Cleavable polyhydric alcohol-based microcapsules

Abstract

The present invention relates to a novel method for producing cleavable polyhydric alcohol-based microcapsules. The cleavable polyhydric alcohol-based microcapsules are also the subject of the present invention. Fragrance compositions and consumer products, particularly perfumed consumer products in the form of home care or personal care products, containing the capsules are also part of the present invention.

Description

[Technical field]

[0001] The present invention relates to a novel method for producing cleavable polyhydric alcohol-based microcapsules. The cleavable polyhydric alcohol-based microcapsules are also the subject of the present invention. Perfume compositions and consumer products containing said capsules, especially perfumed consumer products in the form of home care or personal care products, are also part of the present invention.

[0002] 2. Background of the Invention One of the problems facing the fragrance industry is that the olfactory benefits provided by odoriferous compounds are lost relatively quickly due to their volatility, especially the volatility of the "top notes". To control the release rate of volatile substances, delivery systems such as perfume-containing microcapsules are needed to protect the core payload and release it later when the trigger is pulled. The main requirement from the industry for such systems is to be able to remain suspended in a difficult base without physical dissociation or degradation. This is called the stability of the delivery system. For example, personal and household fragrance detergents that contain high levels of aggressive surfactants are very difficult for microcapsule stability.

[0003] Polyurea and polyurethane-based microcapsule slurries are widely used in the perfume industry and elsewhere, as they provide a long-lasting and pleasant olfactory effect after application to various substrates, and are widely disclosed in the prior art (see, for example, the applicant's WO 2007 / 004166 or EP 2300146).

[0004] There remains a need to provide new microcapsules without compromising on the capsule performance in terms of stability, especially in difficult media such as consumer product bases, nor on providing good performance in terms of delivery of active ingredients, e.g. in the case of fragrance ingredients, good olfactory performance.

[0005] The present invention proposes a solution to the above problems by providing novel cleavable polyhydric alcohol-based microcapsules with a covalently compatible network based on a reversible reaction.

[0006] Summary of the Invention It has now surprisingly been found that the use of cleavable polyhydric alcohols as building blocks for generating the polymeric walls of microcapsules leads to high performance core-shell microcapsules encapsulating hydrophobic components. The presence of a covalently compatible network was found to result in high performance microcapsules.

[0007] Thus, the method of the present invention provides a solution to the above-mentioned problems since it is possible to produce microcapsules that exhibit the desired stability in a bulky base.

[0008] In a first aspect, the present invention provides a method for producing a core-shell microcapsule slurry, the method comprising: a) adding at least one multifunctional monomer to a hydrophobic material, preferably a perfume, to form an oil phase; b) preparing a dispersed phase that is immiscible with the oil phase; c) adding an oil phase to the dispersed phase to form a two-phase dispersion; d) optionally adding reactants to the dispersion obtained in step c); e) carrying out a hardening step to form core-shell microcapsules in the form of a slurry. Including, In step a) and / or step b), a stabilizer is added, In step a) and / or step b) and / or step c) and / or step d), at least one cleavable polyhydric alcohol is added, The cleavable polyhydric alcohol is represented by the following formula (I): [ka] [In the formula, Each R 1 are independently H or CHOH, p and q are integers varying between 1 and 3, preferably p and q are either 1 or 2; X is C2~C 30 a hydrocarbon group, which may contain 1 to 10 heteroatoms selected from O, S and N, thereby forming an ether, ester, carboxylic acid, aldehyde, ketone, alcohol, thiol, disulfide, thioether, thioester, carbamate, amide, oxime, imine, amine or nitrile functional group.

[0009] In a second aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: an oily core containing a hydrophobic material, preferably a fragrance; a shell comprising the reaction product of a polyfunctional monomer with a cleavable polyhydric alcohol as defined above; The present invention relates to a core-shell microcapsule comprising:

[0010] A third object of the present invention is to an oily core containing a hydrophobic material, preferably a fragrance; a shell comprising the reaction product of a polyfunctional monomer with a cleavable polyhydric alcohol as defined above; The core-shell microcapsule slurry includes at least one microcapsule having the following structure:

[0011] A fourth subject of the invention is a core-shell microcapsule slurry obtainable by the method defined above.

[0012] Another subject of the present invention is (i) a microcapsule or a microcapsule slurry as defined above, wherein the hydrophobic material comprises a perfume; (ii) at least one component selected from the group consisting of a perfume carrier and a perfume base; (iii) optionally, at least one flavor adjuvant; The fragrance composition comprises:

[0013] Another subject of the present invention is - a personal care active base; - microcapsules or a microcapsule slurry as defined above, or a fragrance composition as defined above; and is in the form of a personal care composition.

[0014] Another subject of the present invention is - a home or fabric care active base; - microcapsules or a microcapsule slurry as defined above, or a fragrance composition as defined above; and in the form of a home care composition or a fabric care composition.

[0015] Detailed Description of the Invention Unless otherwise indicated, percentages (%) are intended to indicate proportions by weight of a composition.

[0016] "Active ingredient" means a single compound or a combination of ingredients.

[0017] By "fragrance or flavor oil" is meant a single aroma or flavor compound or a mixture of several aroma or flavor compounds.

[0018] "Consumer product" or "final product" means a product that is ready for distribution, sale and use by a consumer.

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

[0020] By "microcapsule" or the like in the present invention is meant a core-shell microcapsule having a particle size distribution in the micron range (e.g., a mean diameter (d(v,0.5)) comprised between about 1 and 3000 microns, preferably between 1 and 1000 microns, more preferably between 1 and 500 microns, even more preferably between 5 and 50 microns) and comprising an outer polymer-based solid shell and an inner continuous oil phase surrounded by the outer shell.

[0021] "Microcapsule slurry" means microcapsules dispersed in a liquid. According to one embodiment, the slurry is an aqueous slurry, i.e., the microcapsules are dispersed in an aqueous phase.

[0022] "Multifunctional monomer" refers to a molecule that chemically reacts or bonds as a unit to form a polymer or supramolecular polymer. The multifunctional monomer of the present invention has at least two functional groups that can react or bond with the functional groups of other monomers to form a (polymeric) microcapsule shell. In the present invention, the terms "shell" and "wall" are used interchangeably.

[0023] The "cleavable polyhydric alcohol" is represented by the following formula: [ka] [In the formula, Each R 1 are independently H or CHOH, p and q are integers varying between 1 and 3, preferably p and q are either 1 or 2; X is C2~C 30 a hydrocarbon group, which may contain 1 to 10 heteroatoms selected from O, S and N, thereby forming an ether, ester, carboxylic acid, aldehyde, ketone, alcohol, thiol, disulfide, thioether, thioester, carbamate, amide, oxime, imine, amine or nitrile functional group.

[0024] According to the present invention, X can be split into at least two distinct moieties by cleavage of one or more covalent bonds as a result of an oxidation-reduction reaction, hydrolysis, retro-1,4-addition, the action of light and / or a combination thereof.

[0025] According to the present invention, the terms "polyacid chloride" and "polyacyl chloride" are used interchangeably.

[0026] It was found that reacting a cleavable polyhydric alcohol with at least one other multifunctional monomer during the formation of the polymer capsule shell resulted in core-shell microcapsules that exhibited good overall performance in difficult bases. The cleavable polyhydric alcohol, when present in the shell as a comonomer, was surprisingly stable in difficult bases. [Brief description of the drawings]

[0027] [Figure 1] FIG. 1 shows optical microscope photographs of poly(urethane) core-shell microcapsules according to the present invention.

[0028] Manufacturing method of microcapsule slurry A first object of the present invention is a method for producing a core-shell microcapsule slurry, comprising the steps of: a) adding at least one multifunctional monomer to a hydrophobic material, preferably a perfume, to form an oil phase; b) preparing a dispersed phase that is immiscible with the oil phase; c) adding an oil phase to the dispersed phase to form a two-phase dispersion; d) optionally adding reactants to the dispersion obtained in step c); e) carrying out a hardening step to form core-shell microcapsules in the form of a slurry. Including, In step a) and / or step b), a stabilizer is added, In step a) and / or step b) and / or step c) and / or step d), at least one cleavable polyhydric alcohol is added, The cleavable polyhydric alcohol is represented by the following formula (I): [ka] [In the formula, Each R 1 are independently H or CHOH, p and q are integers varying between 1 and 3, preferably p and q are either 1 or 2; X is C2~C 30 a hydrocarbon group, which may contain 1 to 10 heteroatoms selected from O, S and N, thereby forming an ether, ester, carboxylic acid, aldehyde, ketone, alcohol, thiol, disulfide, thioether, thioester, carbamate, amide, oxime, imine, amine or nitrile functional group.

[0029] Step a): Adding at least one multifunctional monomer to a hydrophobic material, preferably a fragrance, to form an oil phase. Hydrophobic Materials Hydrophobic materials according to the present invention can be "inert" materials such as solvents and active ingredients.

[0030] When the hydrophobic materials are active ingredients, they are preferably selected from the group consisting of flavors, flavor ingredients, fragrances, fragrance ingredients, dietary supplements, cosmetics, pesticides, biocidal actives, and mixtures thereof.

[0031] According to certain embodiments, the hydrophobic material comprises a mixture of a fragrance and another ingredient selected from the group consisting of a nutraceutical, a cosmetic, a pesticide, and a biocidal active.

[0032] According to certain embodiments, the hydrophobic material comprises a mixture of a biocidal active and another ingredient selected from the group consisting of fragrances, dietary supplements, cosmetics, and pesticides.

[0033] According to certain embodiments, the hydrophobic material comprises a mixture of a pesticide and another ingredient selected from the group consisting of fragrances, dietary supplements, cosmetics, and biocidal actives.

[0034] According to certain embodiments, the hydrophobic material comprises a fragrance.

[0035] According to a particular embodiment, the hydrophobic material consists of a fragrance.

[0036] According to a particular embodiment, the hydrophobic material consists of a biocidal active.

[0037] According to a particular embodiment, the hydrophobic material comprises a pesticide.

[0038] By "fragrance" (also called "perfume oil") herein is meant an ingredient or composition that is liquid at about 20°C. According to any one of the above embodiments, the aforementioned perfume oil may be a fragrance ingredient alone or a mixture of the ingredients in the form of a fragrance composition. By "fragrance ingredient" herein is meant a compound that is used primarily for the purpose of imparting or modulating an odor. In other words, such an ingredient must be recognized by the skilled artisan not only to have an odor but also to be capable of at least imparting or modulating the odor of the composition in a positive or pleasant manner in order to be considered a fragrance ingredient. In the present invention, perfume oil also includes a combination of a fragrance ingredient and a substance that together improves, enhances or modulates the delivery of the fragrance ingredient, such as, for example, a fragrance precursor, emulsion or dispersion, or a combination that imparts additional benefits other than odor modulation or imparting, such as longevity, blooming, malodor neutralization, antibacterial effect, microbial stability, pest control, etc.

[0039] The nature and type of the fragrance ingredients contained in the oil phase are not warranted to be described in detail herein, but in any case they are not exhaustive, and the skilled person can select them according to the use or application and the desired sensory effect based on his general knowledge. Generally, these fragrance ingredients belong to various chemical classes, such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and the aforementioned fragrance co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in references such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest editions, and other works of a similar nature, as well as in the abundant patent literature in the perfumery field. It is also understood that the aforementioned ingredients may be compounds known to release in a controlled manner various types of fragrance ingredients, also known as pro-perfumes or pro-fragrances.Non-limiting examples of suitable propargyl compounds include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2-phenylethyloxo(phenyl)-1-prop ... (Z)-hex-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-ylhexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2-((2-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-methyl and mixtures thereof.

[0040] The fragrance ingredients may be dissolved in a solvent currently used in the fragrance industry. The solvent is preferably not an alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is very hydrophobic and highly sterically hindered, such as Abalyn® or benzyl benzoate. Preferably, the fragrance contains less than 30% solvent. More preferably, the fragrance contains less than 20%, even more preferably less than 10%, all of these percentages being determined by weight relative to the total weight of the fragrance. Most preferably, the fragrance is substantially solvent-free.

[0041] Preferred fragrance ingredients are highly sterically hindered, in particular from one of the following groups: - Group 1: aromatic components comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched C1-C4 alkyl or alkenyl substituent; - Group 2: aromatic components comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted with at least one linear or branched C4-C8 alkyl or alkenyl substituent; - group 3: aromatic components comprising a phenyl ring or a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched C5-C8 alkyl or alkenyl substituent, or substituted with at least one phenyl substituent and optionally one or more linear or branched C1-C3 alkyl or alkenyl substituents; - Group 4: aromatic components comprising at least two fused or linked C5 and / or C6 rings; Group 5: aromatic compounds containing a camphor-like ring structure; - Group 6: at least one C7-C 20 Aromatic components containing ring structures, - Group 7: Fragrance ingredients having a logP value of greater than 3.5 and comprising at least one tert-butyl or at least one trichloromethyl substituent.

