Microcapsules and process for preparing microcapsules
Core-shell microcapsules with a hydrophobic core and a P-CI and inorganic moiety-based shell address the volatility and stability issues in perfumery, providing eco-friendly and controlled release of fragrances in consumer products.
Patent Information
- Application Number
- PCT/EP2024/076854
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-28
- Filing Date
- 2024-09-25
- Publication Date
- 2025-04-03
AI Technical Summary
The perfumery industry faces challenges in maintaining the olfactive benefit of odoriferous compounds due to their volatility, particularly 'top-notes', and requires delivery systems that ensure stability in challenging bases without dissociating or degrading.
The development of core-shell microcapsules with a hydrophobic core and a shell formed from the reaction product of compounds with at least two P-CI functions and inorganic moieties, which provides eco-friendly and stable microcapsules for perfuming compositions.
These microcapsules offer enhanced stability and controlled release of perfuming ingredients, maintaining olfactive performance while being eco-friendly and suitable for use in challenging consumer product bases.
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Abstract
Description
[0001] MICROCAPSULES AND PROCESS FOR PREPARING MICROCAPSULES
[0002] Technical Field
[0003] The present invention relates to core-shell microcapsules. A process for the preparation of said microcapsules 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.
[0004] Background of the Invention
[0005] One of the problems faced by the perfumery industry lies in the relatively rapid loss of olfactive benefit provided by odoriferous compounds due to their volatility, particularly that of “top-notes”. In order to tailor the release rates of volatiles, delivery systems such as microcapsules containing a perfume are needed to protect and later release the core payload when triggered. A key requirement from the industry regarding these systems is to survive suspension in challenging bases without physically dissociating or degrading. This is referred to as stability for the delivery system. For instance, fragranced personal and household cleansers containing high levels of aggressive surfactant detergents are very challenging for the stability of microcapsules.
[0006] Polyurea and polyurethane-based microcapsule slurry are widely used for example in perfumery industry for instance as they provide a long lasting pleasant olfactory effect after their applications on different substrates. Those microcapsules have been widely disclosed in the prior art.
[0007] In addition to the performance in terms of stability and olfactive performance, the consumer demand for eco-friendly delivery systems is more and more important and is driving the development of new delivery systems.
[0008] There is therefore still a need to provide new microcapsules using more eco- friendly materials, while not compromising on the performance of the microcapsules, in particular in terms of stability in a challenging medium such as a consumer product base, as well as in delivering a good performance in terms of active ingredient delivery, e.g. olfactive performance in the case of perfuming ingredients.
[0009] The present invention is proposing a solution to the above-mentioned problem by providing new microcapsules and a process for preparing said microcapsules. Summary of the invention
[0010] It has now been found that performing core-shell microcapsules encapsulating hydrophobic material could be obtained by reacting at least one compound having at least two P-CI functions and at least one compound containing inorganic moieties. The microcapsules of the invention therefore provide a solution to the above-mentioned problems as it allows preparing eco-friendly microcapsules with the desired stability in challenging bases.
[0011] In a first aspect, the present invention relates to a core-shell microcapsule comprising:
[0012] - a core comprising a hydrophobic material, and
[0013] - a shell comprising the reaction product between at least one compound containing inorganic moieties and at least one compound having at least two P-CI functions.
[0014] Another object of the invention is a core-shell microcapsule slurry comprising at least one microcapsule, the microcapsule comprising:
[0015] - a core comprising a hydrophobic material, and
[0016] - a shell comprising the reaction product between at least one compound containing inorganic moieties and at least one compound having at least two P-CI functions.
[0017] Another object of the invention is a process for preparing a core-shell microcapsule slurry comprising the steps of: a) Optionally, providing at least one compound having at least two P-CI functions b) admixing at least one hydrophobic material with the optional compound obtained in step a) to form an oil phase; c) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; d) Optionally, dispersing the two-phases dispersion into a continuous phase C2 comprising optionally at least one compound having at least two P-CI functions to form a multiple dispersion; e) curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and or / step d) and / or step e).
[0018] The present invention also relates to perfumed consumer products and flavoured edible products comprising the microcapsules or microcapsule slurry as defined above.
[0019] Detailed description of the invention
[0020] Unless stated otherwise, percentages (%) are meant to designate a percentage by weight of a composition.
[0021] By “active ingredient”, it is meant a single compound or a combination of ingredients.
[0022] By “perfume or flavour oil”, it is meant a single perfuming or flavouring compound or a mixture of several perfuming or flavouring compounds.
[0023] By “consumer product” or “end-product” it is meant a manufactured product ready to be distributed, sold and used by a consumer.
[0024] For the sake of clarity, by the expression “dispersion” in the present invention it is meant a system in which particles are dispersed in a continuous phase of a different composition and it specifically includes a suspension or an emulsion.
[0025] A “microcapsule”, or the similar, in the present invention it is meant that coreshell microcapsules have a particle size distribution in the micron range (e.g. a mean diameter (d(v, 0.5)) comprised preferably between about 1 and 3000 microns, more preferably between 1 and 500 microns) and comprise an external solid polymeric shell and an internal continuous oil phase enclosed by the external shell.
[0026] By “microcapsule slurry”, it is meant microcapsule(s) that is (are) dispersed in a liquid. According to an embodiment, the slurry is an aqueous slurry, i.e the microcapsule(s) is (are) dispersed in an aqueous phase.
[0027] “Dispersing phase” and “continuous phase” can be used indifferently in the present invention.
[0028] CORE-SHELL MICROCAPSULE In a first aspect, the present invention relates to a core-shell microcapsule comprising:
[0029] - a core comprising a hydrophobic material, and
[0030] - a shell comprising the reaction product between at least one compound containing inorganic moieties and at least one compound having at least two P-CI functions.
[0031] Hydrophobic material
[0032] According to an embodiment, the core is an oil-based core.
[0033] The hydrophobic material according to the invention can be “inert” material like solvents or active ingredients.
[0034] By “hydrophobic material”, it is meant any hydrophobic material which forms a two- phase dispersion when mixed with water. The hydrophobic material is typically liquid at about 20°C.
[0035] According to an embodiment, the hydrophobic material is a hydrophobic active ingredient.
[0036] When the hydrophobic materials is an active ingredient, it is preferably chosen from the group consisting of flavors, flavor ingredients, perfumes, perfume ingredients, nutraceuticals, cosmetics, pest control agents, biocide actives, agrochemical ingredients, and mixtures thereof.
[0037] According to a particular embodiment, the hydrophobic material comprises a phase change material (PCM).
[0038] According to a particular embodiment, the hydrophobic material comprises a mixture of a perfume with another ingredient selected from the group consisting of nutraceuticals, cosmetics, pest control agents and biocide actives.
[0039] According to a particular embodiment, the hydrophobic material comprises a mixture of biocide actives with another ingredient selected from the group consisting of perfumes, nutraceuticals, cosmetics, pest control agents.
[0040] According to a particular embodiment, the hydrophobic material comprises a mixture of pest control agents with another ingredient selected from the group consisting of perfumes, nutraceuticals, cosmetics, biocide actives.
[0041] According to a particular embodiment, the hydrophobic material comprises a perfume. According to a particular embodiment, the hydrophobic material consists of a perfume.
[0042] According to a particular embodiment, the hydrophobic material consists of biocide actives.
[0043] According to a particular embodiment, the hydrophobic material consists of pest control agents.
[0044] By “perfume” (or also “perfume oil”) what is meant here is an ingredient or a composition that is a liquid at about 20°C. According to any one of the above embodiments said perfume oil can be a perfuming ingredient alone or a mixture of ingredients in the form of a perfuming composition. As a “perfuming ingredient” it is meant here a compound, which is used for the primary purpose of conferring or modulating an odor. In other words such an ingredient, to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to at least impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor. For the purpose of the present invention, perfume oil also includes a combination of perfuming ingredients with substances which together improve, enhance or modify the delivery of the perfuming ingredients, such as perfume precursors, modulators, emulsions or dispersions, as well as combinations which impart an additional benefit beyond that of modifying or imparting an odor, such as long-lastingness, blooming, malodor counteraction, antimicrobial effect, microbial stability, pest control.
[0045] The nature and type of the perfuming ingredients present in the oil phase do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to intended use or application and the desired organoleptic effect. In general terms, these perfuming ingredients belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulfurous heterocyclic compounds and essential oils (for example Thyme oil), and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. In particular one may cite perfuming ingredients which are commonly used in perfume formulations, such as:
[0046] - Aldehydic ingredients: decanal, dodecanal, 2-methyl-undecanal, 10- undecenal, octanal, nonanal and / or nonenal;
[0047] - Aromatic-herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5- methyltricyclo[6.2.1.02'7]undecan-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4- dimethyl-1 ,3-oxathiane, 2, 2, 7 / 8, 9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or alpha-pinene;
[0048] - Balsamic ingredients: coumarin, ethylvanillin and / or vanillin;
[0049] - Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-p-menthen-8-yl acetate and / or 1 ,4(8)-p- menthadiene;
[0050] - Floral ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethanol,
[0051] 3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2- cyclohexen-1-yl)-3-buten-2-one, (1 E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1- penten-3-one, 1-(2,6,6-trimethyl-1 ,3-cyclohexadien-1-yl)-2-buten-1-one, (2E)- 1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3- cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2- buten-1-one, 3-(3,3 / 1 ,1-dimethyl-5-indanyl)propanal, 2,5-dimethyl-2- indanmethanol, 2, 6, 6-trimethyl-3-cyclohexene-1 -carboxylate, 3-(4,4-dimethyl- 1-cyclohexen-1-yl)propanal, hexyl salicylate, 3,7-dimethyl-1 ,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate, geraniol, p-menth-1- en-8-ol, 4-(1 ,1-dimethylethyl)-1-cyclohexyle acetate, 1 , 1 -dimethyl-2- phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate , high cis methyl dihydrojasmonate, 3-methyl-5-phenyl-1 -pentanol, verdyl proprionate, geranyl acetate, tetrahydro linalool, cis-7-p-menthanol, propyl (S)-2-(1 ,1- dimethylpropoxyjpropanoate, 2-methoxynaphthalene, 2,2,2-trichloro-1 - phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1 - carbaldehyde, amylcinnamic aldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyle acetate, 4-(1 , 1 -dimethylethyl)-1 -cyclohexyl acetate, verdyl isobutyrate and / or mixture of methylionones isomers; - Fruity ingredients: gamma-undecalactone, 2,2,5-trimethyl-5- pentylcyclopentanone, 2-methyl-4-propyl-1 ,3-oxathiane, 4-decanolide, ethyl 2- methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gammanonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1 ,3- dioxolane-2-acetate, diethyl 1 ,4-cyclohexanedicarboxylate, 3-methyl-2-hexen- 1-yl acetate, 1 -[3,3-dimethylcyclohexyl]ethyl [3-ethyl-2-oxiranyl]acetate and / or diethyl 1 ,4-cyclohexane dicarboxylate;
[0052] - Green ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3- cyclohexene-1 -carbaldehyde, 2-tert-butyl-1 -cyclohexyl acetate, styrallyl acetate, allyl (2-methylbutoxy)acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1 -ol and / or 1 -(5,5-dimethyl-1 -cyclohexen-1 -yl)-4-penten-1 -one;
[0053] Musk ingredients: 1 ,4-dioxa-5, 17-cycloheptadecanedione, (Z)-4- cyclopentadecen-1 -one, 3-methylcyclopentadecanone, 1-oxa-12- cy cl o h exa decen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z)-9- cycloheptadecen-1 -one, 2-{( 1 S)-1 -[(1 R)-3,3-dimethylcyclohexyl]ethoxy}-2- oxoethyl propionate, 3-methyl-5-cyclopentadecen-1-one, 4, 6, 6, 7,8,8- hexamethyl-1 ,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (1 S,1'R)-2-[1- (3',3'-dimethyl-1 '-cyclohexyl)ethoxy]-2-methylpropyl propanoate, oxacyclohexadecan-2-one and / or (1 S, 1 'R)-[1-(3',3'-dimethyl-1 '- cyclohexyl)ethoxycarbonyl]methyl propanoate;
[0054] - Woody ingredients: 1-[(1 RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3- dimethyl-5-[(1 R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'- dimethylspiro[oxirane-2,9'-tricyclo[6.2.1.02'7]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-naphtalenyl)-1 -ethanone, patchouli oil, terpenes fractions of patchouli oil, Clearwood®, (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;
[0055] - Other ingredients (e.g. amber, powdery spicy or watery): dodecahydroSa, 6,6, 9a-tetramethyl-naphtho[2, 1-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(1 ,3- benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1 ,5-benzodioxepin-3(4H)- one, 2,5,5-trimethyl-1 ,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1- phenyl)butanal.
[0056] It is also understood that said ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds also known as properfume or profragrance. Non-limiting examples of suitable properfumes 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-dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1-yl oxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1 -yl) succinate, (2-((2-methylundec-1 -en-1 - yl)oxy)ethyl)benzene, 1 -methoxy-4-(3-methyl-4-phenethoxybut-3-en-1 -yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2- methylundec-1 -ene, (2-((2-methylundec-1 -en-1 -yl)oxy)ethoxy)benzene, 2-methyl-1 - (octan-3-yloxy)undec-1 -ene, 1 -methoxy-4-(1 -phenethoxyprop-1 -en-2-yl)benzene, 1 - methyl-4-(1 -phenethoxyprop-1 -en-2-yl)benzene, 2-(1 -phenethoxyprop-1 -en-2- yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1- yl)oxy)prop-1 -en-2-yl)naphthalene, (2-((2- pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2- phenylvinyl)oxy)benzene, (2-((2-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.
[0057] The perfuming ingredients may be dissolved in a solvent of current use in the perfume industry. The solvent is preferably not an alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, 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, like for example Abalyn® or benzyl benzoate. Preferably the perfume comprises less than 30% of solvent. More preferably the perfume comprises less than 20% and even more preferably less than 10% of solvent, all these percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially free of solvent.
