.7 nm) and had a pH of 2.

[0497] Microcapsule preparation

[0498] Will contain fragrance oils (see Table 1) and The oil phase of (phenylenediisocyanate adduct polymer) was added to the water phase containing the complex coacervate suspension and melamine-formaldehyde resin (MF resin) at an oil-water ratio of 3:7. A homogenizer was then used to form a stable Pickering emulsion. The Pickering emulsion was transferred to a reactor and an interfacial reaction was carried out at 80°C for 2 hours. Ethylene urea was then added and the slurry was cooled to room temperature.

[0499] Table 6: Composition of microcapsule E

[0500]

[0501] 1) Solanic 200, source: Royal Avebe UA, Netherlands

[0502] 2) Melamine formaldehyde resin

[0503] 3) D-110N (75% active solution of trimethylolpropane adduct of xylylene diisocyanate in ethyl acetate), source: Mitsui Chemicals, Inc., Japan

[0504] Microcapsule F:

[0505] Preparation of simple zein particle suspension

[0506] Zein was dissolved in an ethanol / water (70 / 30 v / v) mixture to obtain a solution with a solid content of 2.0%. The zein solution and water were injected into two different streams of a dual-flow multi-inlet vortex. A pump (PHD ULTRA, Harvard) was used to inject at a speed of 40 mL / min. The resulting suspension was evaporated on a rotary evaporator to remove ethanol to obtain a final suspension with a solid content of about 6.8% (average particle size: 615.1 nm).

[0507] Microcapsule preparation

[0508] The oil phase containing the fragrance oil (see Table 1) and ethylene glycol dimethacrylate (EGDMA) was added to the dilute zein simple coagulation suspension (the zein particle content in the suspension was 2.0%), and the oil-water ratio was 3:7. A homogenizer was then used to form a stable Pickering emulsion, and the Pickering emulsion was transferred to a reactor. Ammonium persulfate (APS) solution and sodium bisulfite solution were added to the Pickering emulsion. The reaction was then allowed to react at 40°C for 3 hours under a N2 atmosphere, and then at 60°C for 1 hour.

[0509] Table 7: Composition of microcapsule F

[0510] Element <![CDATA[Effective amount of ingredient (% by weight) a) > water 69.67 Zein 1.34 EGDMA 2.16 APS 0.16 Sodium bisulfite 0.05 Fragrance Oil 26.62

[0511] Example 2

[0512] Characterization and performance of the microcapsules according to the invention

[0513] Size measurement: The average size (D[4,3]) of the microcapsule slurry was measured using a Mastersizer 3000 instrument from Malvern Instruments Ltd., UK

[0514] Zeta potential measurement: Zeta potential of microcapsules was examined using Zetasizer Nano ZS from Malvern Instruments Ltd., UK.

[0515] Example Average size Zeta Potential A 21.8μm -70.0mV B 25.8μm -37.5mV C 8.9μm -37.7mV D 39.7μm -4.5mV E 31.5μm -32.7mV F 48.9μm -12.5mV

[0516] stability

[0517] The storage stability of the capsules was evaluated in a fabric softener formulation (see ingredients in Table 8). The capsule dispersion was diluted in fabric softener (29.73 g) to obtain a final concentration of 0.20 wt% fragrance. The softener was stored at 37°C for up to 3 days. The amount of fragrance leaked from the capsules was then measured by solvent extraction with isooctane (10 mL) under stirring.

[0518] Table 8: Composition of fabric softener

[0519] product source weight% Stepantex VL 90A Stepan 8.88 Calcium chloride solution 10% 0.36 Proxel GXL Avecia 0.04 water 90.72 total 100

[0520] Stability Assessment Program

[0521] Fabric softener base containing microcapsules (2g) was introduced into a 20mL vial. The sample was diluted with water (2mL) using a Socorex 10mL bottle dispenser to reduce viscosity. The sample was shaken for 5 minutes using a Turbulat Shaker set at 40rpm. Isooctane containing 1,4-dibromobenzene as an internal standard was added to a vial (10mL) with a concentration accurate to approximately 90ng / μL. The sample was shaken at 40rpm for 45 minutes to extract free fragrance, and then centrifuged at 3.0G for 10 minutes to separate the two phases. The solvent phase was recovered and dried on MgSO4 for GC analysis.