[0042] Examples of ingredients from each of these groups are as follows: - Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (supplied by Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate (supplied by Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylates, rose oxide, (S)-1,8-p-menthadien-7-ol (supplied by Firmenich SA, Geneva, Switzerland). SA, Geneva, Switzerland), 1-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-menthanyl acetate, (1R,2S,4R)-4,6,6-trimethyl-bicyclo[3,1,1]heptan-2-ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (Supplied by: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-cyclohexanediethyl dicarboxylate (Supplied by: Firmenich SA, Geneva, Switzerland), (3ARS,6SR,7ASR)-perhydro-3,6-dimethylbenzo[B]furan-2-one (Supplied by: Firmenich SA, Geneva, Switzerland), ((6R)-perhydro-3,6-dimethylbenzo[B]furan-2-one (Supplied by: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde, - group 2: (E)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (supplied by Givaudan SA, Vernier, Switzerland), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (supplied by Firmenich SA, Geneva, Switzerland), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-4-penten-2-ol (supplied by Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl-cis-3-oxo-2-pentyl-1-cyclopentane acetate (supplied by Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl-1-cyclopentanone (supplied by Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (supplied by Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (supplied by Givaudan SA, Vernier, Switzerland), - group 3: damascone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (supplied by Firmenich SA, Geneva, Switzerland), nectalactone ((1'R)-2-[2-(4'-methyl-3'-cyclohexen-1'-yl)propyl]cyclopentanone), α-ionone, β-ionone, damascenone, a mixture of 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (supplied by Firmenich SA, Geneva, Switzerland), 1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (supplied by Firmenich SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate (Supplied by: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (Supplied by: International Flavors and Fragrances, USA), 1-(2,2,3,6-tetramethylcyclohexyl)-3-hexanol (Supplied by: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (Supplied by: 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 (Supplied by Firmenich SA, Geneva, Switzerland), 8-Methoxy-1-p-menthene, (1S,1'R)-2-[1-(3',3'-Dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate (Supplier: Firmenich SA, Geneva, Switzerland), p-tert-butylcyclohexanone, menthenthiol, 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,, - Group 4: methyl cedryl ketone (supplied by International Flavors and Fragrances, USA), mixture of (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0~2,6~]dec-3-en-8-yl 2-methylpropanoate and (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0~2,6~]dec-4-en-8-yl 2-methylpropanoate, vetiverol, vetiveron, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone (supplied by International Flavors and Fragrances, USA). 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-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]deca-3,6-diene, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4-indenone (supplied by International Flavors and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3(1,1-dimethyl-5-indanyl)propanal (supplied by Firmenich SA, Geneva, Switzerland), 3',4-dimethyltricyclo[6.2.1.0(2,7)]undec-4-ene-9-spiro-2'-oxirane (Supplied by: Firmenich SA, Geneva, Switzerland), 9 / 10-ethyldiene-3-oxatricyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (Supplied by: Firmenich SA, Geneva, Switzerland), octalinol, dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan (Supplied by: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl acetate, and tricyclo[5.2.1.0(2,6)]dec-4-en-8-yl acetate, and tricyclo[5.2.1.0(2,6)]dec-3-en-8-yl propanoate, and tricyclo[5.2.1.0(2,6)]dec-4-en-8-ylpropanoate, (+)-(1S,2S,3S)-2,6,6-trimethylbicyclo[3.1.1]heptane-3-spiro-2'-cyclohexen-4'-one,. - group 5: camphor, borneol, isobornyl acetate, 8-isopropyl-6-methylbicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxycedrane, (8-methoxy-2,6,6,8-tetramethyltricyclo[5.3.1.0(1,5)]undecane (supplied by Firmenich SA, Geneva, Switzerland), cedrene, cedrenol, cedrol, mixture of 9-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0(2,7)]undecane-4-one (supplied by Firmenich SA, Geneva, Switzerland) SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylenebicyclo[4.3.1]decane (Supplied by Firmenich SA, Geneva, Switzerland), - group 6: (trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (supplied by Firmenich SA, Geneva, Switzerland), Ambrettolide LG ((E)-9-hexadecen-16-olide, supplied by Firmenich SA, Geneva, Switzerland), pentadecenolide (supplied by Firmenich SA, Geneva, Switzerland), Musenone (3-methyl-(4 / 5)-cyclopentadecenone, supplied by Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (supplied by Firmenich SA, Geneva, Switzerland), pentadecanolide (supplied by Firmenich SA, Geneva, Switzerland), cyclopentadecanone (supplied by Firmenich SA, Geneva, Switzerland), 1-ethoxyethoxy)cyclododecane (supplied by Firmenich SA, Geneva, Switzerland) 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 (Supplier: Givaudan SA, Vernier, Switzerland), 2,2,2-trichloro-1-phenylethyl acetate.

[0043] Preferably, the fragrance comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients selected from groups 1 to 7 as defined above. More preferably, said fragrance comprises at least 30%, preferably at least 50% of ingredients selected from groups 3 to 7 as defined above. Most preferably, said fragrance comprises at least 30%, preferably at least 50% of ingredients selected from groups 3, 4, 6 or 7 as defined above.

[0044] According to another preferred embodiment, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients with a logP greater than 3, preferably greater than 3.5, even more preferably greater than 3.75.

[0045] Preferably, the perfume used in the present invention comprises less than 10% by weight of primary alcohols, less than 15% by weight of secondary alcohols, and less than 20% by weight of tertiary alcohols. Advantageously, the perfume used in the present invention comprises no primary alcohols and less than 15% of secondary and tertiary alcohols.

[0046] According to one embodiment, the oily phase (or oily core) comprises: - 25-100% by weight of perfume oil containing at least 15% by weight of high impact perfume raw material with Log T<-4, - Density is 1.07g / cm 3 The density adjusting material is 0 to 75 mass %. Includes.

[0047] High impact fragrance raw material with Log T<-4 and density of 1.07g / cm 3 The properties of the density adjusting material are described in WO 2018 / 115250, the contents of which are incorporated by reference.

[0048] The term "biocide" refers to a chemical that can kill or reduce or prevent the growth and / or accumulation of living organisms (e.g., microorganisms). Biocides are commonly used in medicine, agriculture, forestry, and industry, for example to prevent fouling of water, agricultural products including seeds, and oil pipelines. Biocides can be pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides, and rodenticides, and / or antimicrobials, such as bactericides, antibiotics, antibacterial agents, antivirals, antifungals, antiprotozoals, and / or antiparasitics.

[0049] As used herein, "pesticide" refers to a substance that acts to repel or attract pests, reduce, inhibit or promote their growth, development or activity. A pest refers to any living organism, whether animal, plant or fungus, that invades or harms plants or animals, and includes insects, particularly arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

[0050] According to a particular embodiment, the hydrophobic material does not include any active ingredient (such as fragrances). According to this particular embodiment, the hydrophobic material comprises, and preferably consists of, a hydrophobic solvent, preferably selected from the group consisting of isopropyl myristate, triglycerides (e.g., Neobee® MCT oil, vegetable oil), D-limonene, silicone oil, mineral oil, and mixtures thereof, optionally with a hydrophilic solvent, preferably selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol, glycol ethers, and mixtures thereof.

[0051] According to any one of the embodiments of the present invention, the hydrophobic material represents approximately 10-60% by weight, or even approximately 15-45% by weight, relative to the total weight of the dispersion obtained after step c).

[0052] According to certain embodiments, the oil phase consists essentially of the polyfunctional monomer, the cleavable polyhydric alcohol, and the fragrance or flavor oil.

[0053] Multifunctional Monomers According to one embodiment, the multifunctional monomer is selected from the group consisting of at least one polyisocyanate, polymaleic anhydride, polyacid chloride, polyepoxide, polyacrylate, polymethacrylate, polyalkoxysilane, and mixtures thereof.

[0054] The polyfunctional monomer used in the process according to the invention is present in an amount corresponding to 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 0.8 to 6% by weight, even more preferably 1 to 3% by weight, relative to the total amount of the oil phase.

[0055] According to a particular embodiment, the monomer added in step a) is at least one polyisocyanate having at least two isocyanate functional groups.

[0056] Suitable polyisocyanates for use according to the present invention include aromatic polyisocyanates, aliphatic polyisocyanates, and mixtures thereof. The aforementioned polyisocyanates contain at least two, preferably at least three, isocyanate functional groups, but may contain up to six, or even only four, isocyanate functional groups. According to a particular embodiment, triisocyanates (three isocyanate functional groups) are used.

[0057] According to one embodiment, said polyisocyanate is an aromatic polyisocyanate.

[0058] The term "aromatic polyisocyanate" is meant herein to include any polyisocyanate that contains an aromatic moiety. Preferably, the aromatic polyisocyanate contains a phenyl, toluyl, xylyl, naphthyl, or diphenyl moiety, more preferably a toluyl or xylyl moiety. Preferred aromatic polyisocyanates are biurets, polyisocyanurates, and trimethylolpropane adducts of diisocyanates, more preferably containing one of the specific aromatic moieties listed above. More preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (available under the trade name Desmodur® RC from Bayer), a trimethylolpropane adduct of toluene diisocyanate (available under the trade name Desmodur® L75 from Bayer), or a trimethylolpropane adduct of xylylene diisocyanate (available under the trade name Takenate® D-110N from Mitsui Chemicals, Inc.). In a most preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

[0059] According to another embodiment, the aforementioned polyisocyanate is an aliphatic polyisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain any aromatic moiety. Preferred aliphatic polyisocyanates are the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, the trimethylolpropane adduct of hexamethylene diisocyanate (available from Mitsui Chemicals, Inc.), or the biuret of hexamethylene diisocyanate (commercially available under the trade name Desmodur® N 100 from Bayer), of which the biuret of hexamethylene diisocyanate is even more preferred.

[0060] According to another embodiment, the at least one polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both containing at least two or three isocyanate functional groups, such as a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate, a mixture of a biuret of hexamethylene diisocyanate and a polyisocyanurate of toluene diisocyanate, and a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of toluene diisocyanate. Most preferably, this is a mixture of a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate. Preferably, when used as a mixture, the molar ratio of aliphatic polyisocyanate to aromatic polyisocyanate is in the range of 80:20 to 10:90.

[0061] According to one embodiment, the at least one polyisocyanate used in the process of the invention is present in an amount corresponding to between 0.1 and 15% by weight, preferably between 0.5 and 10% by weight, more preferably between 0.8 and 6% by weight, even more preferably between 1 and 3% by weight relative to the total amount of the oil phase.

[0062] According to another embodiment, the multifunctional polymer used in the present invention is a polyacid chloride.

[0063] According to one embodiment, the polyacyl chloride is selected from the group consisting of benzene-1,3,5-tricarbonyl chloride, benzene-1,2,4-tricarbonyl trichloride, benzene-1,2,4,5-tetracarbonyl tetrachloride, cyclohexane-1,3,5-tricarbonyl trichloride, isophthalol dichloride, diglycolyl dichloride, succinyl dichloride, terephthaloyl chloride, and mixtures thereof.

[0064] According to a particular embodiment, the polyacyl chloride is 1,3,5-benzenetricarbonyl chloride.

[0065] According to a particular embodiment, the polyacyl chloride has the following formula (II): [ka] [In the formula, s is an integer varying between 1 and 8, preferably between 1 and 6, more preferably between 1 and 4; Q is an (s+1)-valent C3 to C6 alkyl group, or (i) to (vi). [ka] [In the formula, R is a hydrogen atom, or a methyl or ethyl group, preferably a hydrogen atom] 45 The aryl group may be any of a hydrocarbon group.

[0066] According to one embodiment, when the hydrocarbon group Q comprises several groups selected from (i) to (vi), they are separated from each other by at least one carbon atom of Q.

[0067] A "hydrocarbon group" is understood to mean that the group consists of hydrogen and carbon atoms and may take the form of an aliphatic hydrocarbon, i.e., a linear or branched, saturated hydrocarbon (e.g., an alkyl group), a linear or branched, unsaturated hydrocarbon (e.g., an alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g., a cycloalkyl), or an unsaturated cyclic hydrocarbon (e.g., a cycloalkenyl or cycloalkynyl), or an aromatic hydrocarbon, i.e., an aryl group, or a mixture of the aforementioned types of groups; for example, a particular group may contain linear alkyl, branched alkenyl (e.g., having one or more carbon-carbon double bonds), (poly)cycloalkyl and aryl moieties, unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when it is referred to that a group is in the form of more than one type of topology (e.g., linear, cyclic or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic or alkenyl), this also means that the group can have any one of the aforementioned topologies or can contain moieties that are saturated or unsaturated as explained above. Similarly, in all embodiments of the present invention, when it is referred to that a group is in the form of one type of saturated or unsaturated (e.g., alkyl), it means that the group can be in any type of topology (e.g., linear, cyclic or branched) and can have multiple moieties with different topologies.

[0068] The term "...hydrocarbon group, which may contain..." is understood to mean that said hydrocarbon group optionally contains heteroatoms, thereby forming ether, thioether, amine, nitrile or carboxylic acid groups. These groups can either replace hydrogen atoms of the hydrocarbon group, thereby being bonded to the side of said hydrocarbon, or replace carbon atoms (where chemically possible) of the hydrocarbon group, thereby being inserted into a hydrocarbon chain or ring.

[0069] According to one embodiment, when group (vi) is present, it is only present in combination with any one of groups (i) to (v).

[0070] According to a particular embodiment, the acyl chloride is selected from the group consisting of propane-1,2,3-tricarbonyl trichloride, cyclohexane-1,2,4,5-tetracarbonyl tetrachloride, 2,2'-disulfanediyldisuccinyl dichloride, 2-(2-chloro-2-oxoethyl)sulfanylbutanedioyl dichloride, (4-chloro-4-oxobutanoyl)-L-glutamoyl dichloride, (S)-4-((1,5-dichloro-1,5-dioxopentan-2-yl)amino)-4-oxobutanoic acid, 2,2-bis[(4-chloro-4-oxobutanoyl)oxymethyl]butyl 4-chloro-4-oxobutanoate, [2-[2,2-bis[(4-chloro-4 [2-[2,2-bis[(2-chlorocarbonylbenzoyl)oxymethyl]butoxymethyl]-2-[(2-chlorocarbonylbenzoyl)oxymethyl]butyl] 2-chlorocarbonylbenzoate, 4-(2,4,5-trichlorocarbonylbenzoyl)oxybutyl 2,4,5-trichlorocarbonylbenzoate, and mixtures thereof.