[0058] Preferred perfuming ingredients are those having a high steric hindrance and in particular those from one of the following groups:
[0059] Group 1 : perfuming ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched Ci to C4 alkyl or alkenyl substituent;
[0060] Group 2: perfuming ingredients comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted with at least one linear or branched C4 to Cs alkyl or alkenyl substituent;
[0061] Group 3: perfuming ingredients comprising a phenyl ring or perfuming ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched C5 to Cs alkyl or alkenyl substituent or with at least one phenyl substituent and optionally one or more linear or branched Ci to C3 alkyl or alkenyl substituents;
[0062] Group 4: perfuming ingredients comprising at least two fused or linked Cs and / or Cs rings;
[0063] Group 5: perfuming ingredients comprising a camphor-like ring structure;
[0064] Group 6: perfuming ingredients comprising at least one C7 to C20 ring structure;
[0065] Group 7: perfuming ingredients having a logP value above 3.5 and comprising at least one tert-butyl or at least one trichloromethyl substitutent;
[0066] Examples of ingredients from each of these groups are:
[0067] Group 1 : 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (origin: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2- dimethyl-6-methylene-1 -cyclohexanecarboxylate (origin: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1 ,8-p- menthadiene-7-ol (origin: Firmenich SA, Geneva, Switzerland), 1-p-menthene-4- ol, (1 RS,3RS,4SR)-3-p-mentanyl acetate, (1 R,2S,4R)-4,6,6-trimethyl- bicyclo[3, 1 , 1 ]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (origin: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1 ,4- cyclohexane diethyldicarboxylate (origin: Firmenich SA, Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (origin: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethyl-benzo[B]furan- 2-one (origin: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1 ,3- dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde;
[0068] Group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (origin: Givaudan SA, Vernier, Switzerland), (1 'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'- cyclopenten-1'-yl)-2-buten-1-ol (origin: Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1 '-yl)-4-penten-2-ol (origin: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-
[0069] 3-oxo-2-pentyl-1 -cyclopentane acetate (origin: Firmenich SA, Geneva, Switzerland), 2, 2, 5-trimethyl-5-pentyl-1 -cyclopentanone (origin: Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4- penten-2-ol (origin: Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3- trimethyl-3-cyclopenten-1-yl)-2-pentanol (origin, Givaudan SA, Vernier, Switzerland);
[0070] Group 3: damascenes, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (origin: Firmenich SA, Geneva, Switzerland), (1 'R)-2-[2-(4'-methyl-3'-cyclohexen-1 '- yl)propyl]cyclopentanone, alpha-ionone, beta-ionone, damascenone, mixture of 1- (5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1- cyclohexen-1-yl)-4-penten-1-one (origin: Firmenich SA, Geneva, Switzerland), 1- (2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (origin: Firmenich SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-Dimethyl-1 '-cyclohexyl)ethoxycarbonyl]methyl propanoate (origin: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1 -cyclohexyl acetate (origin: International Flavors and Fragrances, USA), 1-(2, 2,3,6- tetramethyl-cyclohexyl)-3-hexanol (origin: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (origin: Firmenich SA, Geneva, Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpenyl isobutyrate, 4-(1 , 1 -dimethylethyl)-1 -cyclohexyl acetate (origin: Firmenich SA, Geneva, Switzerland), 8-methoxy-1-p-menthene, (1S,1'R)-2-[1-(3',3'- dimethyl-1 '-cyclohexyl) ethoxy]-2-methylpropyl propanoate (origin: Firmenich SA, Geneva, Switzerland), para tert-butylcyclohexanone, menthenethiol, 1-methyl-4- (4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde, allyl cyclohexylpropionate, cyclohexyl salicylate, 2-methoxy-4-methylphenyl methyl carbonate, ethyl 2- methoxy-4-methylphenyl carbonate, 4-ethyl-2-methoxyphenyl methyl carbonate;
[0071] Group 4: Methyl cedryl ketone (origin: International Flavors and Fragrances, USA), a mixture of (1 RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.02 6]dec-3-en-8-yl 2- methylpropanoate and (1 RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1 ,02'6]dec-4-en-8-yl
[0072] 2-methylpropanoate, vetyverol, vetyverone, 1 -(octahydro-2, 3, 8, 8-tetramethyl-2- naphtalenyl)-1 -ethanone (origin: International Flavors and Fragrances, USA), (5RS.9RS, 10SR)-2,6,9, 10-tetramethyl-1 -oxaspiro[4.5]deca-3,6-diene and the (5RS,9SR, 10RS) isomer, 6-ethy I-2 , 10, 10-tri methyl- 1 -oxaspiro[4.5]deca-3,6- diene, 1 ,2,3,5,6,7-hexahydro-1 ,1 ,2,3,3-pentamethyl-4-indenone (origin: International Flavors and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5- indanyl)propanal and 3-(1 ,1-dimethyl-5-indanyl)propanal (origin: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1 ,0(2,7)]undec-4-ene-9-spiro-2'- oxirane (origin: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3- oxatricyclo[6.2.1 ,0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (origin: Firmenich SA, Geneva, Switzerland), octalynol, (dodecahydroSa, 6,6, 9a-tetramethyl-naphtho[2,1-b]furan, origin: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl acetate and tricyclo[5.2.1 ,0(2,6)]dec-4-en-8-yl acetate as well as tricyclo[5.2.1 ,0(2,6)]dec-3- en-8-yl propanoate and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl propanoate, (+)- (1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1 ,1]heptane-3-spiro-2'-cyclohexen-4'-one; Group 5: camphor, borneol, isobornyl acetate, 8-isopropyl-6-methyl- bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedrane, (8-methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1 .0(1 ,5)]undecane (origin: Firmenich SA, Geneva, Switzerland), cedrene, cedrenol, cedrol, mixture of 9-ethylidene-3- oxatricyclo[6.2.1.0(2,7)]undecan-4-one and 10-ethylidene-3- oxatricyclo[6.2.1.02’7]undecan-4-one (origin: Firmenich SA, Geneva, Switzerland),
[0073] 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1 Jdecane (origin: Firmenich SA, Geneva, Switzerland);
[0074] Group 6: (trimethyl-13-oxabicyclo-[10.1 ,0]-trideca-4,8-diene (origin: Firmenich SA, Geneva, Switzerland), 9-hexadecen-16-olide (origin: Firmenich SA, Geneva, Switzerland), pentadecenolide (origin: Firmenich SA, Geneva, Switzerland), 3-methyl- (4 / 5)-cyclopentadecenone .(origin: Firmenich SA, Geneva, Switzerland), 3- methylcyclopentadecanone (origin: Firmenich SA, Geneva, Switzerland), pentadecanolide (origin: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (origin: Firmenich SA, Geneva, Switzerland), 1-ethoxyethoxy)cyclododecane (origin: Firmenich SA, Geneva, Switzerland), 1 ,4-dioxacycloheptadecane-5, 17-dione, 4,8- cyclododecadien-1 -one; Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (origin: Givaudan SA, Vernier, Switzerland), 2, 2, 2-trichloro-1 -phenylethyl acetate.
[0075] 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 said perfume comprises at least 30%, preferably at least 50% of ingredients from Groups 3 to 7, as defined above. Most preferably said perfume comprises at least 30%, preferably at least 50% of ingredients from Groups 3, 4, 6 or 7, as defined above.
[0076] According to another preferred embodiment, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients having a logP above 3, preferably above 3.5 and even more preferably above 3.75.
[0077] According to a particular embodiment, the perfume used in the invention contains less than 10% of its own weight of primary alcohols, less than 15% of its own weight of secondary alcohols and less than 20% of its own weight of tertiary alcohols. Advantageously, the perfume used in the invention does not contain any primary alcohols and contains less than 15% of secondary and tertiary alcohols.
[0078] According to an embodiment, the oil phase (or the oil-based core) comprises:
[0079] - 25-100wt% of a perfume oil comprising at least 15wt% of high impact perfume raw materials having a Log T<-4, and
[0080] - 0-75wt% of a density balancing material having a density greater than 1.07 g / cm3.
[0081] “High impact perfume raw materials" should be understood as perfume raw materials having a LogT<-4. The odor threshold concentration of a chemical compound is determined in part by its shape, polarity, partial charges and molecular mass. For convenience, the odor threshold concentration is presented as the common logarithm of the threshold concentration, i.e., Log [Threshold] (“LogT”).
[0082] A “density balancing material’ should be understood as a material having a density greater than 1.07 g / cm3and having preferably low or no odor.
[0083] The odor threshold concentration of a perfuming compound is determined by using a gas chromatograph (“GO”). Specifically, the gas chromatograph is calibrated to determine the exact volume of the perfume oil ingredient injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation to last 12 seconds, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of the perfuming compound. To determine the threshold concentration, solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed. The average across all panelists determines the odor threshold concentration of the perfuming compound. The determination of odor threshold is described in more detail in C. Vuilleumier et al., Multidimensional Visualization of Physical and Perceptual Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, Vol. 33, September, 2008, pages 54-61 .
[0084] The nature of high impact perfume raw materials having a Log T<-4 and density balancing material having a density greater than 1.07 g / cm3are described in WO2018115250, the content of which are included by reference.
[0085] According to an embodiment, the high impact perfume raw materials having a Log T<-4 are selected from the group consisting of (+-)-1-methoxy-3-hexanethiol, 4- (4-hydroxy-1-phenyl)-2-butanone, 2-methoxy-4-(1-propenyl)-1 -phenyl acetate, pyrazobutyle, 3-propylphenol, 1-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3- phenylpropyl)pyridine, 1-(3,3 / 5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one , 1- (5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, a mixture comprising (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[b]furan-2-one and
[0086] (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-4alpha,8abeta-dimethyl-4a-naphthalenol, patchoulol, 2- methoxy-4-(1-propenyl)phenol, mixture comprising (+-)-5,6-dihydro-4-methyl-2- phenyl-2H-pyran and tetrahydro-4-methylene-2-phenyl-2H-pyran, mixture comprising 4-methylene-2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,6-dihydro- 2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonylenic aldehyde, 2-methoxy-4- propylphenol, 3-methyl-5-phenyl-2-pentenenitrile, 1-(spiro[4.5]dec-6 / 7-en-7-yl)-4- penten-1-one(, 2-methoxynaphthalene, (-)-(3aR,5AS,9AS,9BR)-3a, 6,6,9a- tetramethyldodecahydronaphtho[2,1-b]furan, 5-nonanolide, (3aR,5AS,9AS,9BR)- 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 7-isopropyl-2H,4H-1 ,5- benzodioxepin-3-one, coumarin, 4-methylphenyl isobutyrate, (2E)-1-(2,6,6-trimethyl-
[0087] 1.3-cyclohexadien-1-yl)-2-buten-1-one, beta, 2,2, 3-tetramethyl-delta-methylene-3- cyclopentene-1 -butanol, delta damascone ((2E)-1-[(1 RS,2SR)-2,6,6-trimethyl-3- cyclohexen-1-yl]-2-buten-1-one), (+-)-3,6-dihydro-4,6-dimethyl-2-phenyl-2h-pyran, anisaldehyde, paracresol, 3-ethoxy-4-hydroxybenzaldehyde, methyl 2- aminobenzoate, ethyl methylphenylglycidate, octalactone gamma, ethyl 3-phenyl-2- propenoate, (-)-(2E)-2-ethyl-4-[(1 R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-2-buten-1-ol, paracresyl acetate, dodecalactone, tricyclone, (+)-(3R,5Z)-3-methyl-5- cyclopentadecen-1-one, undecalactone, (1 R,4R)-8-mercapto-3-p-menthanone, (3S,3AS,6R,7AR)-3,6-dimethylhexahydro-1-benzofuran-2(3H)-one, beta ionone, (+-)- 6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1 ,3,5-undecatriene, 10-undecenal, (9E)- 9-undecenal (9Z)-9-undecenal, (Z)-4-decenal, (+-)-ethyl 2-methylpentanoate, 1 ,2- diallyldisulfane, 2-tridecenenitrile, 3-tridecenenitrile, , (+-)-2-ethyl-4,4-dimethyl-1 ,3- oxathiane, (+)-(3R,5Z)-3-methyl-5-cyclopentadecen-1-one, 3-(4-tert- butylphenyl)propanal, allyl (cyclohexyloxy)acetate, methylnaphthylketone, (+-)-(4E)-3- methyl-4-cyclopentadecen-1 -one, (+-)-5E3-methyl-5-cyclopentadecen-1 -one, cyclopropylmethyl 3-hexenoate, (4E)-4-methyl-5-(4-methylphenyl)-4-pentenal, (+-)-1- (5-propyl-1 ,3-benzodioxol-2-yl)ethanone, 4-methyl-2-pentylpyridine, (+-)-(E)-3- methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, (2S,5R)-5-methyl-2-(2-propanyl)cyclohexanone oxime, 6-hexyltetrahydro-2H-pyran- 2-one, (+-)-3-(3-isopropyl-1-phenyl)butanal, methyl 2-(3-oxo-2- pentylcyclopentyl)acetate, 1-(2,6,6-trimethyl-1-cyclohex-2-enyl)pent-1-en-3-one, indol, 7-propyl-2H,4H-1 ,5-benzodioxepin-3-one, ethyl praline, (4- methylphenoxy)acetaldehyde, ethyl tricyclo[5.2.1.0.2'6]decane-2-carboxylate, (+)- (1'S,2S,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1 '-yl)-4-penten-2-ol, (4E)-
[0088] 3.3-dimethyl-5-[(1 R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-isopropyl-6- methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, methylnonylacetaldehyde, 4-formyl-
[0089] 2-methoxyphenyl 2-methylpropanoate, (E)-4-decenal, (+-)-2-ethyl-4-(2,2,3-trimethyl-
[0090] 3-cyclopenten-1-yl)-2-buten-1-ol, (1 R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]oct-3- ene, (1 R,4R,5R)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane, (-)-(3R)-3,7-dimethyl-1 ,6- octadien-3-ol, (E)-3-phenyl-2-propenenitrile, 4-methoxybenzyl acetate, (E)-3-methyl- 5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, allyl (2 / 3-methylbutoxy)acetate, (+-)-(2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (1 E)-1 -(2,6,6-trimethyl- 1-cyclohexen-1-yl)-1-penten-3-one, and mixtures thereof.
[0091] According to an embodiment, perfume raw materials having a Log T<-4 are chosen in the group consisting of aldehydes, ketones, alcohols, phenols, esters lactones, ethers, epoxydes, nitriles and mixtures thereof.
[0092] According to an embodiment, perfume raw materials having a Log T<-4 comprise at least one compound chosen in the group consisting of alcohols, phenols, esters lactones, ethers, epoxydes, nitriles and mixtures thereof, preferably in amount comprised between 20 and 70% by weight based on the total weight of the perfume raw materials having a Log T<-4.
[0093] According to an embodiment, perfume raw materials having a Log T<-4 comprise between 20 and 70% by weight of aldehydes, ketones, and mixtures thereof based on the total weight of the perfume raw materials having a Log T<-4.
[0094] The remaining perfume raw materials contained in the oil-based core may have therefore a Log T>-4.
[0095] According to an embodiment, the perfume raw materials having a Log T>-4 are chosen in 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, verdyl propionate, 1 -(octahydro-2, 3, 8, 8-tetramethyl-2-naphtalenyl)-1 -ethanone, methyl 2-((1 RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate, (+-)-(E)-4-methyl-3-decen-5- ol, 2,4-dimethyl-3-cyclohexene-1 -carbaldehyde, 1 , 3 , 3-tri methy I-2- oxabicyclo[2.2.2]octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa-12 / 13-cyclohexadecen-2-one, (+-)-3-(4-isopropylphenyl)-2- methylpropanal, aldehyde C11 , (+-)-2,6-dimethyl-7-octen-2-ol, allyl 3- cyclohexylpropanoate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, allyl heptanoate, 2-(2-methyl-2-propanyl)cyclohexyl acetate, 1 , 1 -dimethyl-2- phenylethyl butyrate, geranyl acetate, neryl acetate, (+-)-1 -phenylethyl acetate, 1 ,1- dimethyl-2-phenylethyl acetate, 3-methyl-2-butenyl acetate, ethyl 3-oxobutanoate, (2Z)-ethyl 3-hydroxy-2-butenoate, 8-p-menthanol, 8-p-menthanyl acetate, 1-p- menthanyl acetate, (+-)-2-(4-methyl-3-cyclohexen-1-yl)-2-propanyl acetate, (+-)-2- methylbutyl butanoate, 2-{(1S)-1-[(1 R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethyl propionate, 3, 5, 6-trimethyl-3-cyclohexene-1 -carbaldehyde, 2,4,6-trimethyl-3- cyclohexene-1 -carbaldehyde, 2-cyclohexylethyl acetate, octanal, ethyl butanoate, (+- )-(3E)-4-(2,6,6-trimethyl-1 / 2-cyclohexen-1-yl)-3-buten-2-one, 1-[(1 RS,6SR)-2,2,6- trimethylcyclohexyl]-3-hexanol, 1 ,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, 1 ,3,3- trimethyl-2-oxabicyclo[2.2.2]octane, ethyl hexanoate, undecanal, decanal, 2- phenylethyl acetate, (1S,2S,4S)-1 ,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)- 1 ,7,7-trimethylbicyclo[2.2.1]heptan-2-ol ), (+-)-3,7-dimethyl-3-octanol, 1-methyl-4-(2- propanylidene)cyclohexene, (+)-(R)-4-(2-methoxypropan-2-yl)-1 -methylcyclohex-1 - ene, verdyl acetate, (3R)-1-[(1 R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1- [(1 R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3R)-1-[(1S,6S)-2,2,6- trimethylcyclohexyl]-3-hexanol, (+)-(1 S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]- 2-methylpropyl propanoate, and mixtures thereof.
[0096] According to an embodiment, the core comprises a perfume formulation comprising:
[0097] - 0 to 60 wt.% of a hydrophobic solvent (based on the total weight of the perfume formulation),
[0098] - 40 to 100 wt.% of a perfume oil (based on the total weight of the perfume formulation), wherein the perfume oil has at least two, preferably all of the following characteristics: o at least 35%, preferably at least 40%, preferably at least 50%, more preferably at least 60% of perfuming ingredients having a log P above 3, preferably above 3.5, o at least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40% of Bulky materials of groups 1 to 6, preferably 3 to 6 as herein defined and o at least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least 30% of high impact perfume materials having a Log T < -4, optionally, further hydrophobic active ingredients.