[0522] Table 9: Perfume leakage from microcapsules in fabric softener after storage at 37°C for 3 days

[0523] Microcapsules Leakage amount (%) A 8.3 B 15.1 C 21.3 D 7.1 E 11.2

[0524] Therefore, the microcapsules according to the present invention show good stability in fabric softeners.

[0525] Performance Intensity

[0526] Addition amount of fragrance oil in fabric softener: 0.1%

[0527] Washing program:

[0528] (1) The capsule slurry was added to 26 g of unscented fabric softener, with a fragrance oil dosage of 0.1%, and stirred at 200 rpm for 5 minutes. A cotton towel was washed with the fabric softener.

[0529] (2) Cotton towels (30 cm x 30 cm: 36 towels 1.4 kg) were subjected to a conventional wash cycle in a washing machine (using 65 g of unscented detergent and the fabric softener containing capsules in step 1): water level: 43 L, wash cycle and time: conventional mode 42 minutes, water temperature: room temperature @ 25°C.

[0530] (3) The washed towels were dried at room temperature for 24 hours and then evaluated before and after rubbing.

[0531] A sensory panel test was conducted, asking 8 panelists to rate the intensity of the fragrance on the dry towel before and after rubbing on a scale of 1 (undetectable fragrance) to 7 (very strong fragrance).

[0532] Strength of performance (rating from 1 to 7): for microcapsule A, before kneading, 2.8±0.1; after kneading, 4.5±0.1.

[0533] Strength of performance (rating from 1 to 7): for microcapsule B, before kneading, 3.2±0.1; after kneading, 4.6±0.1.

[0534] Strength of performance (rating from 1 to 7): for microcapsule C, before kneading, 3.0±0.1; after kneading, 4.3±0.1.

[0535] Strength of performance (rating from 1 to 7): for microcapsule D, before kneading, 2.1±0.1; after kneading, 4.7±0.1.

[0536] Example 3

[0537] Liquid detergent composition

[0538] The microcapsules of the present invention were dispersed in the liquid detergent base described below to give a concentration of 0.22% encapsulated fragrance oil.

[0539] Table 10: Liquid detergent composition

[0540] Element Concentration [wt%] <![CDATA[Sodium C14-17 secondary alkyl sulfonate 1) > 7 <![CDATA[C12-18 fatty acids and C18-unsaturated fatty acids 2) > 7.5 <![CDATA[C12 / 14 fatty alcohol polyethylene glycol ether with 7 mol EO 3) > 17 Triethanolamine 7.5 Propylene glycol 11 Citric Acid 6.5 Potassium hydroxide 9.5 Protease 0.2 Amylase 0.2 Mannanase 0.2 <![CDATA[Acrylate / Steareth-20 Methacrylate Structured Crosslinked Polymer 4) > 6 Deionized water 27.4

[0541] 1) SAS 60; Source: Clariant

[0542] 2) K 12-18; Source: Cognis

[0543] 3) LA 070; Source: Clariant

[0544] 4) 88; Source: Dow Chemical

[0545] Example 4

[0546] Rinse-off conditioner

[0547] The microcapsules of the present invention are dispersed in the rinse-off conditioner base described below to give a concentration of 0.5% encapsulated fragrance oil.

[0548] Table 11: Rinse-off Conditioner Composition

[0549]

[0550] 1) Genamin KDM P, Clariant

[0551] 2) Tylose H10 Y G4, Shin Etsu

[0552] 3) Lanette O, BASF

[0553] 4)Arlacel 165-FP-MBAL-PA-(RB),Croda

[0554] 5)Incroquat Behenyl TMS-50-MBAL-PA-(MH)HA4112,Croda

[0555] 6)SP Brij S20 MBAL-PA(RB),Croda

[0556] 7) Xiameter DC MEM-0949 Emulsion, Dow Corning

[0557] 8) Alfa Aesar

[0558] Example 5

[0559] Shampoo composition

[0560] The microcapsules of the present invention are weighed and mixed into a shampoo composition to add the equivalent of 0.2% of perfume.