[0071] Step b): Producing a dispersed phase that is immiscible with the oil phase There are no particular restrictions on the nature of the solvent which can be used in step b), provided it is capable of dissolving the stabilizer.

[0072] According to a particular embodiment, the dispersed phase comprises, and preferably consists of, water.

[0073] According to another particular embodiment, the water content is less than or equal to 10% by weight, preferably less than or equal to 5% by weight and more preferably less than or equal to 3% by weight relative to the total weight of the dispersed phase.

[0074] According to certain embodiments, the dispersed phase does not comprise water.

[0075] According to one embodiment, the dispersed phase comprises a solvent selected from the group consisting of glycerol, 1,4-butanediol, ethylene glycol, and mixtures thereof.

[0076] Step c): Adding an oil phase to the dispersed phase to form a two-phase dispersion. According to the invention, to stabilize the emulsion, a stabilizer is added to the dispersed phase and / or to the oil phase.

[0077] The aforementioned stabilizers can be ionic or non-ionic emulsifiers or colloidal stabilizers.

[0078] The stabilizer can be a molecular emulsifier (standard emulsion) or a solid particle emulsifier (Pickering emulsion).

[0079] In the present invention, the terms "stabilizer" and "emulsifier" are used interchangeably.

[0080] According to one embodiment, the stabilizer is selected from the group consisting of gum arabic, modified starch, polyvinyl alcohol (PVOH), polyvinylpyrrolidone (PVP), carboxymethylcellulose (CMC), anionic polysaccharides, acrylamide copolymers, inorganic particles, proteins such as soy protein, rice protein, whey protein, egg albumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudo collagen, silk protein, sericin powder, and mixtures thereof.

[0081] If a stabilizer is added to the oil phase, the stabilizer is preferably selected from the group consisting of proteins such as soy protein, rice protein, whey protein, egg albumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudo collagen, silk protein, sericin powder, and mixtures thereof.

[0082] When added to the oil phase, the stabilizer may be pre-dispersed in an inert solvent such as benzyl benzoate or may be mixed with the active ingredients, preferably including perfume oils.

[0083] If a stabilizer is added to the aqueous phase, the stabilizer is preferably selected from the group consisting of gum arabic, modified starch, polyvinyl alcohol (PVOH), polyvinylpyrrolidone (PVP), carboxymethylcellulose (CMC), anionic polysaccharides, acrylamide copolymers, inorganic particles, proteins such as soy protein, rice protein, whey protein, egg albumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudo collagen, silk protein, sericin powder, and mixtures thereof.

[0084] According to any one of the above embodiments of the invention, the dispersion comprises about 0.01-3.0% of the stabilizer, where the percentage is expressed on a w / w basis with respect to the total mass of the oil-in-water emulsion obtained after step c). In yet another aspect of the invention, the dispersion comprises at least about 0.05-1.0% of the colloidal stabilizer. In yet another aspect of the invention, the dispersion comprises about 0.1-0.8% of the stabilizer.

[0085] Step d): adding reactants to the dispersion obtained in step c). Among the reactants that can be used in the present invention, nucleophilic compounds can be mentioned.

[0086] In accordance with the present invention, a nucleophilic compound is defined as a chemical species that reactively donates an electron pair to an electrophile to form a chemical bond.

[0087] The nucleophilic compound may be selected from the group consisting of nitrogen nucleophilic compounds, sulfur nucleophilic compounds, oxygen nucleophilic compounds, carbon nucleophilic compounds, phosphorus nucleophilic compounds, and mixtures thereof.

[0088] The nitrogen nucleophilic compound can have at least one functional group selected from the group consisting of ammonia, azide, amine, nitrite, hydroxylamine, hydrazine, carbazide, phenylhydrazine, semicarbazide, and amide, and mixtures thereof.

[0089] The sulfur nucleophilic compound can have at least one functional group selected from the group consisting of hydrogen sulfide and its salts, thiol (RSH), thiolate anion (RS-), anion of thiol carboxylic acid (RC(O)-S-), and anion of dithiocarbonate (RO-C(S)-S-) and anion of dithiocarbamate (RN-C(S)-S-), and mixtures thereof.

[0090] The oxygen nucleophilic compound can have at least one functional group selected from the group consisting of water, hydroxide anion, alcohol, alkoxide anion, carboxylate anion, carbonate, sulfonate, sulfate, sodium phosphate, sodium silicate, borax, sodium tetraborate, and mixtures thereof.

[0091] The carbon nucleophilic compound can have at least one functional group selected from the group consisting of enol, enol carbon nucleophilic compound, malonate, and acetoacetate.

[0092] The phosphorus nucleophilic compound can have at least one functional group selected from the group consisting of phosphines, phosphite anions, and mixtures thereof.

[0093] According to certain embodiments, the reactants are xylylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, L-lysine, L-lysine ethyl ester, O,O'-bis(2-aminopropyl)polypropylene glycol block-polyethylene glycol block-polypropylene glycol, ethylenediamine, 1,3-diamino-2-hydroxypropane, diethylenetriamine, spermine, spermidine, cystamine, cystine, cystine dialkyl esters, aminoguanidine bicarbonate, N,N'-diethylethylenediamine, polyamidoamine (PAMAM), chitosan, 3-aminopropyltriethoxysilane ... orchid, L-arginine, 1,3-diaminopropane, N-ethylguanidine sulfate, 1,6-diaminohexane, guanidine salts, N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, guanazole, 2-amino-1,3-propanediol, ethanolamine, tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, tris[2-(methylamino)ethyl]amine, 1-(2-aminoethyl)piperazine, triethylenetetramine, triethanolamine, dipotassium phthalate, disodium succinate, dithiothreitol, and mixtures thereof.

[0094] According to the invention, at least one cleavable polyhydric alcohol of formula (I) is added in step a) and / or in step b) and / or in step c) and / or in step d). When added in step a), the polyhydric alcohol may be added to the oil phase together with the polyfunctional monomer as a separate component or in the form of a reaction product of at least one cleavable polyhydric alcohol with the polyfunctional monomer.

[0095] According to one embodiment, step a) consists of adding to the hydrophobic material the reaction product of said cleavable polyhydric alcohol and at least one polyfunctional monomer.

[0096] According to another embodiment, step a) consists of adding at least one cleavable polyhydric alcohol and at least one polyfunctional monomer to the hydrophobic material.

[0097] Cleavable polyhydric alcohol According to the present invention, the cleavable polyhydric alcohol is represented by the following formula (I): [ka] [In the formula, Each R 1 are independently H or CHOH, p and q are integers varying between 1 and 3, preferably p and q are either 1 or 2; X is C2~C 30 a hydrocarbon group, which may contain 1 to 10 heteroatoms selected from O, S and N, thereby forming an ether, ester, carboxylic acid, aldehyde, ketone, alcohol, thiol, disulfide, thioether, thioester, carbamate, amide, oxime, imine, amine or nitrile functional group.

[0098] According to the present invention, X can be split into at least two distinct moieties by cleavage of one or more covalent bonds as a result of an oxidation-reduction reaction, hydrolysis, retro-1,4-addition, the action of light and / or a combination thereof.

[0099] According to one embodiment, X is a compound selected from the group consisting of disulfides, oxazolidines, imines, 1,4-addition products, carbonates and aryl ketone derivatives.

[0100] Preferably, X is [ka] wherein: L is an O or S atom or an NH group, preferably an O atom; M is an S atom or NR 6group, preferably a S atom, Y is CH2, CH2-CH2 or a phenyl group, and Z is O(CH2) x O or (CH2) x group, where x is an integer varying between 1 and 4, and A is COOCH2(CR 2 R 2 ) i , C.H.R. 2 OCH2(CR 2 R 2 ) i or (CR 2 R 2 )(CHR 2 ) x It is based on Each R 2 are independently H, CH, CHCH, CHOH, or CHCHOH groups, and each R 3 is independently a CH3 or CH2CH3 group; R 4 is H or CH3, or, if Y is not a phenyl group, two R 4 together can represent a CH2 or CH2-CH2 group, R 5 is either H or CH3, R 6 is H, a C1-C6 alkyl group, or CH2-CH2-(CH2) j -OH group, and when t=1, two R 6 Together they form CH2-CH2-(CH2) i It may form a base, h is an integer varying between 1 and 6, each i is independently 0 or 1, each j is independently an integer varying between 0 and 2, k and l are integers varying between 0 and 2, and m and n are 1 or 2, with the proviso that k+l+m+n=4; t, u, and u' are 0 or 1, and v and w are 1 or 2, provided that u+v+w=3 (for t=0) or u+u'+v+w=4 (for t=1); The dashed and bold lines are bonds to hydrogen atoms or to the aforementioned X and (CHR 1 OH) p Group (dashed line) or (CHR 1 OH) q groups (bold lines) with the proviso that at least one dashed line and at least one bold line of X is a bond to a CHR 1 It is assumed to be bonded to an OH group.

[0101] According to one embodiment, the cleavable polyhydric alcohol is a compound selected from the group consisting of disulfides, oxazolidines, imines / Schiff bases, 1,4-addition products, carbonates, aryl ketone derivatives, and mixtures thereof.

[0102] Non-limiting examples of polyhydric alcohols are compounds selected from the group consisting of: - disulfides selected from the group consisting of 2,2'-disulfanediylbis(ethan-1-ol), 2,2'-disulfanediylbis(propane-1,3-diol), 3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol, 2,2'-(disulfanediylbis(methylene))bis(2-methylpropane-1,3-diol) or 2,2'-(disulfanediylbis(methylene))bis(2-ethylpropane-1,3-diol), bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 3,3'-disulfanediyl dipropionate, tetrakis(2-hydroxyethyl) 2,2'-disulfanediyl disuccinate, and / or - oxazolidines selected from the group consisting of (3-(2-hydroxyethyl)oxazolidine-2,2-diyl)dimethanol, oxazolidine-2,2,4-triyltrimethanol, 2,2'-(ethane-1,2-diylbis(2-methyloxazolidine-2,3-diyl))bis(ethan-1-ol), (ethane-1,2-diylbis(2-methyloxazolidine-2,4,4-triyl))tetramethano 2,2'-(1,4-phenylenebis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(furan-2,5-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(cyclohexane-1,4-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4,12-diyl)bis(ethan-1-ol), (1,4-phenylenebis(oxazolidine-2,4,4-triyl))tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,3,11,11-tetrayl)tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (1,4-phenylenebis(4-ethyloxazolidine-2,4-diyl))dimethanol, (3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, 2,2'-(3,11-bis(hydroxymethyl)-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4,12-diyl)bis(ethan-1-ol), and / or imines and Schiff bases selected from the group consisting of: 2,2'-((1,4-phenylenebis(methanylylidene))bis(azanylidene))bis(propane-1,3-diol), 2,2'-((furan-2,5-diylbis(methanylylidene))bis(azanylidene))bis(propane-1,3-diol), and / or - 1,4-adducts selected from the group consisting of 2-hydroxyethyl 3-((2-hydroxyethyl)thio)propanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 3-((3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)thio)-2-methylpropanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl (S)-3-((2,3-dihydroxypropyl)thio)propanoate, 2-ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((2-hydroxyethyl)thio)propanoate), 4-hydroxyethyl butyl 3-((1,3-dihydroxypropan-2-yl)amino)propanoate, bis(2-hydroxyethyl) 3,3'-(butylazanediyl)dipropionate, bis(2-hydroxyethyl) 3,3'-((4-hydroxybutyl)azanediyl)dipropionate, bis(2-hydroxyethyl) 3,3'-(piperazine-1,4-diyl)dipropionate, tetrakis(2-hydroxyethyl) 3,3',3'',3'''-(propane-1,3-diylbis(azanetriyl))tetrapropionate, bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate, and / or carbonates selected from the group consisting of bis(2,3-dihydroxypropyl)carbonate, bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)carbonate, benzene-1,3,5-triyltris(3-((2-hydroxyethyl)thio)propyl)tricarbonate, and / or aryl ketone derivatives selected from the group consisting of bis(2-hydroxyethyl) 2,2'-(methylenebis(4,1-phenylene)) bis(2-oxoacetate), bis(2,2-bis(hydroxymethyl)butyl) 2,2'-(methylenebis(4,1-phenylene)) bis(2-oxoacetate), bis(2-hydroxyethyl) 2,2'-(ethane-1,2-diylbis(4,1-phenylene)) bis(2-oxoacetate), bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 2,2'-(1,4-phenylene) bis(2-oxoacetate), 1,1'-(1,4-phenylene) bis(5-hydroxypentan-1-one), and mixtures thereof.

[0103] According to a particular embodiment, the cleavable polyhydric alcohol is not trimethylolpropane.

[0104] According to one embodiment, the monomer is present in the hydrophobic material at a concentration comprised between 0.01 and 50%, preferably between 0.02 and 20%, more preferably between 0.1 and 10% and even more preferably between 0.5 and 5%.

[0105] The cleavable polyhydric alcohol compound of the present invention is added to the slurry so that the molar ratio of the OH group of the cleavable polyhydric alcohol compound to the functional group of the above-mentioned monomer is 0.01 to 10, more preferably 0.1 to 5, more preferably 0.2 to 1, and even more preferably 0.25 to 0.75.