[0099] According to a particular embodiment, the perfume comprises 0 to 60 wt.% of a hydrophobic solvent.
[0100] According to a particular embodiment, the hydrophobic solvent is a density balancing material preferably chosen in the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenylacetate, phenylethyl phenylacetate, triacetin, ethyl citrate, methyl and ethyl salicylate, benzyl cinnamate, and mixtures thereof.
[0101] In a particular embodiment, the hydrophobic solvent has Hansen Solubility Parameters compatible with entrapped perfume oil.
[0102] The term "Hansen solubility parameter" is understood refers to a solubility parameter approach proposed by Charles Hansen used to predict polymer solubility and was developed around the basis that the total energy of vaporization of a liquid consists of several individual parts. To calculate the "weighted Hansen solubility parameter" one must combine the effects of (atomic) dispersion forces, (molecular) permanent dipole-permanent dipole forces, and (molecular) hydrogen bonding (electron exchange). The weighted Hansen solubility parameter" is calculated as (6D2+ 6P2+ 6H2)0 5, wherein 6D is the Hansen dispersion value (also referred to in the following as the atomic dispersion fore), 6P is the Hansen polarizability value (also referred to in the following as the dipole moment), and 6H is the Hansen Hydrogenbonding ("h-bonding") value (also referred to in the following as hydrogen bonding). For a more detailed description of the parameters and values, see Charles Hansen, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, Danish Technical Press (Copenhagen, 1967).
[0103] Euclidean difference in solubility parameter between a fragrance and a solvent iS Calculated as (4 (6Dsolvent_6Dfragrance)2+ (6P solvent_6Pfragrance)2 + (SHsolvent-
[0104] CHfragrance)2)0 5, in which 6DSOivent, 6PSOivent, and 6HSoivent, are the Hansen dispersion value, Hansen polarizability value, and Hansen h-bonding values of the solvent, respectively; and 6Dfragrance, QPfragrance, and CHfragrance are the Hansen dispersion value, Hansen polarizability value, and Hansen h-bonding values of the fragrance, respectively.
[0105] In a particular embodiment, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a first group consisting of: an atomic dispersion force (6D) from 12 to 20, a dipole moment (6P) from 1 to 8, and a hydrogen bonding (6H) from 2.5 to 1 1 .
[0106] In a particular embodiment, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of: an atomic dispersion force (6D) from 12 to 20, preferably from 14 to 20, a dipole moment (6P) from 1 to 8, preferably from 1 to 7, and a hydrogen bonding (6H) from 2.5 to 11 , preferably from 4 to 11. In a particular embodiment, at least 90% of the perfume oil, preferably at least 95% of the perfume oil, most preferably at least of 98% of the perfume oil has at least two Hansen solubility parameters selected from a first group consisting of: an atomic dispersion force (6D) from 12 to 20, a dipole moment (6P) from 1 to 8, and a hydrogen bonding (6H) from 2.5 to 11 .
[0107] In a particular embodiment, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of: an atomic dispersion force (6D) from 12 to 20, preferably from 14 to 20, a dipole moment (6P) from 1 to 8, preferably from 1 to 7, and a hydrogen bonding (6H) from 2.5 to 11 , preferably from 4 to 11.
[0108] According to an embodiment, the perfuming formulation comprises a fragrance modulator (that can be used in addition to the hydrophobic solvent when present or as substitution of the hydrophobic solvent when there is no hydrophobic solvent).
[0109] Preferably, the fragrance modulator is defined as a fragrance material with i. a vapor pressure of less than 0.0008 T orr at 22°C; ii. a clogP of 3.5 and higher, preferable 4.0 and higher and more preferable 4.5 iii. at least two Hansen solubility parameters selected from a first group consisting of: an atomic dispersion force from 12 to 20, a dipole moment from 1 to 7, and a hydrogen bonding from 2.5 to 11 , iv. at least two Hansen solubility parameters selected from a second group consisting of: an atomic dispersion force from 14 to 20, a dipole moment from 1 to 8, and a hydrogen bonding from 4 to 11 , when in solution with a compound having a vapor pressure range of 0.0008 to 0.08 Torr at 22°C.
[0110] Preferably, as examples the following ingredients can be listed as modulators but the list in not limited to the following materials: alcohol C12, oxacyclohexadec- 12 / 13-en-2-one, 3-[(2',2',3'-trimethyl-3'-cyclopenten-T-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecen-1-one, cyclopentadecanone, (8Z)- oxacycloheptadec-8-en-2-one, 2-[5-(tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5- methyl-2-furyl]-2-propanol, muguet aldehyde, 1 ,5,8-trimethyl-13- oxabicyclo[10.1.0]trideca-4,8-diene, (+-)-4,6,6,7,8,8-hexamethyl-1 , 3, 4, 6,7,8- hexahydrocyclopenta[g]isochromene, (+)-(1 S,2S,3S,5R)-2,6,6- trimethylspiro[bicyclo[3.1 .1 ]heptane-3, 1 '-cyclohexane]-2'-en-4'-one, oxacyclohexadecan-2-one, 2-{( 1 S)-1 -[(1 R)-3,3-dimethylcyclohexyl]ethoxy}-2- oxoethyl propionate, (+)-(4R,4aS,6R)-4,4a-dimethyl-6-(1 -propen-2-yl)-4,4a,5,6,7,8- hexahydro-2(3H)-naphthalenone, amylcinnamic aldehyde, hexylcinnamic aldehyde, hexyl salicylate, (1 E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1 ,6-heptadien-3-one, (9Z)- 9-cycloheptadecen-1 -one.
[0111] According to a particular embodiment, the hydrophobic material is free of any active ingredient (such as perfume). According to this particular embodiment, it comprises, preferably consists of hydrophobic solvents, preferably chosen in the group consisting of isopropyl myristate, tryglycerides (e.g. Neobee® MCT oil, vegetable oils), D-limonene, silicone oil, mineral oil, and mixtures thereof with optionally hydrophilic solvents preferably chosen in the group consisting of 1 ,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1 ,2- propanediol), 1 ,3-propanediol, dipropylene glycol, glycerol, glycol ethers and mixtures thereof .
[0112] The term "biocide" refers to a chemical substance capable of killing living organisms (e.g. microorganisms) or reducing or preventing their growth and / or accumulation. Biocides are commonly used in medicine, agriculture, forestry, and in industry where they prevent the fouling of, for example, water, agricultural products including seed, and oil pipelines. A biocide can be a pesticide, including a fungicide, herbicide, insecticide, algicide, molluscicide, miticide and rodenticide; and / or an antimicrobial such as a germicide, antibiotic, antibacterial, antiviral, antifungal, antiprotozoal and / or antiparasite.
[0113] As used herein, a "pest control agent" indicates a substance that serves to repel or attract pests, to decrease, inhibit or promote their growth, development or their activity. Pests refer to any living organism, whether animal, plant or fungus, which is invasive or troublesome to plants or animals, pests include insects notably arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.
[0114] By "flavor oil", it is meant here a flavoring ingredient or a mixture of flavoring ingredients, solvents or adjuvants of current use for the preparation of a flavoring formulation, i.e. a particular mixture of ingredients which is intended to be added to an edible composition or chewable product to impart, improve or modify its organoleptic properties, in particular its flavor and / or taste. Flavoring ingredients are well known to a person skilled in the art and their nature does not warrant a detailed description here, which in any case would not be exhaustive, the skilled flavorist being able to select them on the basis of his general knowledge and according to the intended use or application and the organoleptic effect it is desired to achieve. Many of these flavoring ingredients are listed in reference texts such as in the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, N.J., USA, or its more recent versions, or in other works of similar nature such as Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press or Synthetic Food Adjuncts, 1947, by M. B. Jacobs, van Nostrand Co., Inc. Solvents and adjuvants of current use for the preparation of a flavoring formulation are also well known in the art.
[0115] In a particular embodiment, the flavor is a mint flavor. In a more particular embodiment, the mint is selected from the group consisting of peppermint and spearmint.
[0116] In a further embodiment, the flavor is a cooling agent or mixtures thereof.
[0117] In another embodiment, the flavor is a menthol flavor.
[0118] Flavors that are derived from or based on fruits where citric acid is the predominant, naturally-occurring acid include but are not limited to, for example, citrus fruits (e.g. lemon, lime), limonene, strawberry, orange, and pineapple. In one embodiment, the flavors food is lemon, lime or orange juice extracted directly from the fruit. Further embodiments of the flavor comprise the juice or liquid extracted from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, and any other citrus fruit, or variation or hybrid thereof. In a particular embodiment, the flavor comprises a liquid extracted or distilled from oranges, lemons, grapefruits, key limes, citrons, clementines, mandarins, tangerines, any other citrus fruit or variation or hybrid thereof, pomegranates, kiwifruits, watermelons, apples, bananas, blueberries, melons, ginger, bell peppers, cucumbers, passion fruits, mangos, pears, tomatoes, and strawberries.
[0119] In a particular embodiment, the flavor comprises a composition that comprises limonene, in a particular embodiment, the composition is a citrus that further comprises limonene.
[0120] In another particular embodiment, the flavor comprises a flavor selected from the group comprising strawberry, orange, lime, tropical, berry mix, and pineapple.
[0121] The phrase flavor includes not only flavors that impart or modify the smell of foods but include taste imparting or modifying ingredients. The latter do not necessarily have a taste or smell themselves but are capable of modifying the taste that other ingredients provides, for instance, salt enhancing ingredients, sweetness enhancing ingredients, umami enhancing ingredients, bitterness blocking ingredients and so on.
[0122] In a further embodiment, suitable sweetening components may be included in the particles described herein. In a particular embodiment, a sweetening component is selected from the group consisting of sugar (e.g., but not limited to sucrose), a stevia component (such as but not limited to stevioside or rebaudioside A), sodium cyclamate, aspartame, sucralose, sodium saccharine, and Acesulfam K or mixtures thereof.
[0123] Compound having at least two P-CI functions
[0124] According to the invention, the shell of the microcapsule comprises the reaction product between at least one compound having at least two P-CI functions and a compound having inorganic moieties.
[0125] By “compound having at least two P-CI functions” it should be understood that the P-CI functions can be on the same P atom or on two different P atoms in the same molecule.
[0126] According to an embodiment, the term “P-CI function” refers to a covalent bond between a P atom and a Cl atom.
[0127] According to an embodiment, the at least two Cl functions are on the same P atom.
[0128] According to an embodiment, the compound having at least two P-CI functions comprises a P atom that is connected to at least two Cl atoms via covalent bonds.
[0129] The compound having at least two P-CI functions can be selected from the group consisting of compound with formula PXCI3, where X is O, S, or NH or NR1where R1 is any hydrocarbon group, optionally comprising heteroatoms. Preferably, the compound having at least two P-CI functions can be selected from the group consisting of compound phosphorus oxy trichloride (POCI3), thiophosphorus trichloride (PSCI3), phosphorimidic trichloride (PNHCI3), N-substituted-phosphorimidic trichloride (PNR1Cl3), phosphorus trichloride, phosphorus pentachloride, hexachlorocyclophosphazene (HCCP) and its derivatives, R1OPXCl2 (with X is O, NH, NR1or S), such as alkyl phosphorodichloridate (R1OPOCl2) and / or alkyl dichlorothiophosphate (R1OPSCh) (wherein R1 can be any hydrocarbon group optionally with heteroatoms); poly(dichlorophosphazene), 3,9-dichloro-2,4,8, 10- tetraoxa-3A5,9A5-diphosphaspiro[5.5]undecane 3,9-dioxide, and mixtures thereof.
[0130] According to an embodiment, the hydrocarbon group is a functional or not Ci- C50 hydrocarbon group.
[0131] The compound having at least two P-CI functions can be selected from the group consisting of compounds with formula PXCI3, PNHCI3 and PNR1Cl3, where X is O, S, where R1is any hydrocarbon group, optionally comprising heteroatoms. Preferably, the compound having at least two P-CI functions can be selected from the group consisting of compound phosphorus oxy trichloride (POCI3), thiophosphorus trichloride (PSCI3), phosphorimidic trichloride (PNHCI3), N-substituted-phosphorimidic trichloride (PNR1Cl3), phosphorus trichloride, phosphorus pentachloride, hexachlorocyclophosphazene (HCCP), 2,2,4,4-tetraamino-6,6- dichlorocyclotriphosphazene (TCPA), a copolymer of hexa-(4-aldehyde-phenoxy)- cyclo-triphosphazene and 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene (HACP-co-TCPA), R1OPXCI2 (with X is O, NH, NR1or S), such as alkyl phosphorodichloridate (R1OPOCl2) and / or alkyl dichlorothiophosphate (R1OPSCl2) (wherein R1can be any hydrocarbon group optionally with heteroatoms); poly(dichlorophosphazene), 3,9-dichloro-2,4,8,10-tetraoxa-3A5,9A5- diphosphaspiro[5.5]undecane 3,9-dioxide, and mixtures thereof.
[0132] It is understood that by “... hydrocarbon group ...” it is meant that said group consists of hydrogen and carbon atoms and can be in the form of an aliphatic hydrocarbon, i.e. linear or branched saturated hydrocarbon (e.g. alkyl group), a linear or branched unsaturated hydrocarbon (e.g. alkenyl oralkynyl group), a saturated cyclic hydrocarbon (e.g. cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g. cycloalkenyl or cycloalkynyl), or can be in the form of an aromatic hydrocarbon, i.e. aryl group, or can also be in the form of a mixture of said type of groups, e.g. a specific group may comprise a linear alkyl, a branched alkenyl (e.g. having one or more carbon-carbon double bonds), a (poly)cycloalkyl and an aryl moiety, unless a specific limitation to only one type is mentioned. Similarly, in all the embodiments of the invention, when a group is mentioned as being in the form of more than one type of topology (e.g. linear, cyclic or branched) and / or being saturated or unsaturated (e.g. alkyl, aromatic or alkenyl), it is also meant a group which may comprise moieties having any one of said topologies or being saturated or unsaturated, as explained above. Similarly, in all the embodiments of the invention, when a group is mentioned as being in the form of one type of saturation or unsaturation, (e.g. alkyl), it is meant that said group can be in any type of topology (e.g. linear, cyclic or branched) or having several moieties with various topologies.
[0133] It is understood that with the term “... a hydrocarbon group, optionally comprising ...” it is meant that said hydrocarbon group optionally comprises one, two, three or more heteroatoms. These groups can either substitute a hydrogen atom of the hydrocarbon group and thus be laterally attached to said hydrocarbon, or substitute a carbon atom (if chemically possible) of the hydrocarbon group and thus be inserted into the hydrocarbon chain. For example, a -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group comprising an alcohol group (substitution of a hydrogen atom), i.e. a C4 hydrocarbon comprising an oxygen atom; a -CH2-CH2-COO- CH2-CH2CH2-CH2- group represents a C7 hydrocarbon group comprising one ester group (substitution of carbon atoms / insertion into the hydrocarbon chain), i.e. a C7 hydrocarbon comprising two oxygen atoms and, similarly, a -CH2-CH2-O-CH2-CH2-O- CH2-CH2- group represents a Ce hydrocarbon group comprising two ether groups, i.e. a Ce hydrocarbon comprising two oxygen atoms.
[0134] According to a particular embodiment, the compound having at least two P-CI functions is hexachlorocyclophosphazene (HCCP) or its derivatives or its polymer. According to a particular embodiment, the compound having at least two P-CI functions is hexachlorocyclophosphazene (HCCP) 2,2,4,4-tetraamino-6,6- dichlorocyclotriphosphazene (TCPA), a copolymer of hexa-(4-aldehyde-phenoxy)- cyclo-triphosphazene (HACP) and 2,2,4,4-tetraamino-6,6- dichlorocyclotriphosphazene (HACP-co-TCPA) or mixtures thereof..
[0135] According to an embodiment, the compound having at least two P-CI functions is only PCI5 when the inorganic moiety is not a silicone or Ca(OH)2 or when the compound having inorganic moieties does not comprise hydrocarbon moieties.