[0561] Table 12: Shampoo composition

[0562]

[0563] 1)Ucare Polymer JR-400, Noveon

[0564] 2) Schweizerhall

[0565] 3) Glydant, Lonza

[0566] 4)Texapon NSO IS, Cognis

[0567] 5) Tego Betain F 50, Evonik

[0568] 6)Amphotensid GB 2009,Zschimmer&Schwarz

[0569] 7) Monomuls 90L-12, Gruenau

[0570] 8) Monosodium paraben, NIPA

[0571] Example 6

[0572] Antiperspirant roll-on lotion composition

[0573] The microcapsules of the present invention were weighed and mixed into the antiperspirant roll-on emulsion composition to add fragrance equivalent to 0.2%.

[0574] Table 13: Antiperspirant Roll-On Lotion Composition

[0575] Element Amount (weight %) <![CDATA[Stearyl alcohol polyether-2 1) (Part A)]]> 3.25 <![CDATA[Polyoxyethylene (21) Stearyl Ether 2) (Part A)]]> 0.75 <![CDATA[PPG-15 Stearyl Ether 3) (Part A)]]> 4 Deionized water (Part B) 51 <![CDATA[50% aqueous solution of aluminum chlorohydrate 4) (Part C)]]> 40 Fragrances (Part D) 1

[0576] 1) BRIJ 72; Source: ICI

[0577] 2) BRIJ 721; Source: ICI

[0578] 3) ARLAMOL E; Source: UNIQEMA-CRODA

[0579] 4) LOCRON L; Source: CLARIAN

[0580] Heat Part A and Part B separately to 75°C; add Part A to Part B while stirring, and homogenize the mixture for 10 minutes. Then, cool the mixture while stirring. When the mixture reaches 45°C, slowly add Part C, and when the mixture reaches 35°C, slowly add Part D while stirring. Then cool the mixture to room temperature.

[0581] Example 7

[0582] Deodorant spray composition

[0583] The microcapsules of the present invention were weighed and mixed into the antiperspirant roll-on emulsion composition to add fragrance equivalent to 0.2%.

[0584] Table 14: Deodorant Spray Composition

[0585] Element Amount (weight %) Ethanol 95% 90.65 <![CDATA[Triclosan 1) > 0.26 Isopropyl myristate 9.09

[0586] 1) DP 300; Trademark and source: BASF

[0587] All ingredients were mixed and dissolved according to the order of Table 11. The aerosol can was then filled, compacted and the propellant added (aerosol fill: 40% active solution, 60% propane / butane 2.5 bar).

[0588] Example 8

[0589] Shower gel composition

[0590] The microcapsules of the present invention were weighed and mixed into the following composition to add fragrance equivalent to 0.2%.

[0591] Table 15: Body wash composition

[0592] Element Amount (weight %) Function Deionized water 49.350 Solvents <![CDATA[Sodium EDTA 1) > 0.050 Chelating agents <![CDATA[Acrylate copolymer 2) > 6.000 Thickener <![CDATA[Sodium C12-C15 alcohol polyether sulfate 3) > 35.000 Surfactants Sodium hydroxide 20% aqueous solution 1.000 pH Adjusters <![CDATA[Cocamidopropyl betaine 4) > 8.000 Surfactants <![CDATA[Methylchloroisothiazolinone and Methylisothiazolinone 5) > 0.100 preservative Citric acid (40%) 0.500 pH Adjusters

[0593] 2) EDETA B powder; Trademark and source: BASF

[0594] 3) CARBOPOL AQUA SF-1 polymer; Trademark and source: NOVEON

[0595] 4) ZETESOL AO 328U; Trademark and source: ZSCHIMMER&SCHWARZ

[0596] 5)TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0597] 6) KATHON CG; Trademark and source: ROHM & HASS

[0598] Example 9

[0599] Unit dose formulation

[0600] Sufficient exemplary microcapsules are weighed and mixed into a unit dose formulation to add the equivalent of 0.2% flavor.