[0106] The choice of the structure of the polyhydric alcohol according to formula (I) for producing a given polymer depends on the conditions of the polymerization reaction. This means that not every polyhydric alcohol is the most suitable monomer for all types of polymerization reactions. For example, when the polymerization reaction is carried out under conditions of strong hydrolysis, i.e., conditions of very high or low pH, easily hydrolyzable polyhydric alcohols may be less preferred than others that are not easily cleaved under the reaction conditions. In such cases, polyhydric alcohols that cleave under the action of light or redox reactions may be preferred. Similarly, when using photoinduced polymerization reactions, hydrolyzable cleavable polyhydric alcohols may be preferred over light-sensitive structures.

[0107] Step e): A curing step is carried out to form core-shell microcapsules in the form of a slurry. The hardening step e) makes it possible to end up with microcapsules in the form of a slurry.

[0108] According to a preferred embodiment, the aforementioned steps are carried out at a temperature of 60-80° C., possibly under pressure, for 1-4 hours to enhance kinetics. More preferably, the aforementioned steps are carried out at 50-90° C. for 30 minutes to 4 hours. However, the curing step can occur at room temperature.

[0109] Optional step: optional external coating step According to a particular embodiment of the present invention, at the end of step e) or during step e), a polymer selected from the group consisting of non-ionic polysaccharides, cationic polymers and mixtures thereof may also be added to the slurry of the present invention to form an outer coating on the microcapsules.

[0110] Nonionic polysaccharide polymers are well known to those skilled in the art and are described, for example, in WO 2012 / 007438, page 29, lines 1 to 25, and in WO 2013 / 026657, page 2, lines 12 to 19, and page 4, lines 3 to 12. Preferred nonionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

[0111] Cationic polymers are well known to those skilled in the art. Preferred cationic polymers have a cationic charge density of at least 0.5 meq / g, more preferably at least about 1.5 meq / g and preferably less than about 7 meq / g, more preferably less than about 6.2 meq / g. The cationic charge density of the cationic polymer can be determined by the Kjeldahl method described in the United States Pharmacopoeia Chemical Tests for Nitrogen Determination. Preferred cationic polymers are selected from those that contain units that contain primary, secondary, tertiary and / or quaternary amino groups, which may form part of the main polymer chain or may have side chain substituents directly attached thereto. The weight average (Mw) molecular weight of the cationic polymer is preferably between 10,000 and 3.5 M Daltons, more preferably between 50,000 and 1.5 M Daltons. According to particular embodiments, cationic polymers based on acrylamide, methacrylamide, N-vinylpyrrolidone, quaternized N,N-dimethylamino methacrylate, diallyldimethylammonium chloride, quaternized vinylimidazole (3-methyl-1-vinyl-1H-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 are used. Preferably, the copolymer is selected from the group consisting of polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-28, polyquaternium-43, polyquaternium-44, polyquaternium-46, cassia hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride, or polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether, starch hydroxypropyltrimonium chloride, and cellulose hydroxypropyltrimonium chloride.Examples of commercial products that may be mentioned are Salcare® SC60 (cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, supplier: BASF), or Luviquat®, for example PQ 11N, FC 550 or Style (polyquaternium-11 to 68, or quaternized copolymer of vinylpyrrolidone, supplier: BASF), or also Jaguar® (C13S or C17, supplier: Rhodia).

[0112] According to any one of the above embodiments of the present invention, said polymer is added in an amount comprised between about 0 and 5% by weight, even between about 0.1 and 2% by weight, the percentage being expressed on a w / w basis with respect to the total weight of the slurry obtained after step d), it being clearly understood by those skilled in the art that only a portion of said added polymer is incorporated into / deposited on the microcapsule shell.

[0113] Manufacturing method of microcapsule powder Another subject of the invention is a method for the preparation of a microcapsule powder, comprising the steps defined above and an additional step consisting of subjecting the slurry obtained in step e) or f) to a drying process such as spray drying to provide the microcapsules themselves, i.e. the powdered microcapsules. It is understood that any standard method known to the skilled artisan is applicable for carrying out such drying. In particular, the slurry can be spray-dried, preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gum, pectin, xanthan, alginate, carrageenan or cellulose derivatives, to provide the powdered microcapsules.

[0114] However, other drying methods may be mentioned, such as extrusion, plating, spray granulation, fluidized bed or even drying at room temperature using materials (carriers, desiccants) that meet certain criteria, as disclosed in WO 2017 / 134179.

[0115] According to a particular embodiment, the carrier material comprises a free perfume oil which can be the same or different from the perfume of the microcapsule core.

[0116] According to a particular embodiment, the carrier material comprises a free perfume oil which can be the same or different from the perfume of the microcapsule core.

[0117] Another subject of the present invention is a carrier material, preferably a polymeric carrier material selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, vegetable gums, pectin, xanthan, alginates, carrageenans, cellulose derivatives and mixtures thereof; - the microcapsules defined above are encapsulated in the aforementioned carrier material; - optionally a free flavoring encapsulated in said carrier material; The solid particles include

[0118] In the present invention, the solid particles and the microcapsule powder defined above can be used without distinction.

[0119] Multi-Capsule System According to one embodiment, the microcapsules of the present invention (a first type of microcapsule) may be used in combination with a second type of microcapsule.

[0120] Another subject of the present invention is - microcapsules of the invention as a first type of microcapsule, - a second type of microcapsule; wherein the first type of microcapsules and the second type of microcapsules differ in their hydrophobic material and / or their wall material and / or their coating material.

[0121] Microcapsule Slurry Another subject of the present invention is the microcapsule slurry obtainable by the method described above.

[0122] The composition of the shell can provide microcapsules that exhibit the desired stability in a product base (eg, effectively counteracting extraction of perfume by surfactants in consumer products).

[0123] Another subject of the present invention is therefore a core-shell microcapsule or a core-shell microcapsule slurry having at least one core-shell microcapsule, said core-shell microcapsule being characterized in that an oily core containing a hydrophobic material, preferably a fragrance; a shell comprising a reaction product of a polyfunctional monomer and a cleavable polyhydric alcohol; and the cleavable polyhydric alcohol is represented by the following formula (I): [ka] [In the formula, Each R 1 are independently H or CHOH, p and q are integers varying between 1 and 3, preferably p and q are either 1 or 2; X is C2~C 30 a hydrocarbon group, which may contain 1 to 10 heteroatoms selected from O, S and N, thereby forming an ether, ester, carboxylic acid, aldehyde, ketone, alcohol, thiol, disulfide, thioether, thioester, carbamate, amide, oxime, imine, amine or nitrile functional group.

[0124] The embodiments and definitions set forth above for the method (eg, hydrophobic material, polyfunctional monomer, cleavable polyhydric alcohol) also apply to the microcapsules.

[0125] Copolymer The present invention also provides copolymers comprising the reaction product of a polyfunctional monomer as defined above with at least one cleavable polyhydric alcohol.

[0126] The above-described embodiments also apply to the microcapsules and copolymers disclosed above.

[0127] Fragrance compositions and consumer products The microcapsules of the invention can be used in combination with active ingredients. The subject of the invention is therefore (i) a microcapsule as defined above; (ii) an active ingredient, preferably selected from the group consisting of cosmetic ingredients, skin care ingredients, fragrance ingredients, flavor ingredients, malodor counteracting ingredients, bactericide ingredients, fungicide ingredients, pharmaceutical or pesticide ingredients, cleaning ingredients, insect repellents or attractants, and mixtures thereof; A composition comprising:

[0128] The capsules of the present invention exhibit good performance in terms of stability in hostile media.

[0129] Another subject of the present invention is (i) a microcapsule or a microcapsule slurry as defined above, wherein the oil comprises a flavoring; (ii) at least one ingredient selected from the group consisting of perfume carriers, perfume co-ingredients, and mixtures thereof; (iii) optionally, at least one flavor adjuvant; The fragrance composition comprises:

[0130] The liquid perfume carrier may be, as a non-limiting example, an emulsifying system, i.e. a system of solvents and surfactants, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, as a non-limiting example, it may be solvents such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol, or ethyl citrate, which are very commonly used. For compositions that include both perfume carriers and perfume co-ingredients, suitable perfume carriers other than those mentioned above may be ethanol, water / ethanol mixtures, limonene, or other terpenes, isoparaffins, such as those known under the trademark Isopar® (supplied by Exxon Chemical), or glycol ethers and glycol ether esters, such as those known under the trademark Dowanol® (supplied by Dow Chemical Company). By "perfuming co-ingredient" is meant herein a compound, other than a microcapsule as defined above, used in a fragrance preparation or composition to impart a hedonic effect. In other words, to be considered a perfuming ingredient, such a co-ingredient must not only have an aroma, but must also be recognized by the skilled artisan as being at least capable of imparting or modulating the aroma of the composition in a positive or pleasant way.

[0131] The nature and type of fragrance co-ingredients contained in the fragrance composition are not warranted to be described in detail herein, but in any case, they are not exhaustive, and a person skilled in the art can select them according to the use or application and the desired organoleptic effect based on his general knowledge. Generally, these fragrance co-ingredients belong to various chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and the aforementioned fragrance co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in references such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its latest editions, and other works of a similar nature, as well as in the abundant patent literature in the perfumery field. It is also understood that the co-ingredients can be compounds known to release various types of fragrance compounds in a controlled manner.

[0132] By "perfume adjuvant" is meant herein an ingredient capable of imparting additional benefits such as color, specific light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in fragrance bases cannot be exhaustive, but it should be mentioned that said ingredients are well known to those skilled in the art.

[0133] Preferably, the fragrance composition according to the present invention comprises 0.01 to 30% by weight of the microcapsules defined above.

[0134] The microcapsules of the present invention can be advantageously used in many fields of application and can be used in consumer products: they can be used in liquid form for liquid consumer products, as well as in powder form for powder consumer products.

[0135] According to a particular embodiment, the consumer product defined above is liquid, and a) at least one surfactant in an amount of 2 to 65% by weight based on the total weight of the consumer product; b) water or a hydrophilic organic solvent that is miscible with water; c) microcapsules or a microcapsule slurry as defined above; d) optionally, non-encapsulated flavorings; Includes.

[0136] According to a particular embodiment, the consumer product as defined above is in powder form, and a) at least one surfactant in an amount of 2 to 65% by weight based on the total weight of the consumer product; b) a microcapsule powder as defined above; c) optionally, a flavor powder different from the microcapsules defined above; Includes.

[0137] In the case of microcapsules containing an oily core of perfume, the product of the invention can be used in particular in perfumed consumer products, such as those belonging to fine fragrances and "functional" perfumery. Functional perfumery includes in particular personal care products such as hair care, body cleansing, skin care, hygiene care, and home care products such as laundry care, surface care, and air care. Another subject of the invention is therefore a perfumed consumer product comprising as perfume ingredient a microcapsule as defined above or a fragrance composition as defined above. The perfume element of said consumer product can be a combination of perfume microcapsules as defined above with free or non-encapsulated perfume, as well as perfume microcapsules of other types than those disclosed herein.

[0138] In particular, liquid consumer products, a) at least one surfactant in an amount of 2 to 65% by weight based on the total weight of the consumer product; b) water or a hydrophilic organic solvent that is miscible with water; c) a fragrance composition as defined above; A liquid consumer product comprising the compound is another subject of the present invention.

[0139] Also, a powdered consumer product comprising: (a) at least one surfactant, in an amount of from 2 to 65% by weight based on the total weight of the consumer product; (b) a fragrance composition as defined above; A powdered consumer product comprising the compound is also part of the invention.

[0140] Thus, the microcapsules of the present invention can be added directly to perfumed consumer products or as part of fragrance compositions of the present invention.

[0141] For the sake of clarity, it should be mentioned that by "perfumed consumer product" it is meant a consumer product that is expected to deliver, among other benefits, a fragrance effect to the surface to which it is applied (e.g. skin, hair, textiles, paper or surfaces in the home) or in the air (air fresheners, deodorants, etc.) In other words, a perfumed consumer product according to the invention is an article of manufacture that comprises a functional formulation, also called a "base", together with a benefit agent, in particular an effective amount of the microcapsules according to the invention.

[0142] The nature and type of other components of the perfumed consumer product are not warranted to be described in detail herein, but in any case, not exhaustive, and the skilled person can select them according to the nature and desired effect of said product based on his general knowledge.The base formulations of consumer products that can incorporate the microcapsules of the present invention can be found in the abundant literature on such products.These formulations are not warranted to be described in detail herein, but in any case, not exhaustive.The skilled person who formulates such consumer products can have no problem selecting the appropriate ingredients based on his general knowledge and available literature.

[0143] Non-limiting examples of suitable perfumed consumer products include fragrances, such as fine perfumes, colognes, aftershaves, body splashes; fabric care products, such as liquid or solid detergents, tablets and pods, fabric softeners, dryer sheets, fabric refreshers, ironing waters, or bleaches; personal care products, such as hair care products (e.g., shampoos, hair conditioners, colorants, or hairsprays), cosmetics (e.g., vanishing creams, body lotions, or deodorants or antiperspirants), or skin care products (e.g., for example, a perfumed soap, a shower or bath smooth, a body wash, an oil or gel, a bath salt, or a hygiene product; an air care product, an air freshener, or a "ready to use" powder air freshener; or a home care product, for example, an all-purpose cleaner, a liquid or powder or tablet dishwashing product, a toilet cleaner, or a product for cleaning various surfaces, for example, sprays and wipes intended for treating / refreshing textiles or hard surfaces (floors, tiles, stone floors, etc.); a hygiene product, for example, a sanitary napkin, a diaper, a toilet paper.