[0136] According to an embodiment, the compound having at least two P-CI functions is not PCI5.
[0137] Compound having inorganic moieties According to an embodiment, the term inorganic moiety relates to non-carbon- based structural units and in particular wherein the bonding does not rely on carbon frameworks.
[0138] According to an embodiment, a compound having inorganic moieties is a compound with a minority (not more than 50%, preferably not more than 30%, even more preferably not more than 20%, not more than 10%, more preferably not more than 4%, based on the total number of bonds, preferably covalent bonds) or even no carbon-carbon bonds and / or carbon-hydrogen bonds.
[0139] According to an embodiment, a compound having inorganic moieties is a compound with a minority (not more than 30%, preferably not more than 20%, not more than 10%, more preferably not more than 4%, based on the total number of bonds, preferably covalent bonds) or even no carbon-carbon bonds and carbonhydrogen bonds.
[0140] According to an embodiment, the compound having inorganic moieties is a monomer, polymer, oligomer, particles and mixtures thereof.
[0141] When the compound containing inorganic moieties is a particle, it can be chosen in the group consisting of calcium phosphate, silica, silicates, titanium dioxide, aluminium oxide, zinc oxide, iron oxide, mica, kaolin, montmorillonite, laponite, bentonite, perlite, dolomite, diatomite, vermiculite, hectorite, gibbsite, illite, kaolinite, aluminosilicates, gypsum, bauxite, magnesite, talc, magnesium carbonate, calcium carbonate, diatomaceous earth and mixtures.
[0142] According to an embodiment, the compound having inorganic moieties is 1 ,3,5- triaza-2A5,4A5,6A5-triphosphacyclohexa-1 ,3,5-triene-2,2,4,4,6,6-hexamine.
[0143] According to an embodiment, the compound having inorganic moieties is a silicon containing monomer, polymer, oligomers, particles and mixtures thereof, preferably selected from the group consisting of amino functional silanes, sulfur functional silanes, nonfunctional silanes and mixtures thereof.
[0144] The amino functional silane can be chosen in the group consisting of Bis[3- (triethoxysilyl)propyl]amine, 3-aminopropyltriethoxysilane 3-(2-
[0145] Aminoethylamino)propyltriethoxysilane, 1 ,1 ,1-Triethoxysilanamine and its polymers and mixtures thereof. The sulfur functional silane can be chosen in the group consisting of 3- mercaptopropyltriethoxysilane.
[0146] The non-functional silane can be chosen in the group consisting of 1 ,2- bis(triethoxysilyl)ethane, silicone, 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane and tri ethoxysilane and mixtures thereof.
[0147] According to an embodiment, the compound having inorganic moieties is not a mineral.
[0148] According to an embodiment, the compound having inorganic moieties is not an inert mineral.
[0149] According to an embodiment, the compound having inorganic moieties and the compound having at least two P-CI functions are not the same molecule.
[0150] According to an embodiment, the shell contains, preferably consists of, an inorganic part and an organic part,
[0151] According to an embodiment, the shell contains at least 10% of inorganic moiety.
[0152] According to an embodiment, the shell contains at least 20% of inorganic moiety.
[0153] According to an embodiment, the shell contains at least 30% of inorganic moiety.
[0154] According to an embodiment, the shell contains at least 40% of inorganic moiety.
[0155] According to an embodiment, the shell is substantially inorganic.
[0156] By “substantially inorganic”, it should be understood that the shell contains at least 50%, preferably at least 70%, more preferably at least 90%, even most preferably 100% of inorganic moieties.
[0157] Nucleophile
[0158] According to a particular embodiment, the shell comprises the reaction product between at least one compound containing inorganic moieties, at least one compound having at least two P-CI functions and at least a nucleophile.
[0159] According to the invention, a nucleophile compound is defined as a chemical species that donates an electron pair to an electrophile to form a chemical bond in relation to a reaction. The nucleophile compound may be chosen in the group consisting of nitrogen nucleophile, sulfur nucleophile, oxygen nucleophile, carbon nucleophile, phosphor nucleophile, and mixtures thereof.
[0160] Nitrogen nucleophile compound may have at least one functional group chosen in the group consisting of ammonia, azide, amines, nitrites, hydroxylamine, hydrazin, carbazide, phenylhydrazine, semicarbazide, and amide, and mixtures thereof.
[0161] Sulfur nucleophile compound may have at least one functional group chosen in the group consisting of hydrogen sulfide and its salts, thiols (RSH), thiolate anions (RS-), anions of thiolcarboxylic acids (RC(O)-S-), and anions of dithiocarbonates (RO-C(S)-S-) and dithiocarbamates (R2N-C(S)-S-) and mixtures thereof.
[0162] Oxygen nucleophile compound may have at least one functional group chosen in the group consisting of water, hydroxide anion, alcohols, alkoxide anions, carboxylate anions, carbonates, sulfonate, sulfate, sodium phosphates, sodium silicates, borax, sodium tetraborate, and mixtures thereof.
[0163] Carbone nucleophile compound may have at least one functional group chosen in the group consisting of enols carbon nucleophiles, malonate and acetoacetate.
[0164] Phosphor nucleophile compound may have at least one functional group chosen in the group consisting of phosphine, phosphite anion and mixture thereof.
[0165] According to an embodiment, the nucleophile is chosen in the group consisting of alcohol, amine, thiol and mixtures thereof.
[0166] “Alcohol” and “polyol” can be used indifferently in the present invention.
[0167] According to a particular embodiment, the amine is chosen in the group consisting of cystamine, EDA, DETA, Pentamethylenediamine, hexamethylenediamine, poly(L-lysine) (that can be modified), L-lysine, L-lysine ethyl ester, cystine dimethyl ester, and mixtures thereof.
[0168] According to a particular embodiment, the amine is chosen in the group consisting of cystamine, cystamine hydrochloride, cystine, cystine hydrochloride, cystine dialkyl ester, cystine dialkyl ester hydrochloride, a xylylene diamine, 1 ,2-diaminocyclohexane, 1 ,4-diaminocyclohexane, polyetheramines, ethylene diamine, diethylene triamine, spermine, spermidine, polyamidoamine (PAMAM), guanidine carbonate, chitosan, tris-(2-aminoethyl)amine, 1 ,4 Diaminobutane, 2,2Dimethyl-1 ,3-propanediamine, 1 ,3- diaminopentane (Dytek EP diamine), 1 ,2 Diaminopropane, triethylenetetramine , 1 ,3- diaminopropane; urea; ethylene urea; aminoguanidine bicarbonate; 1-(2- aminoethyl)imidazolidin-2-one; N-(3-aminopropyl)-N-dodecylpropane-1 ,3-diamine; N1-(2-Aminoethyl)-N1-dodecyl-1 ,2-ethanediamine; aminoethylethanolamine; N1-(3- aminopropyl)propane-1 ,3-diamine, polyethyleneimine, C36-alkylenediamines, (as an example Priamine™ - (1 E,19E)-10,11-dioctylicosa-1 ,19-diene-1 ,20-diamine (low- viscous, bio-based, dimer diamine), hexaaminocyclotriphosphazene, amino-acid such as lysine, arginine, leucine, histidine, tryptophane, serin, glutamine, threonine, alanine, asparagine, aspartic acid, cysteine, glutamic acid, glycine , isoleucine, methionine, phenylalanine , proline , tyrosine, valine, 2,2,4,4-tetraamino-6,6- dichlorocyclotriphosphazene (TCPA) and mixtures thereof.
[0169] According to a particular embodiment, the alcohol (or polyol) is chosen in the group consisting of phloroglucinol, Hydroquinone, Hydroquinone bis(2- hydroxyethyl)ether, 1 ,4-cyclohexanedimethanol, Resorcinol, Isosorbide, Pentaerythritol, Erythritol, Trimethylolpropane, Di-trimethylolpropane, sorbitol, mannitol, xylitol, triethanolamine, diglycerol, triglycerol and corresponding partial esters, polyglycerol and corresponding partial esters, and mixtures thereof.
[0170] According to a particular embodiment, the thiol (or polythiol) is chosen Ethylene glycol bis-mercaptoacetate, dithiothreitol, trimethylolpropane tris(3- mercaptopropionate), 2,2'-Thiodiethanethiol, Pentaerythritol tetrakis(3- mercaptopropionate), 2-mercaptoethanol, 3-Aminopropane-1 -thiol, 3-Aminopropane- 1 -thiol hydrochloride, 3-mercapto-1 ,2-propanediol, 3-Mercapto-1 -propanol, 1- Mercapto-2-propanol, 6-Mercapto-1 -hexanol, Mercapto-acetic acid 4- mercaptoacetoxy-butyl ester, 1 -Thioglycerol, 2-{2-[2-(2-
[0171] Mercaptoethoxy)ethoxy]ethoxy}ethanol, cysteamine, cysteamine hydrochloride, 4- Mercaptophenol, 4,6-Diamino-2-pyrimidinethiol, 4,6-Dihydroxy-2-mercaptopyrimidine, Propane-1 , 3-dithiol, and mixtures thereof.
[0172] According to an embodiment, the nucleophile and the compound having at least two P-CI functions are the same molecule.
[0173] According to an embodiment, the nucleophile and the compound having at least two P-CI functions are the same molecule, wherein the molecule is 2,2,4,4-tetraamino- 6,6-dichlorocyclotriphosphazene.
[0174] According to an embodiment, the nucleophile and the compound having at least two P-CI functions are not the same molecule. Biodegradability
[0175] In a particular embodiment, the shell material is a biodegradable material.
[0176] In a particular embodiment, the organic part of the shell is biodegradable.
[0177] In a particular embodiment, the shell has a biodegradability of at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%, within 60 days according to OECD301 F.
[0178] In a particular embodiment, the core-shell microcapsule 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 OECD301 F.
[0179] Thereby it is understood that the core-shell microcapsule including all components, such as the core, shell and optionally coating may have a biodegradability of at least 40 %, preferably at least 60 %, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD301 F.
[0180] In a particular embodiment, the oil core, preferably perfume 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 OECD301 F. OECD301 F is a standard test method on the biodegradability from the Organization of Economic Co-operation and Development.
[0181] A typical method for extracting the shell for measuring the biodegradability is disclosed in Gasparini and all in Molecules 2020, 25,718.
[0182] Outer coating
[0183] According to a particular embodiment of the invention, the microcapsule comprises an outer coating, wherein the outer coating comprises a coating material selected from the group consisting of a non-ionic polymer (such as non-ionic polysaccharide), anionic polymer (such as polysaccharide), a cationic polymer, a polysuccinimide derivative (as described for instance in WO2021185724) and mixtures thereof to form an outer coating to the microcapsule.
[0184] According to a particular embodiment, the microcapsule does not comprise an outer coating.
[0185] Non-ionic polysaccharide polymers are well known to a person skilled in the art and are described for instance in WO2012 / 007438 page 29, lines 1 to 25 and in WO2013 / 026657 page 2, lines 12 to 19 and page 4, lines 3 to 12. Preferred non-ionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
[0186] Cationic polymers are well known to a person skilled in the art. Preferred cationic polymers have cationic charge densities of 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 polymers may be determined by the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for Nitrogen determination. The preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and / or quaternary amine groups that can either form part of the main polymer chain or can be borne by a side substituent directly connected thereto. The weight average (Mw) molecular weight of the cationic polymer is preferably between 10,000 and 3.5M Dalton, more preferably between 50,000 and 1.5M Dalton. According to a particular embodiment, one will use cationic polymers based on acrylamide, methacrylamide, N- vinylpyrrolidone, quaternized N,N-dimethylaminomethacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1 -vinyl-1 H- imidazol-3-ium chloride), vinylpyrrolidone, acrylamidopropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride. Preferably copolymers shall be selected from the group consisting of polyquaternium- 5, polyquaternium-6, polyquaternium-7, polyquaterniumIO, polyquaternium-11 , polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride or polygalactomannan 2- hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride. As specific examples of commercially available products, one may cite Salcare® SC60 (cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, origin: BASF) or Luviquat®, such as the PQ 11 N, FC 550 or Style (polyquaternium-11 to 68 or quaternized copolymers of vinylpyrrolidone origin: BASF), or also the Jaguar® (C13S or C17, origin Rhodia).
[0187] According to any one of the above embodiments of the invention, there is added an amount of polymer described above comprised between about 0% and 5% w / w, or even between about 0.1 % and 2% w / w, percentage being expressed on a w / w basis relative to the total weight of the slurry. It is clearly understood by a person skilled in the art that only part of said added polymers will be incorporated into / deposited on the microcapsule shell.
[0188] According to a particular embodiment, the microcapsule of the present invention comprises a mineral layer. The mineral layer preferably comprises a material chosen in the group consisting of iron oxides, iron oxyhydroxide, titanium oxides, zinc oxides, calcium carbonates, calcium phosphates, barium salt, strontium salt, magnesium salt, and mixtures thereof and mixtures thereof.
[0189] Solid particles
[0190] Another object of the invention is a solid particle comprising:
[0191] - a carrier material, preferably a polymeric carrier material chosen in the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, vegetable gums, pectins, xanthans, alginates, carragenans, cellulose derivatives and mixtures thereof, and
[0192] - microcapsules as defined above entrapped in said carrier material, and
[0193] - optionally free perfume entrapped in said carrier material.
[0194] Solid particle as defined above and microcapsule powder can be used indifferently in the present invention.
[0195] PROCESS FOR PREPARING MICROCAPSULES
[0196] Another object of the invention is a process for preparing a core-shell microcapsule slurry comprising the steps of: a) Optionally, providing at least one compound having at least two P-CI functions b) admixing at least one hydrophobic material with the optional compound obtained in step a) to form an oil phase; c) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; d) Optionally, dispersing the two-phases dispersion into a continuous phase C2 comprising optionally at least one compound having at least two P-CI functions to form a multiple dispersion; e) curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and or / step d) and / or step e).
[0197] It should be understood that, according to the invention, at least one compound having at least two P-CI functions is added in step a) and / or in step d).
[0198] It should also be understood that, the at least one compound having at least two P-CI functions used in step a) and / or in step d) can be used as a pure compound (meaning without any reaction with a reactant) or can be used as a modified compound if a reactant is added in step a) and / or step b) and / or step c) and / or step d) and / or in step e).
[0199] According to a particular embodiment, the process comprises the steps of: a) Providing at least one compound having at least two P-CI functions b) admixing at least one hydrophobic material with the compound obtained in step a) to form an oil phase; c) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; d) curing the dispersion obtained in step c) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and / or step d).
[0200] According to an embodiment, the process for preparing a core-shell microcapsule slurry comprises the steps of: a) Preparing a solution comprising at least one compound having at least two P-CI functions b) admixing at least one active ingredient with solution obtained in step a) to form an oil phase; c) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; d) Optionally, dispersing the two-phases dispersion into a continuous phase C2 to form a multiple dispersion; e) curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).
[0201] According to a particular embodiment, the process comprises the steps of: a) Providing at least one compound having at least two P-CI functions b) admixing at least one hydrophobic material with the compound obtained in step a) to form an oil phase; c) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; d) dispersing the two-phases dispersion into a continuous phase C2 comprising at least one compound having at least two P-CI functions to form a multiple dispersion; e) curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and / or step d) and / or in step e).
[0202] The compound having at least two P-CI functions of step d) and be the same or can be different from the compound having at least two P-CI functions of step a).
[0203] According to a particular embodiment, the process comprises the steps of: a) providing at least one hydrophobic material to form an oil phase; b) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; c) dispersing the two-phases dispersion into a continuous phase C2 comprising at least one compound having at least two P-CI functions to form a multiple dispersion; d) curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and / or step d). The embodiments disclosed for the core-shell microcapsules also apply for the process for preparing core-shell microcapsules. It applies notably to the compound having at least two P-CI functions, the hydrophobic material, the compound having inorganic moieties or the nucleophile.
[0204] According to an embodiment, the continuous phase C1 comprises, preferably consists of water.
[0205] According to an embodiment, the continuous phase C1 is a water phase.
[0206] According to an embodiment, the two-phases dispersion is an oil-in-water emulsion.
[0207] According to an embodiment, the two-phases dispersion is a water-in-oil emulsion.