[0601] The unit dose formulation may be contained in a PVOH (polyvinyl alcohol) film.

[0602] Table 16: Composition of unit dose

[0603] Element Concentration [wt%] C12-C14 Alkyl Polyethoxylate 15 C12-C14 Alkyl Polyethoxylate Sulfate Monoethanolamine Salt 9.5 Linear alkylbenzene sulfonic acid 17 Citric Acid 0.5 C12-C18 fatty acids 17 Enzymes 1.2 Fluorescent brightener 0.3 1,2-Propanediol 12 glycerin 9 Sodium hydroxide 1 Monoethanolamine 6 PDMS 2.5 Potassium sulfite 0.2 water 8.8 total 100

Claims

1. A method for preparing a microcapsule slurry, comprising the following steps: 1) suspending the coacervate particles in a solvent to form a dispersed phase; 2) mixing at least one multifunctional monomer with a hydrophobic material to form an oil phase; 3) The oil phase is added to the dispersed phase and they are mixed to form a two-phase Pickering emulsion under conditions that allow the formation of a microcapsule slurry by interfacial polymerization.

2. The method of claim 1, wherein the coacervate particles are prepared by transient nanoprecipitation.

3. The method according to claim 1 or 2, wherein the coacervate particles comprise at least one polymer.

4. The method of any of the preceding claims, wherein the coacervate particles comprise a first polymer and a second polymer.

5. The method according to claim 4, wherein the first polymer contains at least one cationic group, such as an amino group, an azole group, an amide group, a quaternary ammonium cation or a guanidine cation.

6. The method according to any of the preceding claims, wherein the first polymer is selected from the group consisting of proteins, chitosan and its derivatives, cationically modified polysaccharides, polyethyleneimines, poly(amidoamines), poly(amino-co-esters), cationic polyacrylates and mixtures thereof.

7. The method according to any of the preceding claims, wherein the second polymer is selected from the group consisting of modified starch, gum arabic, chitosan, sodium caseinate, alginates, cellulose derivatives, guar gum, pectinates, pectin, carrageenan, polyacrylic and methacrylic acids, xanthan gum or polyanions consisting of sodium triphosphate, trisodium trimetaphosphate, sodium pyrophosphate, dextran sulfate sodium salt and mixtures thereof.

8. The method of any preceding claim, wherein the coacervate particles comprise a polymer and a polyion oppositely charged to the polymer.

9. A method according to any of the preceding claims, wherein the coacervate particles comprise an active ingredient, preferably selected from the group consisting of a cosmetic ingredient, a skin care ingredient, a perfume ingredient, a flavor ingredient, an odor counteracting ingredient, an antimicrobial ingredient, a pharmaceutical or agrochemical ingredient, a disinfectant ingredient, an insect repellent or attractant, and mixtures thereof.

10. The method according to any one of the preceding claims, wherein the multifunctional monomer is selected from the group consisting of at least one isocyanate, anhydride or maleic anhydride, acid chloride, epoxide, (meth)acrylate monomer, alkoxysilane, and mixtures thereof.

11. A microcapsule slurry obtained by the method of any one of the preceding claims, wherein the microcapsules comprise: - a core, preferably an oil-based core, comprising a hydrophobic material, preferably a perfume oil, - A composite shell comprising a first material and a second material, wherein: the first material is different from the second material, the first material is coacervate particles, • The second material is a polymeric material. 12 . The microcapsule slurry according to claim 11 , wherein the weight ratio of the first material to the second material in the slurry is 10:90 to 99:1, preferably 30:70 to 99:

1.

13. The microcapsule slurry according to claim 11 or 12, wherein the second material is present in an amount of less than 5 wt% based on the total weight of the microcapsule slurry.

14. A consumer product comprising: - personal care active bases, and - a microcapsule slurry or microcapsules as defined in any one of claims 11 to 13, Wherein the consumer product is in the form of a personal care composition.

15. A consumer product comprising: - home care or fabric care active bases, and - a microcapsule slurry or microcapsules as defined in any one of claims 11 to 13, Wherein the consumer product is in the form of a home care or fabric care composition.

Images