[0144] Another subject of the present invention is - a personal care active base; - microcapsules or a microcapsule slurry as defined above, or a fragrance composition as defined above; wherein the consumer product is in the form of a personal care composition.

[0145] The personal care active bases that can incorporate the microcapsules of the present invention can be found in the abundant literature related to such products.These formulations are not warranted to be described in detail in this specification, and in any case, are not exhaustive.Those skilled in the art who formulate such consumer products can easily select suitable ingredients based on their general knowledge and available literature.

[0146] The personal care composition is preferably selected from the group consisting of a hair care product (e.g., a shampoo, a hair conditioner, a coloring agent, or a hairspray), a cosmetic product (e.g., a vanishing cream, a body lotion, or a deodorant or antiperspirant), or a skin care product (e.g., a perfumed soap, a shower or bath mousse, a body wash, an oil or gel, a bath salt, or a hygiene product).

[0147] Another subject of the present invention is - a home or fabric care active base; - microcapsules or a microcapsule slurry as defined above, or a fragrance composition as defined above; wherein the consumer product is in the form of a home care or fabric care composition.

[0148] Home care or fabric care active bases that can incorporate the microcapsules of the present invention can be found in the abundant literature on such products.These formulations are not warranted to be described in detail in this specification, and in any case cannot be exhaustive.Those skilled in the art who formulate such consumer products can easily select suitable ingredients based on their general knowledge and available literature.

[0149] Preferably, the consumer product comprises 0.1 to 15% by weight, more preferably 0.2 to 5% by weight, of the microcapsules of the invention, these percentages being determined by weight relative to the total weight of the consumer product. Naturally, the abovementioned concentrations can be adapted depending on the beneficial effect desired in each product.

[0150] Fabric softener One subject of the present invention is a consumer product in the form of a fabric softener composition, comprising: - a fabric softener active base, preferably selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts (ester quats), Hamburg ester quats (HEQ), TEAQ (triethanolamine quats), silicones and mixtures thereof, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; and consumer products, including

[0151] Liquid detergent One subject of the present invention is a consumer product in the form of a liquid detergent composition, - a liquid detergent active base, preferably selected from the group consisting of anionic surfactants, such as alkylbenzenesulfonates (ABS), secondary alkylsulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and non-ionic surfactants, such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; and consumer products, including

[0152] Solid detergent One subject of the present invention is a consumer product in the form of a solid detergent composition, comprising - a solid detergent active base, preferably selected from the group consisting of anionic surfactants, such as alkylbenzenesulfonates (ABS), secondary alkylsulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), methyl ester sulfonates (MES), and non-ionic surfactants, such as alkylamines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; and consumer products, including

[0153] Shampoo / Shower gel One subject of the present invention is a consumer product in the form of a shampoo or shower gel composition, a shampoo or shower gel active base, preferably selected from the group consisting of sodium alkyl ether sulfates, ammonium alkyl ether sulfates, alkyl amphoacetates, cocamidopropyl betaine, cocamide MEA, alkyl glucosides and amino acid surfactants, and mixtures thereof, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition; - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; and consumer products, including

[0154] Rinse-off conditioner One subject of the present invention is a consumer product in the form of a rinse-off conditioner composition, comprising: a rinse-off conditioner active base, preferably selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition, - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; and consumer products, including

[0155] Hair coloring agents One subject of the present invention is a consumer product in the form of an oxidative hair coloring composition, comprising - an oxidizing phase comprising an oxidizing agent and an alkaline phase comprising an alkaline agent, a dye precursor and a coupling compound, said dye precursor and said coupling compound forming an oxidizing hair dye in the presence of the oxidizing agent, preferably in an amount comprised between 85 and 99.95% by weight relative to the total weight of the composition; - microcapsules or a microcapsule slurry as defined above, preferably in an amount comprised between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, relative to the total weight of the composition; and consumer products, including

[0156] By "oxidative hair coloring composition" is meant a composition that contains two groups of colorless dye molecules: dye precursors and coupling agents. When these react with each other through an oxidative process, they form a wide range of colored molecules (dyes) that are trapped in the hair due to their size. In other words, the dye precursors and coupling compounds form an oxidative hair dye in the presence of an oxidizing agent.

[0157] The terms "dye precursor" and "oxidative dye precursor" are used interchangeably in the present invention.

[0158] The dye precursors may be aromatic compounds derived from benzene substituted with at least two electron donating groups such as NH2 or OH at the para or ortho positions to impart the property of being easily oxidized.

[0159] According to one embodiment, the dye precursor is selected from the group consisting of p-phenylenediamine, 2,5-diaminotoluene, N,N-bis(2-hydroxymethyl)-p-phenylenediamine, 4-aminophenol, 1,4-diaminobenzene, and mixtures thereof.

[0160] The primary dye precursors are used in combination with a coupling agent, preferably an aromatic compound derived from benzene and substituted in the meta position with groups such as NH2 or OH, which does not produce color by itself but modifies the hue, shade or strength of the color produced by the dye precursor.

[0161] According to one embodiment, the coupling agent is selected from the group consisting of resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2,5-diaminotoluene, 1,3-diaminobenzene, 2,4-diaminophenoxyethanol HCl, 2-aminohydroxyethylaminoanisole sulfate, 4-amino-2-hydroxytoluene, and mixtures thereof.

[0162] The oxidative dye precursor is preferably used in an amount comprised between 0.001 and 5% by weight, preferably between 0.1 and 4% by weight, relative to the total weight of the composition.

[0163] The use of oxidative dye precursors and coupling agents in hair coloring formulations is widely disclosed in the prior art and is well known to those skilled in the art, for example in EP 0 946 133 A1, the contents of which are incorporated by reference.

[0164] The alkaline phase comprises an alkaline agent, which is preferably selected from the group consisting of ammonium hydroxide, ammonium carbonate, ethanolamine, potassium hydroxide, sodium borate, sodium carbonate, triethanolamine, and mixtures thereof.

[0165] The alkaline agent is preferably used in an amount comprised between 1 and 10% by weight, preferably between 3 and 9% by weight, relative to the total weight of the composition.

[0166] According to the present invention, a coupling agent and a dye precursor in an alkaline medium form an oxidative hair dye in the presence of an oxidizing agent.

[0167] The oxidizing agent provides the oxygen gas necessary to cause the color molecules to form, resulting in a color change in the hair.

[0168] The oxidizing agent should be safe and effective for use in the compositions described herein.

[0169] Preferably, the oxidizing agents suitable for use in the present invention are soluble in the composition according to the invention when in liquid form and / or in the form in which they are intended for use.

[0170] Preferably, the oxidizing agents suitable for use in the present invention are water soluble. The oxidizing agents suitable for use in the present invention are selected from inorganic peroxygen oxidizing agents, preformed organic peroxyacid oxidizing agents and organic peroxide oxidizing agents, or mixtures thereof.

[0171] The oxidizing agent is preferably used in an amount comprised between 5 and 30% by weight, preferably between 5 and 25% by weight relative to the total weight of the composition.

[0172] The hair coloring composition defined in the present invention may contain ingredients commonly used in cosmetic compositions, such as surfactants, cationic polymers, oily substances, silicone derivatives, free-form fragrances, preservatives, UV absorbers, antioxidants, germicides, propellants, and thickeners.

[0173] According to certain embodiments, the hair coloring composition comprises one or more quaternary ammonium compounds to impart hair conditioner benefits, preferably selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride, and mixtures thereof.

[0174] aroma composition According to a particular embodiment, the consumer product is in the form of a fragrance composition comprising: Relative to the total mass of the fragrance composition, - 0.1 to 30% by weight, preferably 0.1 to 20% by weight, of the microcapsules or microcapsule slurry defined above, - 0 to 40% by weight, preferably 3 to 40% by weight, of a fragrance, and Ethanol, 20 to 90% by mass, preferably 40 to 90% by mass.

[0175] The invention will now be further illustrated by means of examples, it will be understood that these examples are not intended to limit in any way the invention as claimed.

[0176] Working Example The invention will now be described in more detail by the following examples, in which the abbreviations have their usual meaning in the art, temperatures are given in degrees Celsius (°C), and NMR spectral data was obtained on a Bruker AMX 500 spectrometer using deuterated dimethylsulfoxide (DMSO)-d6 unless otherwise indicated. 1 H is 500MHz, 13 C was recorded at 125.8 MHz, chemical displacements δ are given in ppm relative to Si(CH3)4 as standard, and coupling constants J are given in Hz (br. = broad peak). Reactions were carried out in standard glassware under N2. Commercially available reagents and solvents were used without purification unless otherwise noted.

[0177] Although a particular conformation or configuration is shown for some compounds, this is not meant to limit the use of these compounds to the depicted isomers, and all possible conformational or configurational isomers are expected to have similar effectiveness according to the present invention.

[0178] 2,2'-disulfanediylbis(ethan-1-ol) (polyhydric alcohol 1) is commercially available and other non-limiting examples of polyhydric alcohols according to formula (I) were prepared as described in Example 1.

[0179] Example 1 Preparation of cleavable polyhydric alcohols according to formula (I) (a) Synthesis of 2,2'-disulfanediylbis(propane-1,3-diol) (polyhydric alcohol 2) Amberlyst 15H (3.0 g) was added to a biphasic mixture of 1,3-di(tert-butyldimethylsilyloxy)-propane-2-thiol (38.1 g, 0.11 mol, prepared as described in JE Casida et al., Bioorganic & Medicinal Chemistry, 2010, 18, 1942-1947) and methanol (300 mL). After stirring overnight at room temperature, the suspension was filtered, washed with methanol (50 mL) and the filtrate was concentrated to give 25.0 g of a biphasic mixture. Acetone (50 mL) was added and heated to about 50° C. to give a solution. This was allowed to cool to room temperature and then placed in a freezer to crystallize. The solid was filtered off, washed with ice-cold acetone and dried under vacuum (0.43 mbar) to give 3.4 g of white crystals. The mother liquor was concentrated, suspended in acetone (50 mL) and placed on an ice bath for 2 h. Filtration, washing with ice-cold acetone (25 mL) and drying under vacuum gave an additional 4.0 g of white crystals as the desired compound (30%).

[0180] [ka]

[0181] (b) Synthesis of (±)-3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol (polyhydric alcohol 3) To a stirred solution of 3-mercaptopropane-1,2-diol (35 mL, 390.0 mmol) in water (35 mL) was added ferrous sulfate hydrate (FeSO4×7H2O, 85 mg, 0.3 mmol). Hydrogen peroxide (35%, 29.15 g, 300.0 mmol) was then added dropwise over 20 min. The reaction was exothermic and the temperature was kept at about 40 °C with an ice bath during the addition of H2O2. After removing the ice bath, the reaction was stirred for 5 h and then poured into a separatory funnel containing ethyl acetate (100 mL). After extraction, the phases were separated and the aqueous layer was re-extracted with ethyl acetate (100 mL) and the organic layer was washed with water (50 mL). After concentration of the aqueous phase, toluene (250 mL) was added and the mixture was further concentrated. Drying under vacuum (0.14 mbar) gave 44.0 g (quantitative) of crude product.

[0182] [ka]

[0183] (c) Synthesis of 2,2'-(disulfanediylbis(methylene))bis(2-methylpropane-1,3-diol) (polyhydric alcohol 4) To a stirred emulsion of (2,2,5-trimethyl-1,3-dioxan-5-yl)methanethiol (8.81 g, 50.0 mmol) in water (50 mL) was added ferrous sulfate hydrate (FeSO4×7H2O, 28 mg, 0.04 mmol) at room temperature. Hydrogen peroxide (35%, 3.7 g, 38.5 mmol) was then added dropwise (exothermic reaction). The mixture was stirred overnight and then poured into a separatory funnel containing ethyl acetate (100 mL). After extraction, the phases were separated, the aqueous layer was re-extracted with ethyl acetate (100 mL), and the organic layer was washed with water (50 mL) and a saturated aqueous solution of NaCl (50 mL), dried (Na2SO4), and concentrated to give 2.06 g (30%) of the desired compound.

[0184] [ka]

[0185] (d) Synthesis of (3-(2-hydroxyethyl)oxazolidine-2,2-diyl)dimethanol (polyhydric alcohol 5) 1,3-Dihydroxypropan-2-one (4.06 g, 50.0 mmol) was suspended in tetrahydrofuran (THF, 150 mL). Then, 2,2'-azanediylbis(ethan-1-ol) (6.31 g, 60.0 mmol) and anhydrous Na2SO4 (10.0 g) were added. After stirring at room temperature for about 90 hours, the reaction mixture was filtered and concentrated. The product was successively treated with cyclohexane (25 mL), stirred at 50°C for 15 minutes, decanted, and treated with toluene (50 mL), stirred at 50°C for 15 minutes, and decanted. The remaining product was concentrated and dried under vacuum to give 8.64 g of crude product.

[0186] [ka]

[0187] (e) Synthesis of (±)-oxazolidine-2,2,4-triyltrimethanol (polyhydric alcohol 6) 2-Aminopropane-1,3-diol (2.78 g, 30.0 mmol) was suspended in THF (75 mL). Na2SO4 (2.00 g, 14.1 mmol, previously oven-dried at 150° C.) and 1,3-dihydroxypropan-2-one (2.70 g, 30.0 mmol) were then added. After stirring at room temperature for about 5 days, the reaction mixture was concentrated and dried under vacuum to give 2.93 g (52%) of the desired compound containing about 13% by weight of THF.