[0208] According to an embodiment, the continuous phase C1 comprises water and an alcohol such as glycerol, 1 ,4-butanediol, ethylene glycol and mixtures thereof.
[0209] According to an embodiment, the continuous phase C1 consists of alcohol.
[0210] A stabilizer can be added in the oil phase and / or in the continuous phase C1 .
[0211] By “stabilizer”, it is meant a compound capable to stabilize oil / dispersing phase interface (typically oil / water interface) as an emulsion.
[0212] The stabilizer is preferably used in an amount comprised between 0.05% to 20 %, preferably between 0.1 to 10%, even more preferably between 0.1 and 5% by weight based on the two-phases dispersion, preferably oil-in-water emulsion.
[0213] “Stabilizer” or “emulsifier” can be used indifferently in the present invention.
[0214] According to an embodiment, the stabilizer can act as a nucleophile. Therefore, according to an embodiment, the stabilizer is the nucleophile of the present invention.
[0215] According to an embodiment, the stabilizer is a colloidal stabilizer.
[0216] The colloidal stabilizer can be a polymeric emulsifier (standard emulsion), a surfactant, or solid particles (Pickering emulsion).
[0217] By “polymeric emulsifier”, it meant an emulsifier having both a polar group with an affinity for water (hydrophilic) and a nonpolar group with an affinity for oil (hydrophobic). The hydrophilic part will dissolve in the water phase and the hydrophobic part will dissolve in the oil phase providing a film around droplets.
[0218] By “surfactant”, it meant a substance with a polar and a non-polar group that is added to the liquid to reduce the liquid surface tension. According to an embodiment, the stabilizer is chosen in the group consisting of inorganic particles, polymeric emulsifier such as polysaccharides, proteins, glycoproteins, and mixtures thereof.
[0219] When the stabilizer is solid particles, it can be chosen in the group consisting of calcium phosphate, silica, silicates, titanium dioxide, aluminium oxide, zinc oxide, iron oxide, mica, kaolin, montmorillonite, laponite, bentonite, perlite, dolomite, diatomite, vermiculite, hectorite, gibbsite, illite, kaolinite, aluminosilicates, gypsum, bauxite, magnesite, talc, magnesium carbonate, calcium carbonate, diatomaceous earth and mixtures thereof.
[0220] According to a particular embodiment, the stabilizer is a biopolymer.
[0221] By “biopolymers” it is meant biomacromolecules produced by living organisms. Biopolymers are characterized by molecular weight distributions ranging from 1 ,000 (1 thousand) to 1 ,000,000,000 (1 billion) Daltons. These macromolecules may be carbohydrates (sugar based) or proteins (amino-acid based) or a combination of both (gums) and can be linear or branched.
[0222] According to an embodiment, the polymeric emulsifier is chosen in the group consisting of gum Arabic, modified starch, polyvinyl alcohol, polyvinylpyrolidone (PVP), carboxymethylcellulose (CMC), anionic polysaccharides, acrylamide copolymer, protein such as soy protein, rice protein, whey protein, white egg albumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, and mixtures thereof.
[0223] Potato proteins are typically extracted from potato tuber (Solanum tuberosum). According to an embodiment, the potato protein is a native potato protein and preferably patatin.
[0224] The protein used in this invention may be native, partially or completely denaturated by any suitable method. Denaturation is a process which modify the conformational structure of a protein by unfolding, i.e., it involves the disruption and possible destruction of both the secondary and tertiary structures of the protein. Indeed, denaturation implicates the breaking of many of the weak linkages, or bonds (e.g., hydrogen bonds), within a protein molecule that are responsible for the highly ordered structure of the protein in its native state. Denaturation is reversible (the proteins can regain their native state when the denaturating influence is removed) or irreversible.
[0225] Denaturation can be brought about in various ways. Proteins can be denatured by exposure to temperature, radiation or mechanical stress including shear, changes in pH (treatment with a base or an acid), treatment with oxidizing or reducing agents, inorganic salt, certain organic solvents, chaotropic agents (i.e, compounds having a positive chaotropic value - kJ Kg-1mole on the Hallsworth Scale - such as guanidine salts - e.g., guanidine carbonate, guanidine hydrochloride -, urea, calcium chloride, n- butanol, ethanol, lithium perchlorate, lithium acetate, magnesium chloride, phenol, 2- propanol, sodium dodecyl sulfate, thiourea).
[0226] The protein used in this invention can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, peptides or chemical groups such as phosphates or methyl.
[0227] According to an embodiment, the compound having at least two P-CI functions is added in an amount comprised between 0.5 and 10%, preferably between 1 and 5% by weight based on the total weight of the multiple dispersion.
[0228] According to an embodiment, the compound having inorganic moieties is added in an amount comprised between 1 and 15%, preferably between 1 and 8% by weight based on the total weight of the multiple dispersion.
[0229] According to an embodiment, a base is added in the continuous phase C1. Preferably the base is chosen in the group consisting of guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof.
[0230] When used, the base is typically used in an amount comprised between 0.1 and 10%, preferably between 3 and 7% by weight based on the total weight of the continuous phase C1 .
[0231] According to an embodiment, a nucleophile chosen in the group consisting of nitrogen nucleophile, sulfur nucleophile, enol carbon nucleophile, oxygen nucleophile, phosphor nucleophile and mixtures thereof is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).
[0232] The nucleophile is defined as previously. According to an embodiment, the nucleophile can be added in the oil phase and / or in the continuous phase C1.
[0233] The nucleophile can be added in an amount comprised between 0.5 and 10%, preferably between 1 and 4% by weight based on the total weight of the two-phases dispersion.
[0234] In step e), the dispersion obtained in step d) or e) is cured to form microcapsules in the form of a slurry.
[0235] Optionally, a non-ionic polymer (such as non-ionic polysaccharide), anionic polymer (such as polysaccharide), a cationic polymer, a polysuccinimide derivative (as described for instance in WO2021185724) and mixtures thereof, as defined previously, can be added in step e) or after step e) to form an outer coating.
[0236] According to a preferred embodiment, to enhance the kinetics, said step is performed at a temperature comprised between 5 and 90°C, possibly under pressure, for 1 to 24 hours. More preferably it is performed at between 10 and 80°C for between 30 minutes and 5 hours.
[0237] MULTIPLE MICROCAPSULES SYSTEM
[0238] According to an embodiment, the microcapsules of the invention (first type of microcapsule) can be used in combination with a second type of microcapsules.
[0239] Another object of the invention is a microcapsule delivery system comprising:
[0240] • the microcapsules of the present invention as a first type of microcapsule, and
[0241] • a second type of microcapsules, wherein the first type of microcapsule and the second type of microcapsules differ in their hydrophobic material and / or their wall material and / or in their coating material.
[0242] According to a particular embodiment, the microcapsule delivery system is in the form of a slurry.
[0243] 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 polyurea, polyurethane, polyamide, polyhydroxyalkanoates, polyacrylate, polyesters, polyaminoesters, polyepoxides, organosilicon, polycarbonate, polysulfonamide, urea formaldehyde, melamine formaldehyde resin, melamine formaldehyde resin cross-linked with polyisocyanate or aromatic polyols, melamine urea resin, melamine glyoxal resin, gelatin / gum arabic shell wall, and mixtures thereof.
[0244] The second type of microcapsule can comprise an oil-based core comprising a hydrophobic active, preferably perfume, 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, the second material is a polymeric material. In a particular embodiment, the weight ratio between the first material and the second material is comprised between 50:50 and 99.9:0.1. In a particular embodiment, the coacervate comprises a first polyelectrolyte, preferably selected among proteins (such as gelatin), polypeptides or polysaccharides (such as chitosan), most preferably Gelatin and a second polyelectrolyte, preferably alginate salts, cellulose derivatives guar gum, pectinate salts, carrageenan, polyacrylic and methacrylic acid or xanthan gum, or yet plant gums such as acacia gum (Gum Arabic), most preferably Gum Arabic. The coacervate first material can be hardened chemically using a suitable cross-linker such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin or can be hardened enzymatically using an enzyme such as transglutaminase. The second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, organosilicon, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount less than 3 wt.%, preferably less than 1 wt.% based on the total weight of the second type of microcapsule slurry.
[0245] As non-limiting examples, the shell of the second type of microcapsules can be aminoplast-based, polyurea-based or polyurethane-based. The shell of the second type of microcapsules can also be hybrid, namely organic-inorganic such as a hybrid shell composed of at least two types of inorganic particles that are cross-linked, or yet a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macro-monomeric composition.
[0246] According to an aspect, the shell of the second type of microcapsules comprises an aminoplast copolymer, such as melamine-formaldehyde or ureaformaldehyde or cross-linked melamine formaldehyde or melamine glyoxal. According to another aspect the shell of the second type of microcapsules is polyurea-based made from, for example but not limited to isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules comprise a polyurea wall which is the reaction product of the polymerisation between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (for example a water-soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated perfume. However, the use of an amine can be omitted. According to a particular aspect, the colloidal stabilizer includes an aqueous solution of between 0.1% and 0.4% of polyvinyl alcohol, between 0.6% and 1% of a cationic copolymer of vinylpyrrolidone and of a quaternized vinylimidazol (all percentages being defined by weight relative to the total weight of the colloidal stabilizer). According to another aspect, the emulsifier is an anionic or amphiphilic biopolymer, which may be, in one aspect, chosen from the group consisting of gum Arabic, soy protein, gelatin, sodium caseinate and mixtures thereof.
[0247] According to another embodiment, the microcapsule wall material of the second type of microcapsules may comprise any suitable resin and especially including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include the reaction product of an aldehyde and an amine, 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, urearesorcinol, and mixtures thereof. Suitable materials for making may be obtained from one or more of the following companies Solutia Inc. (St Louis, Missouri U.S.A.), Cytec Industries (West Paterson, New Jersey U.S.A.), Sigma-Aldrich (St. Louis, Missouri U.S.A.).
[0248] According to another embodiment, the second type of microcapsules is a one-shell aminoplast core-shell microcapsule obtainable by a process comprising the steps of:
[0249] 1) admixing a perfume oil with at least a polyisocyanate having at least two isocyanate functional groups to form an oil phase;
[0250] 2) dispersing or dissolving into water an aminoplast resin and optionally a stabilizer to form a dispersing phase; 3) preparing an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 100 microns, by admixing the oil phase and the dispersing phase;
[0251] 4) performing a curing step to form the wall of said microcapsule; and
[0252] 5) optionally drying the final dispersion to obtain the dried core-shell microcapsule. According to an embodiment, the second type of microcapsules is a formaldehyde- free capsule. A typical process for the preparation of aminoplast formaldehyde-free microcapsules slurry comprises the steps of
[0253] 1) preparing an oligomeric composition comprising the reaction product of, or obtainable by reacting together: a. a polyamine component in the form of melamine or of a mixture of melamine and at least one C1-C4 compound comprising two NH2 functional groups; b. an aldehyde component in the form of a mixture of glyoxal, a C4-6 2,2- dialkoxy-ethanal and optionally a glyoxalate, said mixture having a molar ratio glyoxal / C4-6 2,2-dialkoxy-ethanal comprised between 1 / 1 and10 / 1 ; and c. a protic acid catalyst;
[0254] 2) preparing an oil-in-water dispersion, wherein the droplet size is comprised between 1 and 600 microns, and comprising: a. an oil; b. a water medium: c. at least an oligomeric composition as obtained in step 1 ; d. at least a cross-linker selected amongst: i. C4-C12 aromatic or aliphatic di- or tri-isocyanates and their biurets, triurets, trimmers, trimethylol propane-adduct and mixtures thereof; and / or ii. a di- or tri-oxiran compounds of formula:
[0255] A-(oxiran-2-ylmethyl)nwhereinnstands for 2 or 3 and 1 represents a C2-C6 group optionally comprising from 2 to 6 nitrogen and / or oxygen atoms; e. optionally a C1-C4 compounds comprising two NH2 functional groups;
[0256] 3) Heating the dispersion; and 4) Cooling the dispersion.
[0257] In another particular embodiment, the second type of microcapsule comprises
[0258] - an oil-based core comprising a hydrophobic active, preferably perfume,
[0259] - optionally an inner shell made of a polymerized polyfunctional monomer;
[0260] - a biopolymer shell comprising a protein, wherein at least one protein is crosslinked.
[0261] According to a particular embodiment, the protein is chosen in the group consisting of milk proteins, caseinate salts such as sodium caseinate or calcium caseinate, casein, whey protein, hydrolyzed proteins, gelatins, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate, most preferably sodium caseinate
[0262] According to a particular embodiment, the protein comprises sodium caseinate and a globular protein, preferably chosen in the group consisting of whey protein, betalactoglobulin, ovalbumine, bovine serum albumin, vegetable proteins, and mixtures thereof.
[0263] The protein is preferably a mixture of sodium caseinate and whey protein.
[0264] According to a particular embodiment, the biopolymer shell comprises a crosslinked protein chosen in the group consisting of sodium caseinate and / or whey protein.
[0265] According to a particular embodiment, the second type of microcapsules slurry comprises at least one microcapsule made of:
[0266] - an oil-based core comprising the hydrophobic active, preferably perfume;
[0267] - an inner shell made of a polymerized polyfunctional monomer; preferably a polyisocyanate having at least two isocyanate functional groups
[0268] - a biopolymer shell comprising a protein, wherein at least one protein is crosslinked; wherein the protein contains preferably a mixture comprising sodium caseinate and a globular protein, preferably whey protein,
[0269] - optionally at least an outer mineral layer.
[0270] According to an embodiment, sodium caseinate and / or whey protein is (are) cross-linked protein(s).
[0271] The weight ratio between sodium caseinate and whey protein is preferably comprised between 0.01 and 100, preferably between 0.1 and 10, more preferably between 0.2 and 5. In another particular embodiment, the second type of microcapsules is a polyamide core-shell polyamide microcapsule comprising:
[0272] - an oil-based core comprising comprising a hydrophobic active, preferably perfume, and
[0273] - a polyamide shell comprising or being obtainable from:
[0274] • an acyl chloride,
[0275] • a first amino compound,
[0276] • a second amino compound,
[0277] • optionally, a carbohydrate.
[0278] According to a particular embodiment, the second type of microcapsules comprises:
[0279] - an oil-based core comprising a hydrophobic active, preferably perfume, and
[0280] - a polyamide shell comprising or being obtainable from:
[0281] • an acyl chloride, preferably in an amount comprised between 5 and 98%, preferably between 20 and 98%, more preferably between 30 and 85% w / w
[0282] • a first amino compound, preferably in an amount comprised between 1 % and 50% w / w, preferably between 7 and 40% w / w;
[0283] • a second amino compound, preferably in an amount comprised between 1 % and 50% w / w, preferably between 2 and 25% w / w
[0284] • a stabilizer, preferably a biopolymer, preferably in an amount comprised between 0 and 90%, preferably between 0.1 and 75%, more preferably between 1 and 70%,
[0285] • optionally, a carbohydrate.
[0286] According to a particular embodiment, the second type of microcapsules comprises:
[0287] - an oil-based core comprising a hydrophobic active, preferably perfume, and
[0288] - a polyamide shell comprising or being obtainable from:
[0289] • an acyl chloride, • a first amino-compound being an amino-acid, preferably chosen in the group consisting of L-Lysine, L-Arginine, L-Histidine, L- Tryptophane and / or mixtures thereof.
[0290] • a second amino-compound, preferably chosen in the group consisting of ethylene diamine, diethylene triamine, cystamine and / or mixtures thereof, and
[0291] • a biopolymer, preferably chosen in the group consisting of potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, soy protein, rice protein, whey protein, white egg albumin, casein, sodium caseinate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin and mixtures thereof,
[0292] • optionally a carbohydrate, preferably selected from the group consisting of anionic salt of alginic acid, preferably alginic acid sodium salt, pectin, lignin, anionic modified starch, carboxymethylcellulose, carrageenan and mixtures thereof.