[0188] [ka]

[0189] (f) Synthesis of (±)-2,2'-(ethane-1,2-diylbis(2-methyloxazolidine-2,3-diyl))bis(ethan-1-ol) (polyhydric alcohol 7) 2,2'-Azanediylbis(ethan-1-ol) (4.2 g, 39.9 mmol) was added to a solution of 2,5-hexanedione (1.17 g, 10.3 mmol) in toluene (50 mL). The reaction mixture was heated under reflux overnight in a Dean-Stark apparatus. After cooling to room temperature on a cold water bath, a biphasic mixture was obtained. The toluene layer was decanted and centrifuged. Concentration and repeated bulb-to-bulb distillation (room temperature and 50 °C at 0.011 mbar) to remove the remaining toluene gave 1.70 g of the desired compound as a mixture of diastereoisomers, together with some mono-reacted product and the remaining 2,2'-azanediylbis(ethan-1-ol).

[0190] [ka]

[0191] (g) Synthesis of (±)-2,2'-(1,4-phenylenebis(oxazolidine-2,3-diyl))bis(ethan-1-ol) (polyhydric alcohol 8) Terephthalaldehyde (4.11 g, 30.0 mmol) was dissolved in toluene (75 mL). Then, 2,2'-azanediylbis(ethan-1-ol) (7.01 g, 66.0 mmol) and 4-methylbenzenesulfonic acid monohydrate (0.29 g, 1.5 mmol) were added. The mixture was heated under reflux overnight with azeotropic removal of water (Dean-Stark). After cooling to room temperature, a two-phase system was obtained. The toluene layer was decanted and the oil was washed with toluene (25 mL). The oil was dissolved in hot 2-propanol (10 mL), allowed to cool to room temperature, and stored in a refrigerator. After a few days, crystals formed, which were washed with cold 2-propanol, dissolved in methanol, concentrated, and dried under vacuum to give a white solid. Recrystallization from 2-propanol (15 mL), cooling to room temperature, and storing in a refrigerator gave 2.55 g of white crystals. The toluene decanted after the reaction was concentrated to give an oil. This oil was dissolved in hot 2-propanol (5 mL), allowed to cool to room temperature, and stored in a refrigerator to give an additional 1.07 g of white crystals as a mixture of diastereoisomers. A total of 3.62 g (39%) of the desired compound was obtained.

[0192] [ka]

[0193] (h) Synthesis of (±)-2,2'-(furan-2,5-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol) (polyhydric alcohol 9) 5-(Hydroxymethyl)furan-2-carbaldehyde (5.04 g, 40.0 mmol) was dissolved in DMSO (80 mL). NaBr (1.24 g, 40.0 mmol) was added and the mixture was heated at 150 °C for 18 h. After cooling to room temperature, the reaction mixture was taken up in ethyl acetate (100 mL) and washed with water (100 mL, 3x) and a saturated solution of NaCl (100 mL). The aqueous phase was re-extracted with ethyl acetate (100 mL). The organic phase was dried (Na2SO4) and concentrated. Column chromatography (SiO2, heptane / ethyl acetate 7:3) gave 2.17 g (44%) of furan-2,5-dicarbaldehyde (see, for example, C. Laugel et al., ChemCatChem, 2014, 6, 1195-1198).

[0194] [ka]

[0195] Furan-2,5-dicarboxaldehyde (0.75 g, 6.0 mmol) was dissolved in toluene (50 mL). Then, 2,2'-azanediylbis(ethan-1-ol) (1.51 g, 14.4 mmol) and some more toluene were added. After stirring at room temperature for 5 min, it was heated under reflux for 15 h with azeotropic removal of water (Dean-Stark) to give a mixture of a brown solid and a yellow solution. The liquid was decanted, concentrated, and dried under vacuum to give 1.38 g (77%) of the desired compound as a mixture of diastereoisomers, still containing toluene and some residual 2,2'-azanediylbis(ethan-1-ol).

[0196] [ka]

[0197] (i) Synthesis of (±)-2,2'-(cyclohexane-1,4-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol) (polyhydric alcohol 10) Cyclohexane-1,4-diyldimethanol (molten, 13.24 g, 90.0 mmol) was dissolved in ethyl acetate (300 mL). The immobilized polymer (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) (PIPO AF 944 974265, 1.0 g, 4.9 mmol), KBr (0.1 g, 0.8 mmol), and KHCO3 (2.25 g, 22.5 mmol) were added. An aqueous solution of NaOCl (10%, 165 mL) was then added dropwise over 2 h while maintaining the reaction temperature at 28-30 °C. The biphasic mixture was stirred for 2 h, after which the phases were separated. The aqueous layer was extracted with ethyl acetate (150 mL) and the combined organic phases were washed with a saturated aqueous solution of NaCl (150 mL), a saturated aqueous solution of NaHCO3 (2x), and again with a saturated aqueous solution of NaCl (150 mL), dried (Na2SO4), and concentrated to give 4.12 g (33%) of cyclohexane-1,4-dicarboxaldehyde as a mixture of cis / trans isomers (major / minor ca. 3:1), with spectroscopic data assigned as follows:

[0198] [ka]

[0199] Cyclohexane-1,4-dicarboxaldehyde (1.00 g, 7.2 mmol) was dissolved in toluene (25 mL). Then, 2,2'-azanediylbis(ethan-1-ol) (1.82 g, 17.3 mmol) was added. The mixture was heated under reflux for 20 h with azeotropic removal of water (Dean-Stark). After cooling to room temperature, a biphasic mixture was obtained. The toluene was decanted, concentrated, and dried under vacuum to give an oil. The oil was taken up in ethanol and stored in a freezer. The ethanol was concentrated, and finally crystals were obtained. The supernatant was pipetted and the residue was washed with cold ethanol to give 0.88 g (12%) of the desired compound as a mixture of diastereoisomers.

[0200] [ka]

[0201] (j) Synthesis of (±)-2,2'-(1,9-dioxa-4,12-diazadispiro[4.2.48.25]tetradecane-4,12-diyl)bis(ethan-1-ol) (polyhydric alcohol 11) Cyclohexane-1,4-dione (2.86 g, 25.0 mmol) was dissolved in toluene (50 mL). After stirring at room temperature for 10 min, 2,2'-azanediylbis(ethan-1-ol) (7.96 g, 75.0 mmol) was added. The mixture was stirred at room temperature for 5 min, then heated under reflux with azeotropic removal of water (Dean-Stark) for 3 h and stirred at room temperature overnight. Crystal formation was observed. The toluene was decanted and the residue was dissolved in hot ethanol (50 mL). After cooling to room temperature, the product was placed in the refrigerator and then in the freezer to crystallize. After filtration and washing the residue with ice-cold ethanol, 4.20 g of crystals were obtained. The mother liquor was concentrated and placed in the refrigerator to recrystallize. After filtration, an additional 1.56 g of crystals were recovered. A total of 5.76 g (80%) of the desired compound was obtained.

[0202] [ka]

[0203] (k) Synthesis of (±)-(1,4-phenylenebis(oxazolidine-2,4,4-triyl))tetramethanol (polyhydric alcohol 12) 2-Amino-2-(hydroxymethyl)propane-1,3-diol (4.86 g, 40.0 mmol) was suspended in ethanol (90 mL). Terephthalaldehyde (2.74 g, 20.0 mmol) was then added and the mixture was heated at reflux for 16 h. Concentration and drying under vacuum gave a white crystalline solid. Dissolution in hot ethanol (30 mL), cooling to room temperature and storing in a refrigerator gave white crystals. This was filtered, washed with cold ethanol and dried under vacuum to give 4.19 g (62%) of the desired compound as a mixture of diastereoisomers along with a small amount of (((1E,1'E)-1,4-phenylenebis(methanylylidene))bis(azanylylidene))bis(2-(hydroxymethyl)propane-1,3-diol) (ca. 10%).

[0204] [ka]

[0205] (l) Synthesis of (±)-(1,9-dioxa-4,12-diazadispiro[4.2.48.25]tetradecane-3,3,11,11-tetrayl)tetramethanol (polyhydric alcohol 13) Cyclohexane-1,4-dione (3.96 g, 34.6 mmol) was dissolved in toluene (90 mL). Then, 2-amino-2-(hydroxymethyl)propane-1,3-diol (7.27 g, 59.9 mmol) and 4-methylbenzenesulfonic acid monohydrate (0.1 g, 0.5 mmol) were added. The mixture was heated under reflux for 16 h with azeotropic removal of water (Dean-Stark) to give a white suspension. The suspension was stirred at room temperature for 1 h and filtered. The solid was washed with toluene (20 mL) and dried under vacuum in a desiccator to give 9.46 g (99%) of the desired compound.

[0206] [ka]

[0207] (m) (±)-(1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 Synthesis of ]tetradecane-3,11-diyl)dimethanol (polyhydric alcohol 14) Cyclohexane-1,4-dione (2.28 g, 19.9 mmol) was dissolved in toluene (50 mL). 2-Aminopropane-1,3-diol (5.58 g, 60.0 mmol) was then added. The mixture was heated under reflux overnight with azeotropic removal of water (Dean-Stark). Formation of a precipitate was observed. After cooling to room temperature, the solvent was decanted and the residue was washed with toluene and dissolved in hot ethanol (30 mL). Upon cooling to room temperature and storing in the refrigerator, crystals formed. Filtration and washing with ice-cold ethanol gave 3.87 g (75%) of the desired compound.

[0208] [ka]

[0209] (n) (±)-(3,11-dimethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 Synthesis of ]tetradecane-3,11-diyl)dimethanol (polyhydric alcohol 15) Cyclohexane-1,4-dione (4.00 g, 35.0 mmol) was dissolved in toluene (90 mL). 2-Amino-2-methylpropane-1,3-diol (6.31 g, 60.0 mmol) and 4-methylbenzenesulfonic acid monohydrate (0.1 g, 0.5 mmol) were then added. The mixture was heated under reflux for 16 h with azeotropic removal of water (Dean-Stark) to give a mixture of a brown solid and a pale yellow solution. The liquid was decanted and cooled to room temperature, whereupon a white precipitate formed. The suspension was stirred at room temperature for 1 h and then filtered. The solid was washed with toluene (20 mL) and pentane (20 mL) and dried under vacuum in a desiccator to give 5.74 g (67%) of the desired compound as a mixture of diastereoisomers in a ratio of approximately 2:1.

[0210] [ka]

[0211] (o) Synthesis of (±)-(1,4-phenylenebis(4-ethyloxazolidine-2,4-diyl))dimethanol (polyhydric alcohol 16) Terephthalaldehyde (2.74 g, 20.0 mmol) was dissolved in ethanol (90 mL) at 50° C. Then, 2-amino-2-ethylpropane-1,3-diol (4.91 g, 40.0 mmol) was added. The mixture was stirred at room temperature for several days. After concentration and drying under vacuum, a viscous light yellow oil was obtained. This oil slowly crystallized and consisted of the target compound and 2,2'-(((1E,1'E)-1,4-phenylenebis(methanylylidene))bis(azanylylidene))-bis(2-ethylpropane-1,3-diol), which existed as a mixture of diastereoisomers in a ratio of about 4:1.

[0212] (p) (±)-(3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 Synthesis of ]tetradecane-3,11-diyl)dimethanol (polyhydric alcohol 17) Cyclohexane-1,4-dione (3.96 g, 34.6 mmol) was dissolved in toluene (90 mL). 2-Amino-2-ethylpropane-1,3-diol (7.34 g, 59.7 mmol) and 4-methylbenzenesulfonic acid monohydrate (0.1 g, 0.5 mmol) were then added. The mixture was heated under reflux for 16 h with azeotropic removal of water (Dean-Stark), giving a mixture of a brown solid and a brown solution. The liquid was decanted and cooled to room temperature, whereupon a beige precipitate formed. The suspension was stirred at room temperature for 1 h and then filtered. The solid was washed with toluene (20 mL) and dried under vacuum in a desiccator to give 2.58 g of white crystals. The mother liquor was concentrated and redissolved in ethanol (10 mL) and crystallized to give an additional 1.01 g of crystals. A total of 3.59 g (38%) of the desired compound was obtained.

[0213] [ka]

[0214] (q) Synthesis of 2,2'-(((1E,1'E)-1,4-phenylenebis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol) (polyhydric alcohol 18) 2-Aminopropane-1,3-diol (3.72 g, 40.0 mmol) was dissolved in ethanol (90 mL). Terephthalaldehyde (2.74 g, 20.0 mmol) and ethanol (60 mL) were then added. The mixture was heated under reflux for 19 h to give a white suspension. After cooling to room temperature, filtering, washing with ethanol (15 mL) and drying under vacuum, 4.95 g (88%) of the desired compound was obtained.

[0215] [ka]

[0216] (r) Synthesis of 2,2'-(((1E,1'E)-furan-2,5-diylbis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol) (polyhydric alcohol 19) 2-Aminopropane-1,3-diol (3.72 g, 40.0 mmol) was dissolved in ethanol (150 mL). Furan-2,5-dicarbaldehyde (2.48 g, 20.0 mmol, prepared as described in Example 1h) was then added. The mixture was heated under reflux for 16 h to give an orange solution. After cooling to room temperature, the product crystallized. Chilling in an ice bath, filtration, and washing with cold ethanol (20 mL) gave 3.97 g of product, and the filtrate was concentrated to give an additional 1.42 g of product. A total of 5.39 g (99%) of the desired compound was obtained.