[0293] According to another aspect, the shell of the second type of microcapsules is polyurea-or polyurethane-based. Examples of processes for the preparation of polyurea and polyurethane-based microcapsule slurry are for instance described in International Patent Application Publication No. W02007 / 004166, European Patent Application Publication No. EP 2300146, and European Patent Application Publication No. EP25799. Typically a process for the preparation of polyurea or polyurethane-based microcapsule slurry include the following steps: a) Dissolving at least one polyisocyanate having at least two isocyanate groups in an oil to form an oil phase; b) Preparing an aqueous solution of an emulsifier or colloidal stabilizer to form a dispersing phase; c) Adding the oil phase to the dispersing phase to form an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 500 pm, preferably between 5 and 50 pm; and d) Applying conditions sufficient to induce interfacial polymerisation and form microcapsules in the form of a slurry.
[0294] PERFUMING COMPOSITION AND CONSUMER PRODUCTS
[0295] The present invention also relates to a perfuming composition comprising
[0296] - a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above,
[0297] - at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base, and
[0298] - optionally, at least one perfumery adjuvant.
[0299] In a particular embodiment, the composition comprises:
[0300] - a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above;
[0301] - an active ingredient, preferably chosen in the group consisting of a cosmetic ingredient, skin caring ingredient, perfume ingredient, flavor ingredient, malodour counteracting ingredient, bactericide ingredient, fungicide ingredient, pharmaceutical or agrochemical ingredient, a sanitizing ingredient, an insect repellent or attractant, and mixtures thereof.
[0302] In a particular embodiment, a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above can also be added in different perfumed consumer products
[0303] In a particular embodiment, present invention relates to a perfuming composition comprising
[0304] • a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above and
[0305] • optionally, a free perfume oil.
[0306] Preferably, the perfuming composition according to the invention comprises between 0.1 and 40 %, preferably between 0.1 and 30% by weight of a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above. By “free perfume” it is herein understood a perfume or perfume oil which is comprised in the perfuming composition and not entrapped in the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above.
[0307] In a particular embodiment, the total amount of the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above is 0.05 to 5 wt.% (based on the total weight of the perfuming composition) and the total amount of the free perfume oil is 0.05 to 5 wt.% (based on the total weight of the perfuming composition).
[0308] In a particular embodiment, the total perfume oil of the perfume formulation entrapped in the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above and total free perfume oil are present in the perfuming composition in a weight ratio of 1 :20 to 20:1 , preferably 10:1 to 1 :10.
[0309] The perfuming composition can further comprise at least one perfuming coingredient and, optionally a perfumery adjuvant,
[0310] By “perfuming co-ingredient” it is herein understood a compound, which is used in a perfuming preparation or a composition to impart a hedonic effect and which is not a microcapsule as 20 defined above. In other words such a co-ingredient, to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor. The nature and type of the perfuming coingredients present in the perfuming composition do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulfur heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-30 ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds. Co-ingredients may be chosen in 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-
[0311] (dodecylthio)octan-4-one, 2-phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6- dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1-yl oxo(phenyl)acetate, 3,7-dimethyl-2,6- octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl) succinate, (2-((2- methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut- 3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en- 1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2- methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1 -phenethoxyprop-1 -en-2- yl)benzene, 1 -methyl-4-(1 -phenethoxyprop-1 -en-2-yl)benzene, 2-(1 -phenethoxyprop- 1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1- yl)oxy)prop-1 -en-2-yl)naphthalene, (2-((2- pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2- phenylvinyl)oxy)benzene, (2-((2-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 or a mixture thereof.
[0312] By “perfumery adjuvant” it is herein understood an ingredient capable of imparting additional 5 added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfuming bases cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.
[0313] The core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above can advantageously be used in many application fields and used in consumer products. The present invention also relates to a perfumed consumer product comprising
[0314] - a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above, and
[0315] - a personal care, home care, or fabric care active base. The consumer products of the invention, can in particular be of used in perfumed consumer products such as product belonging to fine fragrance or “functional” perfumery. Functional perfumery includes in particular personal-care products including hair-care, body cleansing, skin care, hygiene-care as well as homecare products including laundry care and air care.
[0316] In particular a liquid consumer product comprising:
[0317] - from 2 to 65% by weight, relative to the total weight of the consumer product, of at least one surfactant;
[0318] - water or a water-miscible hydrophilic organic solvent; and
[0319] - a perfuming composition or the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above.
[0320] Also a powder consumer product comprising
[0321] - from 2 to 65% by weight, relative to the total weight of the consumer product, of at least one surfactant; and
[0322] - a perfuming composition or the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above.
[0323] For the sake of clarity, it has to be mentioned that, by “perfumed consumer product” it is meant a consumer product which is expected to deliver among different benefits a perfuming effect to the surface to which it is applied (e.g. skin, hair, textile, paper, or home surface) or in the air (air-freshener, deodorizer etc). In other words, a perfumed consumer product according to the invention is a manufactured product which comprises a functional formulation also referred to as “base”, together with benefit agents, among which an effective amount of microcapsules according to the invention.
[0324] The nature and type of the other constituents of the perfumed consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of said product. Base formulations of consumer products in which the microcapsules of the invention can be incorporated can be found in the abundant literature relative to such products. These formulations do not warrant a detailed description here which would in any case not be exhaustive. The person skilled in the art of formulating such consumer products is perfectly able to select the suitable components on the basis of his general knowledge and of the available literature.
[0325] Non-limiting examples of suitable perfumed consumer products can be a fine perfume, a splash or eau de perfume, a cologne, a shave or after-shave lotion, a liquid or solid detergent, a mono or multi chamber unidose detergent , a fabric softener, a fabric refresher, liquid or solid scent-boosters (PEG I urea or salts), a dryer sheet, an ironing water, a paper, a bleach, a carpet cleaners, curtain-care products, a shampoo, a coloring preparation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, a hair conditioning product, a vanishing cream, a deodorant or antiperspirant, hair remover, tanning or sun product, nail products, skin cleansing, a makeup, a perfumed soap, shower or bath mousse, oil or gel, or a foot / hand care products, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, furnisher care, wipe, a dish detergent or hard-surface detergent, a leather care product, a car care product.
[0326] In a particular embodiment, the perfumed consumer product is preferably selected from the group consisting of personal care composition, home care composition or fabric care composition, most preferably in form of antiperspirants, hair care products, such as shampoo or hair-conditioner, body care products such as a shower gel, oral care products, laundry care products, preferably a detergent or a fabric softener.
[0327] Another object of the invention is a consumer product comprising: a personal care active base, and microcapsules or a microcapsule slurry as defined above or the perfuming composition as defined above, wherein the consumer product is in the form of a personal care composition.
[0328] Personal care active bases in which the microcapsules of the invention can be incorporated can be found in the abundant literature relative to such products. These formulations do not warrant a detailed description here which would in any case not be exhaustive. The person skilled in the art of formulating such consumer products is perfectly able to select the suitable components on the basis of his general knowledge and of the available literature. The personal care composition is preferably chosen in the group consisting of a haircare product (e.g. a shampoo, hair conditioner, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream, body lotion or a deodorant or antiperspirant), or a skin-care product (e.g. a perfumed soap, shower or bath mousse, body wash, oil or gel, bath salts, or a hygiene product);
[0329] Another object of the invention is a consumer product comprising: a home care or a fabric care active base, and microcapsules or a microcapsule slurry as defined above or the perfuming composition as defined above, wherein the consumer product is in the form of a home care or a fabric care composition.
[0330] Home care or fabric care active bases in which the microcapsules of the invention can be incorporated can be found in the abundant literature relative to such products. These formulations do not warrant a detailed description here which would in any case not be exhaustive. The person skilled in the art of formulating such consumer products is perfectly able to select the suitable components on the basis of his general knowledge and of the available literature.
[0331] Preferably, the consumer product comprises from 0.1 to 15 wt%, more preferably between 0.2 and 5 wt% of the microcapsules of the present invention, these percentages being defined by weight relative to the total weight of the consumer product. Of course, the above concentrations may be adapted according to the benefit effect desired in each product.
[0332] For liquid consumer product mentioned below, by “active base”, it should be understood that the active base includes active materials (typically including surfactants).
[0333] For solid consumer product mention below, by “active base”, it should be understood that the active base includes active materials (typically including surfactants) and auxiliary agents (such as bleaching agents, buffering agent; builders; soil release or soil suspension polymers; granulated enzyme particles, corrosion inhibitors, antifoaming, sud suppressing agents; dyes, fillers, and mixtures thereof).
[0334] The home or fabric care composition is preferably chosen in the group consisting of fabric softener, liquid detergent, powder detergent, liquid scent booster and solid scent booster. Fabric softener
[0335] An object of the invention is a consumer product in the form of a fabric softener composition comprising:
[0336] - a fabric softener active base; preferably comprising at least one active material chosen in the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (esterquats), Hamburg esterquat (HEQ), TEAQ (triethanolamine quat), silicones and mixtures thereof, the active base being used preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
[0337] - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0338] - optionally free perfume oil.
[0339] Liquid detergent
[0340] An object of the invention is a consumer product in the form of a liquid detergent composition comprising:
[0341] - a liquid detergent active base; preferably comprising at least one active material chosen in the group consisting of anionic surfactant such as alkylbenzenesulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol polyethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxydes, alkyl polyglucosides, alkyl polyglucosamides, the active base being used preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
[0342] - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0343] - optionally free perfume oil. Solid detergent
[0344] An object of the invention is a consumer product in the form of a solid detergent composition comprising:
[0345] - a solid detergent active base; preferably comprising at least one active material chosen in the group consisting of anionic surfactant such as alkylbenzenesulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol polyethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxydes, alkyl polyglucosides, alkyl polyglucosamides, the active base being used preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
[0346] - a microcapsule powder or microcapsule slurry as defined above, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0347] - optionally free perfume oil.
[0348] Shampoo / shower gel
[0349] An object of the invention is a consumer product in the form of a shampoo or a shower gel composition comprising:
[0350] - a shampoo or a shower gel active base; preferably comprising at least one active material chosen in the group consisting of sodium alkylether sulfate, ammonium alkylether sulfates, alkylamphoacetate, cocamidopropyl betaine, cocamide MEA, alkylglucosides and aminoacid based surfactants and mixtures thereof, the active base being used preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
[0351] - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0352] - optionally free perfume oil.
[0353] Rinse-Off Conditioner An object of the invention is a consumer product in the form of a rinse-off conditioner composition comprising:
[0354] - a rinse-off conditioner active base; preferably comprising at least one active material chosen in the group consisting of cetyltrimonium chloride, stearyl trimonium chloride, benzalkonium chloride, behentrimonium chloride and mixture thereof, the active base being used preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
[0355] - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0356] - optionally free perfume oil.
[0357] Solid scent booster
[0358] An object of the invention is a consumer product in the form of a solid scent booster composition comprising:
[0359] - a solid carrier, preferably chosen in the group consisting of urea, sodium chloride, sodium sulphate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, saccharides such as sucrose, mono-, di-, and polysaccharides and derivatives such as starch, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol, and isomalt, PEG, PVP, citric acid orany water soluble solid acid, fatty alcohols or fatty acids and mixtures thereof,
[0360] - microcapsules or a microcapsule slurry as defined above, in a powdered form, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0361] - optionally free perfume oil.
[0362] Liquid scent booster
[0363] An object of the invention is a consumer product in the form of a liquid scent booster composition comprising: - an aqueous phase,
[0364] - a surfactant system essentially consisting of one or more than one nonionic surfactant, wherein the surfactant system has a mean HLB between 10 and 14, preferably chosen in the group consisting of ethoxylated aliphatic alcohols, POE / PPG (polyoxyethylene and polyoxypropylene) ethers, mono and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxylesters, alkyl polyglucosides, amine oxides and combinations thereof;
[0365] - a linker chosen in the group consisting of alcohols, salts and esters of carboxylic acids, salts and esters of hydroxyl carboxylic acids, fatty acids, fatty acid salts, glycerol fatty acids, surfactant having an HLB less than 10 and mixtures thereof, and
[0366] - microcapsules or a microcapsule slurry as defined above, in the form of a slurry, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0367] - optionally free perfume oil.
[0368] Hair coloration
[0369] An object of the invention is a consumer product in the form of an oxidative hair coloring composition comprising:
[0370] - an oxidizing phase comprising an oxidizing agent and an alkaline phase comprising an alkakine agent, a dye precursor and a coupling compound; wherein said dye precursor and said coupling compound form an oxidative hair dye in the presence of the oxidizing agent, preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
[0371] - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
[0372] - optionally free perfume oil.
[0373] Perfuming composition
[0374] According to a particular embodiment, the consumer product is in the form of a perfuming composition comprising: - 0.1 to 30%, preferably 0.1 to 20% of microcapsules or a microcapsule slurry as defined previously,
[0375] - 0 to 40%, preferably 3-40% of perfume, and
[0376] - 20-90%, preferably 40-90% of ethanol, by weight based on the total weight of the perfuming composition.
[0377] The invention will now be further described by way of examples. It will be appreciated that the invention as claimed is not intended to be limited in any way by these examples
[0378] EXAMPLES
[0379] Example 1
[0380] Modification of HCCP with Silane-containinq monomer
[0381] In a 500mL round bottom flask, Hexachlorocyclophosphazene (HCCP; origin: Sigma Aldrich, Switzerland) (15 g, 43 mmol) is dissolved in dry ethyl acetate (150 ml). The solution is maintained under nitrogen flow and cooled to 0°C using an iced-water bath. Meanwhile, a solution of Bis[3-(triethoxysilyl)propyl]amine (Origin: Gelest, Switzerland) (19 mL, 43 mmol) and triethylamine (6 mL, 43 mmol) in dry ethyl acetate (150 mL) is prepared. This solution is added dropwise to the HCCP solution for approximately 1 h 30 min. Then, the reaction medium is heated to 60°C and maintained at 60°C for 3 h. The reaction mixture is subsequently cooled to room temperature and filtered. The filtrate is recovered and concentrated under reduced pressure to give a an orangish / brownish viscous oil (around 30 g).
[0382] Example 2
[0383] Preparation of capsules with HCCP in oil phase; Bis[3-(triethoxysilyl)propyl]amine, sodium hydroxide and optionally L-Lysine and Gum arabic in a 80 glycerol / 20 water continuous phase.
[0384] An oil phase is prepared by mixing 30 g of perfume oil A (see Table 1), hexachlorocyclophosphazene (HCCP) and optionally Solanic 200 (potato protein, origin: Avebe, Netherlands). In a separate container, a continuous phase is prepared by first dissolving L-Lysine (origin: Sigma Aldrich, Switzerland), sodium hydroxide and Gum Arabic (Acacia gum Superstab AA; origin: Nexira, France) in 14 g of water and then mixing this solution with 56 g of glycerol (origin: Sigma Aldrich, Switzerland) (80% glycerol / 20% water). Bis[3-(triethoxysilyl)propyl]amine is then introduced in the continuous phase before the emulsification process.
[0385] The continuous phase is introduced in a double jacketed reactor previously heated at 80°C and the oil phase is poured into the continuous phase. The mixture is emulsified using a stirring blade at 900 rpm for 2 min 30 sec to form the oil-in-glycerol / water emulsion. The reaction mixture is then stirred at 80°C for 6 h. The final product is a milky dispersion. Table 1 : Perfume oil A formulation Table 2: Capsule compositions:
[0386] Example 3:
[0387] Preparation of capsules with HCCP and potato protein in oil phase; Bis[3- (triethoxysilyl)propyllamine, sodium hydroxide, L-Lysine and Gum arabic in a 80 qlycerol / 20 water continuous phase.
[0388] An oil phase is prepared by mixing 30 g of perfume oil, 4 g of hexachlorocyclophosphazene (HCCP) and 0.5 g of Solanic 200 (potato protein). In a separate container, a continuous phase is prepared by first dissolving 1 g of L-Lysine, 0.7 g of Gum Arabic and 0.44 g of sodium hydroxide in 14 g of water and then mixing this solution with 56 g of glycerol (80% glycerol / 20% water). Different quantities of Bis[3-(triethoxysilyl)propyl]amine are then introduced in the continuous phase before the emulsification process.
[0389] The continuous phase is introduced in a double jacketed reactor and the oil phase is poured into the continuous phase. The mixture is emulsified using a stirring blade at 500 rpm for 2 min 30 sec to form the oil-in-glycerol / water emulsion. The reaction mixture is then heated to 80°C and stirred at 80°C for 6 h. The final product is a milky dispersion.
[0390] Table 3: Capsule compositions: Example 4
[0391] Preparation of capsules with HCCP in oil phase; Bis[3-(triethoxysilyl)propyl1amine, sodium hydroxide, L-Lysine and Gum arabic in a 80 qlycerol / 20 water continuous phase.
[0392] The capsules are prepared following the same procedure than disclosed in example 3 except that the emulsification process is done at 700 rpm. Also, the oil phase is composed of perfume oil and / or hydrophobic solvent (benzyl benzoate), the amount of L-Lysine is varied and the amount of Bis[3-(triethoxysilyl)propyl]amine is kept fixed at 7.3 g.
[0393] Table 4: Capsule compositions:
[0394] Example 5:
[0395] Preparation of capsules with HCCP and Bis[3-(triethoxysilyl)propyl]amine in oil phase; sodium hydroxide, L-Lysine and Gum arabic in a 80 qlycerol / 20 water or in water as continuous phase.
[0396] The capsules are prepared following the same procedure than disclosed in example 4 except that the Bis[3-(triethoxysilyl)propyl]amine is introduced in the oil phase composed of 22.5 g of perfume oil and 7.5 g of hydrophobic solvent instead of in the continuous phase. Table 5: Capsule compositions:
[0397] Example 6
[0398] Shell composition by elemental analysis
[0399] Polymer shells of microcapsules from examples 1 to 5 were purified according to the protocol published by Gasparini et al. in Molecules (2020), 25(3), 718.
[0400] Shell composition has been analyzed by elemental analysis and showed that the shell of the exemplified microcapsules contains more than 50% of inorganic moieties.
[0401] Example 7
[0402] Preparation of capsules with HCCP and Bis[3-(triethoxysilyl)propyl]amine in oil phase; sodium hydroxide, L-Lysine and Gum arabic in water as continuous phase.
[0403] An oil phase is prepared by mixing 22.5 g of perfume oil, 7.5 g of benzyl benzoate, 4 g of hexachlorocyclophosphazene (HCCP) and 7.30 g of Bis[3- (triethoxysilyl)propyl]amine. In a separate container, a continuous phase is prepared by dissolving L-Lysine (variable quantities), 0.7 g of Gum Arabic and 0.44 g of sodium hydroxide in 70 g of water.
[0404] The oil phase is emulsified into the water phase using an Ultraturax (10 000 RPM, 2 min) and the emulsion is introduced in a double jacketed reactor. The reaction mixture is then stirred at a given temperature for 6 h. The final product is a milky dispersion. Table 6: Capsule compositions:
[0405] Example 8
[0406] Preparation of capsules with HCCP and Bis[3-(triethoxysilyl)propyl]amine in oil phase; sodium hydroxide, L-Lysine and Gum arabic in water as continuous phase.
[0407] An oil phase is prepared by mixing 22.5 g of perfume oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP) and 1.83 g of Bis[3- (triethoxysilyl)propyl]amine. In a separate container, a continuous phase is prepared by dissolving L-Lysine (variable quantities), 0.7 g of Gum Arabic and sodium hydroxide (variable quantities) in 70 g of water.
[0408] The oil phase is emulsified into the water phase using an Ultraturax (10 000 RPM, 2 min) and the emulsion is introduced in a double jacketed reactor. The reaction mixture is then stirred at room temperature for 6 h. The final product is a milky dispersion.
[0409] Table 7: Capsule compositions:
[0410] Example 9
[0411] Preparation of capsules with HCCP and Bis(3-(triethoxysilyl)propyl1amine in oil phase; sodium hydroxide, L-Lysine and Gum arabic in water as continuous phase.
[0412] Same procedure than before except that variable quantities of Bis[3- (triethoxysilyl)propyl]amine are introduced in the oil phase. The quantity of L-Lysine and sodium hydroxide in the water phase are kept constant to respectively 1 .5 g and 0.22 g.
[0413] Table 8: Capsule compositions:
[0414] Example 10
[0415] Preparation of capsules with HCCP and Bis(3-(triethoxysilyl)propyl1amine in oil phase: sodium hydroxide, different amino-acids and Gum arabic in water as continuous phase.
[0416] An oil phase is prepared by mixing 22.5 g of perfume oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP) and 1.83 g of Bis[3- (triethoxysilyl)propyl]amine. In a separate container, a continuous phase is prepared by dissolving different amino acids (variable quantities), 0.7 g of Gum Arabic and 0.22 g of sodium hydroxide in 70 g of water.
[0417] The oil phase is emulsified into the water phase using an Ultraturax (10 000 RPM, 2 min) and the emulsion is introduced in a double jacketed reactor. The reaction mixture is then stirred at room temperature for 6 h. The final product is a milky dispersion.
[0418] Table 9: Capsule compositions:
[0419] Example 11
[0420] Preparation of capsules with HCCP and mixture of silanes in oil phase; sodium hydroxide, L-Lysine and Gum arabic in water as continuous phase.
[0421] An oil phase is prepared by mixing 22.5 g of perfume oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP) and different mixtures of silane-containing monomers (variable quantities). In a separate container, a continuous phase is prepared by dissolving L-Lysine (variable quantities), 0.7 g of Gum Arabic and sodium hydroxide (variable quantities) in 70 g of water.
[0422] The oil phase is emulsified into the water phase using an Ultraturax (10 000 RPM, 2 min) and the emulsion is introduced in a double jacketed reactor. The reaction mixture is then stirred at room temperature for 6 h. The final product is a milky dispersion.
[0423] Table 10: Capsule compositions:
[0424] Example 12
[0425] Preparation of capsules with HCCP, Bis[3-(triethoxysilyl)propyl]amine and a multifunctional polyol in oil phase: sodium hydroxide, L-Lysine and Gum arabic in water as continuous phase.
[0426] An oil phase is prepared by mixing 22.5 g of perfume oil, 7.5 g of benzyl benzoate, 2 g of hexachlorocyclophosphazene (HCCP), 3.65 g of Bis[3-(triethoxysilyl)propyl]amine and a multifunctional polyol (variable quantities). In a separate container, a continuous phase is prepared by dissolving 1.5 g of L-Lysine, 0.7 g of Gum Arabic and 0.3 g of sodium hydroxide in 70 g of water.
[0427] The oil phase is emulsified into the water phase using an Ultraturax (10 000 RPM, 2 min) and the emulsion is introduced in a double jacketed reactor. The reaction mixture is then stirred at room temperature for 6 h. The final product is a milky dispersion.
[0428] Table 11: Capsule compositions:
[0429] Capa™ 3031 from Perstorp
[0430] Emerox® 14555 from Emery oleochemicals
[0431] Example 13
[0432] Preparation of microcapsules based on 6,6-dichloro-1 ,3,5,2l5,4l5,6l5- triazatriphosphinine-2,2,4,4-tetraamine (TCPA) and HCCP
[0433] Preparation of 6,6-dichloro-1 ,3,5,2l5,4l5,6l5-triazatriphosphinine-2,2,4,4-tetraamine (TCPA): Ammonia solution 0.5 M in dioxane (77 ml_, 38.5 mmol) was placed in a 250 mL three-necked round-bottom flask equipped with a condenser and a stirring bar, the setup was purged with N2. HCCP (1.04 g, 3 mmol) was dissolved in acetone (30 mL) and introduced dropwise with a dropping funnel for 30 minutes. The reaction mixture was stirred for 2 h to form white precipitate. Then the precipitate was filtered and washed with excess of hot acetonitrile. The filtrate was concentrated, the solid obtained from the filtrate was precipitated with diethyl ether. The product was dried on air overnight to afford a white powder (m = 0.59 g). Yield: 73%.1H NMR, 6 ppm (500 MHz, DMSO-de): 3.87 (s, NH2);31P NMR (202.5 MHz, DMSO-d6), 6 (ppm): 19.50 (t, J = 52 Hz, 1 P, P-CI), 12.45 (d, J = 52 Hz, 2P, P-NH2). HRMS, m / z: for [M+H]+calc. 269.94, found 269.95. IR: P=N (1347, 1216, 1159 cm’1), P-N (1405, 944 cm’1), H-N-H (1563 cm’1), N-H (797 cm’1) and P-CI (608 cm’1).
[0434] Preparation of TCPA / HCCP microcapsules: TCPA (0.55 g) was dissolved in 25 mL of 1 wt% HDK® H30 silica dispersion in DMSO. HCCP (1.1 g) and TBA (2 mL) were dissolved in cyclohexane (8 mL). 4.5 mL of the TCPA / SiO2 / DMSO part and 0.5 mL of the HCCP / TBA part were combined in a 10 mL vial and stirred with Ultra Turrax for 1 min. Then the vial was placed in water bath and was left stirring at 80°C for 8 h. Then the mixture was stirred at rt overnight.
[0435] Example 14 Fabric softener composition
[0436] A sufficient amount of exemplified microcapsules is weighed and mixed in a fabric softener composition to add the equivalent of 0.116% perfume. Table 12: Fabric Softener composition
[0437] Example 15
[0438] Powder detergent composition
[0439] A sufficient amount of exemplified microcapsules is weighed and mixed in a powder detergent composition to add the equivalent of 0.2% perfume.
[0440] Table 13: Powder detergent composition Example 16
[0441] Spray-dried microcapsules preparation
[0442] Emulsions A-E having the following ingredients are prepared.
[0443] Table 14: Composition of Emulsions A-E and composition of granulated powder A-E after spray-drying
[0444] 1) CapsulTM, Ingredion
[0445] 2) Maltodextrin 10DE origin: Roquette
[0446] 3) Maltose, Lehmann & Voss 4) Silica, Evonik
[0447] 5) see table 8
[0448] Table 15: Composition of Perfume B
[0449]
[0450] 1) Firmenich SA, Switzerland
[0451] 2) 3-(4-tert-butylphenyl)-2-methylpropanal, Givaudan SA, Vernier, Switzerland
[0452] 3)1 -(octahydro-2, 3, 8, 8-tetramethyl-2-naphtalenyl)-1 -ethanone, International Flavors & Fragrances, USA
[0453] 4) Firmenich SA, Switzerland
[0454] 5) Methyl dihydrojasmonate, Firmenich SA, Switzerland
[0455] 6) Firmenich SA, Switzerland
[0456] Components for the polymeric matrix (Maltodextrin and capsul™, or capsulTM , citric acid and tripotassium citrate) are added in water at 45-50°C until complete dissolution. For emulsion D, free perfume B is added to the aqueous phase.
[0457] Microcapsules slurry is added to the obtained mixture. Then, the resulting mixture is then mixed gently at 25°C (room temperature).
[0458] Granulated powder A-E are prepared by spray-drying Emulsion A-E using a Sodeva Spray Dryer (Origin France), with an air inlet temperature set to 215°C and a throughput set to 500 ml per hour. The air outlet temperature is of 105°C. The emulsion before atomization is at ambient temperature.
[0459] Example 17
[0460] Liquid scent booster composition
[0461] A sufficient amount of exemplified microcapsules is weighed and mixed in a liquid scent booster to add the equivalent of 0.2% perfume. Table 16: Liquid scent booster composition
[0462] 1) Deceth-8; trademark and origin : KLK Oleo
[0463] 2) Laureth-9; ; trademark and origin 3) Plantacare 2000UP; trademark and origin : BASF
[0464] Different ringing gel compositions are prepared (compositions 1-6) according to the following protocol.
[0465] In a first step, the aqueous phase (water), the solvent (propylene glycol) if present and surfactants are mixed together at room temperature under agitation with magnetic stirrer at 300 rpm for 5 min.
[0466] In a second step, the linker is dissolved in the hydrophobic active ingredient (fragrance) at room temperature under agitation with magnetic stirrer at 300 rpm. The resulting mixture is mixed for 5 min. Then, the aqueous phase and the oil phase are mixed together at room temperature for 5 min leading to the formation of a transparent or opalescent ringing gel.
[0467] Example 18
[0468] Liquid detergent composition
[0469] A sufficient amount of exemplified microcapsules is weighed and mixed in a liquid detergent to add the equivalent of 0.2% perfume.
[0470] Table 17: Liquid detergent composition
[0471] 1) Hostapur SAS 60; Origin: Clariant
[0472] 2) Edenor K 12-18; Origin: Cognis
[0473] 3) Genapol LA 070; Origin: Clariant
[0474] 4) Origin: Genencor International 5) Aculyn 88; Origin: Dow Chemical
[0475] Example 19
[0476] Unit dose formulation A sufficient amount of exemplified microcapsules is weighed and mixed in a unit dose formulation to add the equivalent of 0.2% perfume.
[0477] The unit dose formulation can be contained in a PVOH (polyvinyl alcohol) film.
[0478] Table 18: Unit dose composition Example 20
[0479] Concentrated All Purpose Cleaner composition
[0480] A sufficient amount of exemplified microcapsules is weighed and mixed in a concentrated all-purpose cleaner composition to add the equivalent of 0.2% perfume.
[0481] Table 19: concentrated all-purpose cleaner composition
[0482] 1) Neodol 91-8 ®; trademark and origin : Shell Chemical
[0483] 2) Biosoft D-40®; trademark and origin : Stepan Company
[0484] 3) Stepanate SCS®; trademark and origin : Stepan Company
[0485] 4) Kathon CG®; trademark and origin : Dow Chemical Company
[0486] All ingredients are mixed together and then the mixture was diluted with water to 100%.
[0487] Example 21
[0488] Solid scent booster composition
[0489] The following compositions are prepared.
[0490] Table 20: Salt-based solid scent booster compositions Table 21 : Urea-based solid scent booster compositions
[0491] Example 22
[0492] Shampoo composition A sufficient amount of exemplified microcapsules is weighed and mixed in a shampoo composition to add the equivalent of 0.2% perfume.
[0493] Table 22: Shampoo composition
[0494] 2) Schweizerhall
[0495] 3) Glydant, Lonza
[0496] 4) Texapon NSO IS, Cognis
[0497] 5) Tego Betain F 50, Evonik
[0498] 6) Amphotensid GB 2009, Zschimmer & Schwarz
[0499] 7) Monomuls 90 L-12, Gruenau
[0500] 8) Nipagin Monosodium, NIPA
[0501] Polyquaternium-10 is dispersed in water. The remaining ingredients of phase A are mixed separately by addition of one after the other while mixing well after each adjunction. Then this pre-mix is added to the Polyquaternium-10 dispersion and was mixed for 5 min. Then Phase B and the premixed Phase C (heat to melt Monomuls 90L-12 in Texapon NSO IS) are added. The mixture is mixed well. Then, Phase D and Phase E are added while agitating. The pH was adjusted with citric acid solution till pH: 5.5 - 6.0. Example 23
[0502] Shampoo composition
[0503] A sufficient amount of exemplified microcapsules is weighed and mixed in a shampoo composition to add the equivalent of 0.2% perfume.
[0504] Table 23: Shampoo composition
[0505] 1 ) EDETA B Powder, BASF
[0506] 2) Jaguar C14 S, Rhodia
[0507] 3) Ucare Polymer J R-400, Noveon
[0508] 4) Sulfetal LA B-E, Zschimmer & Schwarz
[0509] 5) Zetesol LA, Zschimmer & Schwarz
[0510] 6) Tego Betain F 50, Evonik
[0511] 7) Xiameter MEM- 1691 , Dow Corning
[0512] 8) Lanette 16, BASF
[0513] 9) Comperlan 100, Cognis
[0514] 10) Cutina AGS, Cognis
[0515] 11) Kathon CG, Rohm & Haas
[0516] 12) D-Panthenol, Roche
[0517] A premix comprising Guar Hydroxypropyltrimonium Chloride and Polyquaternium-10 are added to water and Tetrasodium EDTA while mixing. When the mixture is homogeneous, NaOH is added. Then, Phase C ingredients are added and the mixture was heat to 75 °C. Phase D ingredients are added and mixed till homogeneous. The heating is stopped and temperature of the mixture is decreased to RT. At 45 °C, ingredients of Phase E while mixing final viscosity is adjusted with 25% NaCI solution and pH of 5.5-6 is adjusted with 10% NaOH solution.