[0217] [ka]

[0218] (s) Synthesis of 2-hydroxyethyl 3-((2-hydroxyethyl)thio)propanoate (polyhydric alcohol 20) 2-Mercaptoethanol (9.3 mL, 132.0 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 0.1 mL, 120.0 mmol) were added to anhydrous THF (150 mL) in a drying apparatus under nitrogen. After cooling to 0-5 °C in an ice bath, 2-hydroxyethyl acrylate (13.93 g, 120.0 mmol) was added dropwise to the stirred solution over 20 min. After rinsing with THF (15 mL), the reaction mixture was stirred on an ice bath for 3 h and then at room temperature overnight. The reaction mixture was then concentrated, poured into aqueous HCl (1%), and extracted with ethyl acetate (100 mL, 2x). The organic layer was washed with water (50 mL, 2x) and a saturated aqueous solution of NaCl (50 mL). The combined organic layers were dried (Na2SO4) and concentrated to give 6.11 g of crude product. The aqueous layer was then extracted with ethyl acetate, saturated with NaCl, and re-extracted with ethyl acetate (100 mL). Drying (Na2SO4) and concentration gave 7.59 g of crude product. Column chromatography (SiO2, ethyl acetate / ethanol 19:1) of the second portion of the product gave 3.13 g of the desired compound.

[0219] [ka]

[0220] (t) Synthesis of 2-ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((2-hydroxyethyl)thio)propanoate) (polyhydric alcohol 21) In a drying apparatus under nitrogen, 2-mercaptoethanol (16.0 mL, 228.0 mmol) and DBU (0.1 mL, 120.0 mmol) were added to anhydrous THF (150 mL). After cooling to 0-5 °C in an ice bath, 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-diyl diacrylate (trimethylolpropane triacrylate, 22.00 g, 74.2 mmol) was added dropwise over 20 min to the stirred solution. After rinsing with THF (15 mL), the reaction mixture was stirred on an ice bath for 3 h and then at room temperature overnight. The reaction mixture was then concentrated, poured into aqueous HCl (1%), and extracted with ethyl acetate (100 mL, 2x). The organic layer was washed with water (50 mL, 2x) and a saturated aqueous solution of NaCl (50 mL). The combined organic layers were dried (Na2SO4) and concentrated to give 39.43 g (quantitative) of the desired compound.

[0221] [ka]

[0222] (u) Synthesis of 4-hydroxybutyl 3-((1,3-dihydroxypropan-2-yl)amino)propanoate (polyhydric alcohol 22) 2-Aminopropane-1,3-diol (1.86 g, 20.0 mmol) was added to a solution of 4-hydroxybutyl acrylate (2.97 g, 20.0 mmol) in acetonitrile (250 mL). The reaction mixture was stirred at room temperature for several days. The reaction mixture was concentrated (0.4 mbar, 45° C.) to give 4.75 g (quantitative) of the desired compound along with some remaining starting material.

[0223] [ka]

[0224] (v) Synthesis of bis(2-hydroxyethyl) 3,3'-(butylazanediyl) dipropionate (polyhydric alcohol 23) Butan-1-amine (2.52 g, 34.5 mmol) in acetonitrile (10 g) was added dropwise over 1 h to a solution of 2-hydroxyethyl acrylate (8.00 g, 69.0 mmol) in acetonitrile (28 g) at 0° C. After stirring overnight at room temperature, the solvent was evaporated. Column chromatography (SiO2, ethyl acetate) afforded 5.60 g of the target compound along with some partially hydrolyzed products and ethane-1,2-diol.

[0225] [ka]

[0226] (w) Synthesis of bis(2-hydroxyethyl) 3,3'-((4-hydroxybutyl)azanediyl) dipropionate (polyhydric alcohol 24) 4-Amino-1-butanol (3.06 g, 34.3 mmol) in acetonitrile (10 g) was added dropwise over 45 min to a solution of 2-hydroxyethyl acrylate (8.02 g, 69.1 mmol) in acetonitrile (27 g) at 0° C. After stirring overnight at room temperature, the solvent was evaporated. Column chromatography (SiO2, ethyl acetate / ethanol 4:1) afforded 9.25 g of the target compound along with some partially hydrolyzed products and ethane-1,2-diol.

[0227] [ka]

[0228] (x) Synthesis of bis(2-hydroxyethyl) 3,3'-(piperazine-1,4-diyl) dipropionate (polyhydric alcohol 25) A solution of 2-hydroxyethyl acrylate (8.30 g, 71.5 mmol), piperazine (3.08 g, 35.8 mmol) in acetonitrile (35.9 g) was stirred at room temperature for 4 h. A precipitate formed which was filtered, washed with fresh acetonitrile and dried under vacuum to give 9.15 g of the desired compound along with some partially hydrolyzed product and ethane-1,2-diol.

[0229] [ka]

[0230] (y) Synthesis of tetrakis(2-hydroxyethyl) 3,3',3'',3'''-(propane-1,3-diylbis(azanetriyl)) tetrapropionate (polyhydric alcohol 26) 1,3-Diaminopropane (1.44 g, 19.4 mmol) in acetonitrile (9 g) was added dropwise over 45 min to a solution of 2-hydroxyethyl acrylate (9.02 g, 77.7 mmol) in acetonitrile (30 g) at 0° C. After stirring overnight at room temperature, the solvent was evaporated. Column chromatography (SiO2, ethyl acetate / ethanol 4:1) afforded 11.40 g of the target compound along with some partially hydrolyzed products and ethane-1,2-diol.

[0231] [ka]

[0232] (z) Synthesis of bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 3,3'-disulfanediyl dipropionate (polyhydric alcohol 27) A solution of 3-(2-carboxyethyldisulfanyl)propanoic acid (10.73 g, 50.0 mmol), 1,1,1-tris(hydroxymethyl)ethane (18.39 g, 150.0 mmol) and toluene-4-sulfonic acid monohydrate (0.30 g, 1.7 mmol) in toluene (125 mL) was heated under reflux in a Dean-Stark apparatus for 24 h. After cooling to room temperature, a heterogeneous mixture was obtained. The toluene layer was decanted and the remaining solid was taken up in ethyl acetate (100 mL) and stirred at 0 °C for 30 min. The solid was filtered off, washed with cold ethyl acetate (25 mL) and the filtrate was concentrated to give 18.75 g of crude compound. Column chromatography (SiO2, ethyl acetate / ethanol 95:5) and drying under high vacuum (0.06 mbar, gentle heating) afforded 11.41 g (55%) of the desired compound.

[0233] [ka]

[0234] (aa) Synthesis of (±)-tetrakis(2-hydroxyethyl) 2,2'-disulfanediyl disuccinate (polyhydric alcohol 28) Ferrous sulfate hydrate (FeSO4×7H2O, 80 mg, 0.3 mmol) was added to a stirred solution of 2-mercaptosuccinic acid (29.6 g, 197.1 mmol) in water (250 mL). Hydrogen peroxide (35%, 14.59 g, 150.1 mmol) was then added dropwise over 5-10 min while maintaining the temperature below 35 °C with an ice bath. After stirring overnight at room temperature, the reaction mixture was extracted with ethyl acetate (250 mL, 3x). The aqueous layer was re-extracted with ethyl acetate (250 mL) and the combined organic layers were washed with a saturated aqueous solution of NaCl (100 mL, 2x), dried (Na2SO4) and concentrated (45 °C, 5 mbar) to give 23.40 g of a solid. The solid (22.38 g) was crushed and dried in a desiccator (0.06 mbar) to give 22.10 g (79%) of 2,2'-disulfanediyldisuccinic acid as a mixture of diastereoisomers.

[0235] [ka]

[0236] A mixture of 2,2'-disulfanediyldisuccinic acid (1.00 g, 3.4 mmol) and toluene-4-sulfonic acid monohydrate (0.05 g, 0.3 mmol) in ethane-1,2-diol (25 mL) was heated at 120 °C overnight in a Dean-Stark apparatus. Excess ethane-1,2-diol was removed by bulb-to-bulb distillation (0.067 mbar, 130 °C) to give 1.78 g of crude product. This was taken up in ethyl acetate (20 mL) and washed with a saturated aqueous solution of NaHCO3 (5 mL). The aqueous phase was re-extracted with ethyl acetate (25 mL) and the combined organic layers were dried (Na2SO4), concentrated and dried under vacuum at 0.087 mbar to give 1.04 g of the desired compound as a mixture of diastereoisomers.

[0237] [ka]

[0238] (ab) Synthesis of bis(2-hydroxyethyl) 2,2'-(methylenebis(4,1-phenylene)) bis(2-oxoacetate) (polyhydric alcohol 29) Under nitrogen, a solution of ethyl 2-chloro-2-oxoacetate (41.80 g, 306.2 mmol) in CHCl (75 mL) was added dropwise over 40 min to a suspension of AlCl (40.80 g, 306.0 mmol) in CHCl (250 mL) at 2-3 °C. After stirring for 30 min at 2-3 °C, a solution of diphenylmethane (16.80 g, 99.9 mmol) in CHCl (75 mL) was added dropwise over 45 min. The mixture was continued to stir at 2-3 °C for 3 h and then allowed to warm to room temperature overnight. The reaction mixture was poured onto ice (200 g), decanted, and the organic layer was washed with water (200 mL, 3x). The aqueous phase was re-extracted with CHCl (50 mL) and the combined organic layers were dried (NaSO) and concentrated to give 35.52 g of crude compound. Column chromatography (SiO2, n-heptane / ethyl acetate 4:1) of 27.77 g gave 10.05 g (35%) of diethyl 2,2'-(methylenebis(4,1-phenylene))bis(2-oxoacetate).

[0239] [ka]

[0240] Potassium carbonate (0.50 g) was added to a mixture of diethyl 2,2'-(methylenebis(4,1-phenylene))bis(2-oxoacetate) (10.19 g, 27.7 mmol) and ethane-1,2-diol (75.00 g). The reaction mixture was stirred at 80 °C for 1 h, then allowed to cool to room temperature and stirred overnight. After dilution with ethyl acetate (150 mL) and water (250 mL), the organic layer was decanted and the aqueous phase was extracted with ethyl acetate (100 mL, 2x). The combined organic layers were washed with a saturated aqueous solution of NaCl (100 mL, 3x), dried (Na2SO4), and concentrated. Remaining volatile compounds were removed by bulb-to-bulb distillation (70 °C, 0.057 mbar) to give 8.00 g (72%) of the desired compound.

[0241] [ka]

[0242] (ac) Synthesis of bis(2,2-bis(hydroxymethyl)butyl) 2,2'-(methylenebis(4,1-phenylene)) bis(2-oxoacetate) (polyhydric alcohol 30) Potassium carbonate (0.05 g) was added to a mixture of diethyl 2,2'-(methylenebis(4,1-phenylene))bis(2-oxoacetate) (1.00 g, 2.7 mmol, prepared as described in Example 1ab) and 2-ethyl-2-(hydroxymethyl)propane-1,3-diol (5.00 g). The reaction mixture was stirred at 80°C for 20 h, cooled to room temperature, and then diluted with methyl tert-butyl ether (MTBE) and water. The aqueous phase was decanted and re-extracted with MTBE (50 mL). The organic layer was washed with water (25 mL, 3x) and a saturated aqueous solution of NaCl (25 mL). The combined organic layers were dried (Na2SO4) and concentrated to give 1.11 g (74%) of the desired compound.

[0243] [ka]

[0244] (ad) Synthesis of bis(2-hydroxyethyl) 2,2'-(ethane-1,2-diylbis(4,1-phenylene)) bis(2-oxoacetate) (polyhydric alcohol 31) Under nitrogen, a solution of ethyl 2-chloro-2-oxoacetate (41.80 g, 306.2 mmol) in CHCl (75 mL) was added dropwise over 50 min to a suspension of AlCl (40.80 g, 306.0 mmol) in CHCl (250 mL) at 2-3 °C. After stirring for 30 min at 2-3 °C, a solution of 1,2-diphenylethane (18.60 g, 100.0 mmol) in CHCl (75 mL) was added dropwise over 45 min. The mixture was allowed to stir for 1 h at 2-3 °C and for 4 h at room temperature. The reaction mixture was slowly poured onto ice (200 g), diluted with CHCl (100 mL), decanted, and the organic layer was washed with water (150 mL, 3x). The aqueous phase was re-extracted with CH2Cl2 (50 mL) and the combined organic layers were dried (Na2SO4) and concentrated to give 39.22 g of crude compound as a pale yellow-green solid. Repeated recrystallization from acetone (2x) at -20 °C and from n-heptane / diethyl ether (2:1) at room temperature gave a total of 22.69 g (59%) of diethyl 2,2'-(ethane-1,2-diylbis(4,1-phenylene))bis(2-oxoacetate).

[0245] [ka]

[0246] To a suspension of diethyl 2,2'-(ethane-1,2-diylbis(4,1-phenylene))bis(2-oxoacetate) (23.01 g, 60.2 mmol) in ethane-1,2-diol (144 g) was added potassium carbonate (0.25 g). The reaction mixture was stirred at 80° C. for 20 h. Then, more potassium carbonate (0.75 g) was added and the reaction was continued to stir at 80° C. for 8 h. After cooling to room temperature overnight, a solid product was obtained. The reaction mixture was heated and then diluted with ethyl acetate (150 mL) and water (250 mL). The organic layer was decanted and the aqueous layer was extracted with ethyl acetate (100 mL, 2×). The combined organic layers were washed with a saturated aqueous solution of NaCl, dried (Na2SO4) and concentrated to give 22.33 g of crude product. Recrystallization from acetone (50 mL) in the refrigerator gave 3.25 g (13%) of the desired compound.