[0518] Example 24
[0519] Rinse-off hair composition A sufficient amount of exemplified microcapsules is weighed and mixed in a rinse-off composition to add the equivalent of 0.2% perfume.
[0520] Table 24: rinse-off composition 1) Genamin KDMP, Clariant
[0521] 2) Tylose H10 Y G4, Shin Etsu
[0522] 3) Lanette O, BASF 4) Arlacel 165, Croda
[0523] 5) Incroquat Behenyl TMS-50-PA- (MH), Croda
[0524] 6) Brij S20, Croda
[0525] 7) Xiameter MEM-949, Dow Corning
[0526] 8) Alfa Aesar
[0527] Ingredients of Phase A are mixed until an uniform mixture was obtained. Tylose is allowed to completely dissolve. Then the mixture is heated up to 70-75°C. Ingredients of Phase B are combined and melted at 70-75°C. Then ingredients of Phase B are added to Phase A with good agitation and the mixing is continued until cooled down to 60°C. Then, ingredients of Phase C are added while agitating and keeping mixing until the mixture cooled down to 40°C. The pH is adjusted with citric acid solution till pH: 3.5 - 4.0.
[0528] Example 25
[0529] Antiperspirant spray anhydrous composition
[0530] A sufficient amount of exemplified microcapsules is weighed and mixed in an antiperspirant spray anhydrous composition to add the equivalent of 0.2% perfume.
[0531] Table 25: antiperspirant spray anhydrous composition
[0532] 1) Dow Corning® 345 Fluid; trademark and origin: Dow Corning
[0533] 2) Aerosil® 200 ; trademark and origin : Evonik
[0534] 3) Bentone® 38; trademark and origin : Elementis Specialities
[0535] 4) Micro Dry Ultrafine; origin : Reheis Using a high speed stirrer, Silica and Quaternium-18-Hectorite are added to the Isopropyl miristate and Cyclomethicone mixture. Once completely swollen, Aluminium Chlorohydrate is added portion wise under stirring until the mixture was homogeneous and without lumps. The aerosol cans are filled with 25 % Suspension of the suspension and 75 % of Propane / Butane (2,5 bar).
[0536] Example 26
[0537] Antiperspirant spray emulsion composition A sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant spray emulsion composition to add the equivalent of 0.2% perfume.
[0538] Table 26: antiperspirant spray emulsion composition
[0539] 1) Tween 65; trademark and origin : CRODA 2) Dehymuls PGPH; trademark and origin : BASF
[0540] 3) Abil EM-90; trademark and origin : BASF
[0541] 4) Dow Corning 345 fluid; trademark and origin : Dow Corning
[0542] 5) Crodamol ipis; trademark and origin : CRODA
[0543] 6) Phenoxyethanol; trademark and origin : LANXESS
[0544] 7) Sensiva sc 50; trademark and origin : KRAFT
[0545] 8) Tegosoft TN; trademark and origin : Evonik
[0546] 9) Aerosil R 812; trademark and origin : Evonik
[0547] 10)Nipagin mna; trademark and origin : CLARIANT
[0548] 11)Locron L; trademark and origin : CLARIANT
[0549] The ingredients of Part A and Part B are weighted separately. Ingredients of Part A are heated up to 60°C and ingredients of Part B are heated to 55 °C. Ingredients of Part B are poured small parts while continuous stirring into A. Mixture were stirred well until the room temperature was reached. Then, ingredients of part C are added. The emulsion is mixed and is introduced into the aerosol cans. The propellant is crimped and added.
[0550] Aerosol filling: 30% Emulsion: 70% Propane I Butane 2,5 bar
[0551] Example 27
[0552] Deodorant spray composition
[0553] A sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant deodorant spray composition to add the equivalent of 0.2% perfume.
[0554] Table 27: deodorant spray composition
[0555] 1) Irgasan® DP 300; trademark and origin : BASF All the ingredients according to the sequence of the Table 24 are mixed and dissolved. Then the aerosol cans are filled, crimp and the propellant is added (Aerosol filling: 40% active solution 60% Propane / Butane 2.5 bar).
[0556] Example 28
[0557] Antiperspirant roll-on emulsion composition
[0558] A sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.
[0559] Table 28: antiperspirant roll-on emulsion composition
[0560] 1) BRU 72; origin : ICI
[0561] 2) BRU 721 ; origin : ICI
[0562] 3) ARLAMOL E; origin : UNIQEMA-CRODA
[0563] 4) LOCRON L; origin : CLARIAN
[0564] Part A and B are heated separately to 75°C; Part A is added to part B under stirring and the mixture is homogenized for 10 minutes. Then, the mixture is cooled down under stirring; and part C is slowly added when the mixture reached 45°C and part D when the mixture reached at 35 °C while stirring. Then the mixture is cooled down to RT. Example 29
[0565] Antiperspirant roll-on composition
[0566] A sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant roll-on composition to add the equivalent of 0.2% perfume.
[0567] Table 29: antiperspirant roll-on composition
[0568] 1) LOCRON L; origin: CLARIANT
[0569] 2) EUMULGIN B-1 ; origin : BASF
[0570] 3) EUMULGIN B-3; origin : BASF
[0571] The ingredients of part B are mixed in the vessel then ingredient of part A is added. Then dissolved part C in part A and B. With perfume, 1 part of Cremophor RH40 for 1 part of perfume is added while mixing well
[0572] Example 30
[0573] Antiperspirant roll-on composition
[0574] A sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.
[0575] Table 30: antiperspirant roll-on emulsion composition
[0576] 2) Irgasan® DP 300; trademark and origin : BASF
[0577] 3) Cremophor® RH 40; trademark and origin : BASF Part A is prepared by sprinkling little by little the Hydroxyethylcellulose in the water whilst rapidly stirring with the turbine. Stirring is continued until the Hydroxyethylcellulose is entirely swollen and giving a limpid gel. Then, Part B is poured little by little in Part A whilst continuing stirring until the whole is homogeneous. Part C is added.
[0578] Example 31
[0579] Deodorant pump without alcohol formulation
[0580] A sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
[0581] Table 31: deodorant composition 1 ) Ceraphyl 41 ; trademark and origin ASHLAND
[0582] 2) DOW CORNING 200 FLUID 0.65cs; trademark and origin DOW CORNING CORPORATION
[0583] 3) Ceraphyl 28; trademark and origin ASHLAND
[0584] 4) Eutanol G; trademark and origin BASF
[0585] 5) Irgasan® DP 300; trademark and origin : BASF
[0586] All the ingredients are mixed according to the sequence of the table and the mixture is heated slightly to dissolve the Cetyl Lactate.
[0587] Example 32
[0588] Deodorant pump with alcohol formulation
[0589] A sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
[0590] Table 32: deodorant composition
[0591] 1) Softigen 767; trademark and origin CRODA
[0592] 2) Cremophor® RH 40; trademark and origin : BASF
[0593] Ingredients from Part B are mixed together. Ingredients of Part A are dissolved according to the sequence of the Table and are poured into part B.
[0594] Example 32
[0595] Talc formulation A sufficient amount of granules A-E is weighed and mixed in introduced in a standard talc base: 100% talc, very slight characteristic odor, white powder, origin: LUZENAC to add the equivalent of 0.2% perfume.
[0596] Example 33
[0597] Shower-gel Reference
[0598] A sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
[0599] Table 33: shower gel composition
[0600] 2) CARBOPOL AQUA SF-1 POLYMER; trademark and origin: NOVEON
[0601] 3) ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ
[0602] 4) TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT
[0603] 5) KATHON CG; trademark and origin: ROHM & HASS
[0604] Ingredients are mixed, pH is adjusted to 6-6.3 (Viscosity: 4500cPo + / -1500cPo (Brookfield RV / Spindle#4 / 20RPM)).
[0605] Example 34 Shower-gel composition
[0606] A sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
[0607] Table 34: shower gel composition
[0608] 1) EDETA B POWDER; trademark and origin: BASF
[0609] 2) ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ
[0610] 3) TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT
[0611] 4) MERQUAT 550; trademark and origin: LUBRIZOL
[0612] Ingredients are mixed, pH is adjusted to 4.5 (Viscosity: 3000cPo + / -1500cPo (Brookfield RV / Spindle#4 / 20RPM)).
[0613] Example 35
[0614] Shower-gel composition
[0615] A sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume. Table 35: shower gel composition
[0616] 1) EDETA B POWDER; trademark and origin: BASF
[0617] 2) Texapon NSO IS; trademark and origin: COGNIS 3) MERQUAT 550; trademark and origin: LUBRIZOL
[0618] 4) DEHYTON AB-30; trademark and origin: COGNIS
[0619] 5) GLUCAMATE LT; trademark and origin: LUBRIZOL
[0620] 6) EUPERLAN PK 3000 AM; trademark and origin: COGNIS
[0621] 7) CREMOPHOR RH 40; trademark and origin: BASF
[0622] Ingredients are mixed, pH is adjusted to 4.5 (Viscosity: 4000cPo + / -1500cPo
[0623] (Brookfield RV / Spindle#4 / 20RPM))
[0624] Example 36 Soap bar
[0625] A sufficient amount of exemplified microcapsules is weighed and mixed in a soap bar formulation a concentration of 7.5% w / w. Table 36: composition of soap formulation
[0626] Example 37 Cosmetic day cream
[0627] A sufficient amount of exemplified microcapsules is weighed and mixed into a cosmetic skin cream (see composition below) at a concentration of 5%w / w.
[0628] Table 37: Cream composition
[0629] 1) ARLATONE 985
[0630] 2) TEFOSE 2561 3) COSBIOL
[0631] 4) GLYDANT PLUS Example 38
[0632] Hand Dishwash
[0633] A sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
[0634] Table 38: Hand dishwash composition
[0635] 1 ) Biosoft S-118®; trademark and origin : Stepan Company
[0636] 2) Ninol 40-CO®; trademark and origin : Stepan Company
[0637] 3) Stepanate SXS®; trademark and origin : Stepan Company
[0638] 4) Tergitol 15-S-9®; trademark and origin : Dow Chemical Company
[0639] Water with sodium hydroxide and diethanolamide are mixed. LAS is added. After the LAS is neutralized, the remaining ingredients are added. The pH was Checked (=7-8) and adjusted if necessary.
[0640] Example 39
[0641] Toothpaste formulation A sufficient amount of a microcapsule slurry M (prepared according to the protocol disclosed in example 1 except that a menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor. Table 39: Toothpaste formulation
[0642] 1) Tixosil 73; trademark and origin :
[0643] 2) Tixosil 43; trademark and origin : Example 40
[0644] Dicalcium Phosphate based toothpaste formulation
[0645] A sufficient amount of a microcapsule slurry M (prepared according to the protocol disclosed in example 1 except that a menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor.
[0646] Table 40: Toothpaste formulation
[0647] 1) Aerosil®200; trademark and origin:
[0648] Example 41
[0649] Mouthwash alcohol free formulation
[0650] A sufficient amount of a microcapsule slurry M (prepared according to the protocol disclosed in example 1 except that a menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor. Table 41: Mouthwash formulation
[0651] Example 42
[0652] Mouthwash formulation
[0653] A sufficient amount of a microcapsule slurry M (prepared according to the protocol disclosed in example 1 except that a menthol flavor is encapsulated) is weighed and mixed in the following composition to add the equivalent of 0.2% flavor. Table 42: Mouthwash formulation
Claims
CLAIMS1- A core-shell microcapsule comprising :- a core comprising a hydrophobic material, and- a shell comprising the reaction product between at least one compound containing inorganic moieties and at least one compound having at least two P-CI functions.2- The core-shell microcapsule according to claim 1 , wherein the shell contains at least 50%, preferably at least 70%, more preferably at least 90%, even most preferably 100% of inorganic moieties.3- The core-shell microcapsule according to claim 1 or 2, wherein the compound having at least two P-CI functions is selected from the group consisting of compound with formula PXCI3, where X is O, S, or NH or NR1where R1is any hydrocarbon group, optionally comprising heteroatoms. Preferably, the compound having at least two P-CI functions can be selected from the group consisting of compound phosphorus oxy trichloride (POCI3), thiophosphorus trichloride (PSCI3), phosphorimidic trichloride (PNHCI3), N-substituted- phosphorimidic trichloride (PNR1Cl3), phosphorus trichloride, phosphorus pentachloride, hexachlorocyclophosphazene (HCCP) and its derivatives, R1OPXCl2 (with X is O, NH, NR1or S), such as alkyl phosphorodichloridate (R1OPOCh) and / or alkyl dichlorothiophosphate (R1OPSCh) (wherein R1can be any hydrocarbon group optionally with heteroatoms); poly(dichlorophosphazene), 3,9-dichloro-2,4,8,10-tetraoxa-3A5,9A5- diphosphaspiro[5.5]undecane 3,9-dioxide, and mixtures thereof.4- The core-shell microcapsule according to claim 3, wherein the compound having at least two P-CI functions is hexachlorocyclophosphazene (HCCP) or its derivatives or its polymers.5- The core-shell microcapsule according to anyone of the preceding claims, wherein the compound having inorganic moieties is a silicon containing monomer, polymer, oligomers or particle and mixtures thereof, preferablyselected from the group consisting of amino functional silanes, sulfur functional silanes, nonfunctional silanes and mixtures thereof.6- The core-shell microcapsule according to claim 5, wherein the amino functional silane is chosen in the group consisting of Bis[3-(triethoxysilyl)propyl]amine, 3- aminopropyltriethoxysilane 3-(2-Aminoethylamino)propyltriethoxysilane, N- phenylaminomethyltriethoxysilane, 1 ,1 ,1-Triethoxysilanamine and its polymers and mixtures thereof, wherein the sulfur functional silanes is chosen in the group consisting of 3-mercaptopropyltriethoxysilane, wherein the nonfunctional silane is chosen in the group consisting of 1 ,2- bis(triethoxysilyl)ethane, 1 -(triethoxysilyl)-2-(diethoxymethylsilyl)ethane and tri ethoxysilane and mixtures thereof.7- The core-shell microcapsule according to anyone of the preceding claims, wherein the hydrophobic material comprises a perfume.8- A process for preparing a core-shell microcapsule slurry comprising the steps of: a) Optionally, providing at least one compound having at least two P-CI functions b) admixing at least one hydrophobic material with the optional compound obtained in step a) to form an oil phase; c) Dispersing the oil phase into a continuous phase C1 or dispersing a continuous phase C1 into the oil phase to form a two-phases dispersion; d) Optionally, dispersing the two-phases dispersion into a continuous phase C2 comprising optionally at least one compound having at least two P-CI functions to form a multiple dispersion; e) curing the dispersion obtained in step c) or d) to form microcapsules in the form of a slurry, wherein a compound having inorganic moieties is added in step a) and / or step b) and / or step c) and or / step d) and / or step e).9- The process according to claim 8, wherein a stabilizer is added in the oil phase and / or in the dispersing phase.10-The process according to claim 8, wherein the stabilizer is chosen in the group consisting of inorganic particles, surfactant, polymeric emulsifier such as polysaccharides, proteins, glycoproteins, and mixtures thereof.11 -The process according to anyone of the claims 8 to 10, wherein a nucleophile chosen in the group consisting of nitrogen nucleophile, sulfur nucleophile, enol carbon nucleophile, oxygen nucleophile, phosphor nucleophile and mixtures thereof is added in step a) and / or step b) and / or step c) and / or step d) and / or step e).12-The process according to any one of claims 8 to 11 , wherein the compound having at least two P-CI functions is added in an amount comprised between 0.5 and 10%, preferably between 1 and 5% by weight based on the total weight of the multiple dispersion.13- The process according to any one of claims 8 to 12, wherein the compound having inorganic moieties is added in an amount comprised between 1 and 15%, preferably between 1 and 8% by weight based on the total weight of the multiple dispersion.14- The process according to any one of claims 8 to 13, wherein the multiple dispersion is a two-phases dispersion.15- Consumer product, preferably in the form of a home-care product or personal care product or fabric care product, comprising the microcapsules as defined in anyone of claims 1 to 7.
Citation Information
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