[0247] [ka]

[0248] (ae) Synthesis of benzene-1,3,5-triyltris(3-((2-hydroxyethyl)thio)propyl)tricarbonate (polyhydric alcohol 32) Benzene-1,3,5-triol (7 g, 55.6 mmol) and triethylamine (24 mL, 172 mmol) were dissolved in THF (100 mL) in a 250 mL round bottom flask. The temperature of the reaction mixture was reduced with ice and allyl carbonochloridate (18 mL, 169 mmol) was added. A white precipitate formed and the reaction mixture was stirred at 0° C. for 3 h. The white solid was filtered and the reaction mixture was concentrated under reduced pressure. A colorless oil was obtained and dissolved in ethyl acetate (100 mL). The organic solution was washed with a solution of K2CO3 (5%, x 3 100 mL). The organic layer was dried over anhydrous Na2SO4, filtered and concentrated to give triallylbenzene-1,3,5-triyl tricarbonate.

[0249] [ka]

[0250] The oil (6.0 g, 15.8 mmol) and 2,2-dimethoxy-1,2-diphenylethanone (0.1 g, 0.39 mmol) were dissolved in THF (30 mL) in a 250 mL round-bottom flask to give a colorless solution. 2-Mercaptoethanol (3.96 g, 50.7 mmol) was then added and the reaction mixture was exposed to UV-A light at 2 mW / cm. 2 The mixture was irradiated at rt for 5 h. The reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate (40 mL) and washed with a solution of K2CO3 (5% in water, 25 mLx2). The organic layer was dried over anhydrous Na2SO4, filtered and concentrated to give benzene-1,3,5-triyltris(3-((2-hydroxyethyl)thio)propyl)tricarbonate.

[0251] [ka]

[0252] (af) Synthesis of bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate (polyhydric alcohol 33) In a 100 mL round bottom flask, diallyl maleate (3 mL, 16.39 mmol) and triethylamine (0.25 mL, 1.794 mmol) were dissolved in THF (50 mL) to give a colorless solution. 2-Mercaptoethanol (1.4 mL, 19.98 mmol) was added and the reaction mixture was stirred at 0° C. 2,3,4,6,7,8,9,10-Octahydropyrimido[1,2-a]azepine (0.1 mL, 16.39 mmol) was added and the reaction mixture was stirred at room temperature for 5 h and finally concentrated under reduced pressure to give diallyl 2-((2-hydroxyethyl)thio)succinate.

[0253] [ka]

[0254] In a 100 mL round-bottom flask, diallyl 2-((2-hydroxyethyl)thio)succinate (3.5 g, 12.7 mmol) and 2-mercaptoethanol (1.9 mL, 27.1 mmol) were dissolved in THF (50 mL) to give a colorless solution. 2,2-Dimethoxy-1,2-diphenylethanone (0.1 g, 0.39 mmol) was added and the reaction mixture was exposed to UV-A light at 2 mW / cm. 2 The mixture was irradiated at rt for 3 h. The reaction mixture was concentrated under reduced pressure and ethyl acetate (50 mL) was added. The organic solution was washed with a solution of K2CO3 (5% in water, 25 mL) and water (25 mL). The organic layer was dried over anhydrous Na2SO4, filtered and concentrated to give bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate.

[0255] [ka]

[0256] (ag) Synthesis of bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)carbonate (polyhydric alcohol 34) 1,1,1-Tris(hydroxymethyl)ethane (24.5 g, 200.0 mmol) was suspended in THF (250 mL). Then, 2,2-dimethoxypropane (32 mL, 0.84 g mL -1 , 258.1 mmol) and p-toluenesulfonic acid (50 mg) were added. After stirring for 1 h, K2CO3 (1.0 g) was added and the mixture was stirred for 1 h, then filtered and concentrated under reduced pressure (45° C., 4 mbar). After addition of Primol™ (5.06 g) as ballast, fractional distillation (0.2 mbar, 70° C.) gave a total of 31.0 g (97%) of (2,2,5-trimethyl-1,3-dioxan-5-yl)methanol as a colorless oil.

[0257] [ka]

[0258] A mixture of (2,2,5-trimethyl-1,3-dioxan-5-yl)methanol (3.88 g, 24.2 mmol), diethyl carbonate (1.20 g, 10.0 mmol), and sodium methylate (11 mg) was heated at 90° C. for 5 h and then at 125° C. overnight. After cooling to room temperature, the product crystallized. Recrystallization with heptane (10 mL, hot), filtration, washing with heptane, and drying under vacuum gave 1.02 g (29%) of bis((2,2,5-trimethyl-1,3-dioxan-5-yl)methyl)carbonate as white crystals.

[0259] [ka]

[0260] A mixture of bis((2,2,5-trimethyl-1,3-dioxan-5-yl)methyl)carbonate (1.00 g, 2.9 mmol) and KHSO4 (33 mg) in methanol (9 mL) and water (1 mL) was stirred at room temperature for 3 h. Then NaHCO3 (250 mg) was added and the solvent was evaporated. The reaction mixture was taken up in ethyl acetate (20 mL) and washed with a saturated aqueous solution of NaCl (10 mL). The organic layer was dried (Na2SO4), filtered and concentrated. The product was recrystallized in acetone. After placing in the freezer, the crystals were filtered and washed with a minimum amount of ice-cold acetone to give 0.06 g (8%) of the desired compound.

[0261] [ka]

[0262] Example 2 Preparation of polyurethane core-shell microcapsules containing cleavable polyhydric alcohol according to formula (I) and their ability to release fragrance onto cotton upon rubbing (a) Manufacture of fragrance 1 Perfume 1 was prepared as an equal weight mixture of methyl 2,2-dimethyl-6-methylidenecyclohexanecarboxylate (supplied by Firmenich SA), 2-tert-butyl-1-cyclohexyl acetate (supplied by International Flavors and Fragrances), 4-tert-butyl-1-cyclohexyl acetate, 3-(4-isopropylphenyl)-2-methylpropanal and (2Z)-2-phenyl-2-hexenenitrile (supplied by Firmenich SA).

[0263] (b) Copolymerization of polyhydric alcohol and isocyanate at the oil-water interface To investigate the formation of polyurethanes by copolymerization of cleavable polyhydric alcohols with isocyanates in the presence of fragrance, membranes were formed at the interface between the aqueous phase and the oil phase on top of the aqueous phase using a 2D approach.

[0264] To a 1% by weight solution of polyvinyl alcohol (PVOH) in water (5 g), an appropriate amount of sodium citrate (about 0.4 equivalents) was added to dissolve the polyhydric alcohol (1 equivalent of -OH group). Commercially available polyisocyanate Takenate® D-110N (supplied by Mitsui Chemicals, Inc., 0.33 g, 0.86 mmol, 0.7 equivalents of -NCO group) was separately dissolved in fragrance 1 (4.7 g) and gently pipetted onto the aqueous solution in a 30 mL vial. The vial was left in a water bath without stirring, held at 25°C for 30 minutes, heated to 70°C in four steps over 1 hour (40°C, 50°C, 60°C, 70°C), held at 70°C for 2 hours, and finally cooled to room temperature.

[0265] The film formed at the interphase was carefully removed from the polymerization bottle using tweezers. The aqueous phase was carefully transferred to a round-bottom flask and frozen in dry ice. All water was removed by lyophilization (Christ Alpha 1-4, Fischer Science) and the resulting powder was characterized by NMR spectroscopy in D2O. 13 The ratio of the average signal of all triplets in the C spectrum compared to that of citric acid (triplet peak at 47–49 ppm) was used to calculate the percentage of monomer that remained in the aqueous phase, i.e., that did not react with the isocyanate.

[0266] The following proportions of cleavable polyhydric alcohols were reacted with the isocyanates and thus incorporated into the polymer film: [Table 1]

[0267] In this way, different polyhydric alcohols were successfully incorporated into 2D membranes via interfacial reactions with polyisocyanates.

[0268] (c) Production of Microcapsules 1 to 3 Sodium citrate (about 0.91 g) and one of the polyhydric alcohols (1 equivalent of -OH group) according to formula (I) prepared as described in Example 1 were dissolved in a 1% by weight solution of PVOH in water (35 g). Takenate® D-110N - adduct of trimethylolpropane-xylylene diisocyanate, supplied by Mitsui Chemicals, Inc., Japan, 75% solution of polyisocyanate in ethyl acetate (3.12 g, 8.2 mmol, 0.7 equivalent of -NCO group) was dissolved in perfume 1 (21 g). The oil phase was emulsified in the 1% by weight solution of PVOH with polyhydric alcohol (35 g) by Ultra-Turrax® (IKA 25, 3 min at maximum speed). The emulsion was transferred to a reactor equipped with a mechanical stirrer (RW20, IKA Labortechnik) and a water bath. After 1 hour at 25°C, the mixture was heated to 70°C in four stages over 1 hour (40°C, 50°C, 60°C, 70°C). Water (10 g) was added and the mixture was kept at 70°C for 2 hours and then cooled to room temperature to give a dispersion of microcapsules 1-3. Approximately 1 hour after removing the water bath, a micrograph of the capsules was taken (see Figure 1).

[0269] The following core-shell microcapsules were prepared: [Table 2]

[0270] As shown in Figure 1, core-shell microcapsules were formed.

[0271] (d) Fragrance release onto cotton with and without rubbing To demonstrate the release characteristics of the microcapsules, headspace concentrations of methyl 2,2-dimethyl-6-methylidenecyclohexanecarboxylate were measured for microcapsules attached to a cotton tissue with and without rubbing. The release of methyl 2,2-dimethyl-6-methylidenecyclohexanecarboxylate is considered representative of other perfume molecules for perfume 1.

[0272] Approximately 0.15 g of the dispersion of microcapsules 1 to 3 was diluted with approximately 15 g of demineralized water. For each sample, 3 to 4 cotton sheets were prewashed and 12 × 12 cm 2 The cotton sheets were cut into strips and marked with a circle of 10 cm in diameter. A diluted dispersion of microcapsules (1 mL) was pipetted onto one cotton sheet to fill the marked circular area. The sheets were hung to dry for 1 h and then stored in aluminum foil. The next day, each cotton sheet was left to equilibrate for 5 min in a 1 L beaker covered with aluminum foil. The amount of methyl 2,2-dimethyl-6-methylidenecyclohexanecarboxylate was then measured by atmospheric pressure chemical ionization mass spectrometry for 2 min (see, for example, O. Viry et al., Food Res. Int., 2018, 109, p. 52-58). The cotton sheets were then rubbed by hand 10 times and left in the beaker for another 5 min to equilibrate and measured again for 2 min. The average intensities of the molar masses of the protonated ions of the different fragrances (139, 172, 183, 191 g / mol) recorded over 1 min were subtracted from the background and divided by the concentration of microcapsules in the diluted dispersion to obtain the relative headspace intensities.

[0273] The following amounts of methyl 2,2-dimethyl-6-methylidenecyclohexanecarboxylate were released from the microcapsules: [Table 3]

[0274] Thus, microcapsules 1-3 containing cleavable polyhydric alcohols according to formula (I) are suitable for encapsulating and delivering fragrance to cotton.

[0275] Example 3 Preparation of polyamide microcapsules containing cleavable polyhydric alcohols of formula (I) [Table 4]

[0276] Preparation of microcapsules 4 using polyhydric alcohol 1 (bis(2-hydroxyethyl) disulfide) In a round bottom flask, trimesoyl chloride (TMCl, 0.18 g) was dissolved in benzyl benzoate (0.5 g). Bis(2-hydroxyethyl) disulfide (0.16 g) was dissolved in benzyl benzoate (5 g) and this solution was added to the first solution and stirred at 60° C. for 10 minutes (solution A). Sodium caseinate (1 g) was dispersed in perfume 2 (25 g). A second solution of TMCl (1.56 g) in benzyl benzoate (2 g) was prepared and added to the perfume dispersion. Finally, solution A was added to this dispersion to obtain the oil phase. This oil phase was dispersed in a solution of L-lysine (2.55 g) in water (95 g) with an Ultra Turrax T25 (S 25 N - 10G) at 24,000 rpm for 5 minutes. A solution of ethylenediamine (EDA, 0.22 g) in water (5 g) was added dropwise over 5 min. The reaction mixture was stirred at 30° C. and 250 rpm on an orbital shaker (IKA KS 3000) for 4 h, resulting in a white dispersion.

[0277] Microcapsule 5 was prepared following the protocol for Microcapsule 4, but using 0.16 g of polyhydric alcohol 1.

[0278] Preparation of microcapsules 6 using polyhydric alcohol 2 (2,2'-disulfanediylbis(propane-1,3-diol)) Microcapsule 6: In a round-bottom flask, bovine serum albumin (BSA, 0.95 g) was dispersed in benzyl benzoate (5.00 g) at 60° C. To this BSA dispersion, a solution of TMCl (0.88 g) in benzyl benzoate (2.50 g) was added. In another round-bottom flask, a solution of polyhydric alcohol 2 (0.38 g) in acetone (5.00 g) was added to a solution of TMCl (0.88 g) in benzyl benzoate (2.50 g) and the reaction mixture was stirred for a few minutes. This solution and dispersion were added to perfume 2 (25.14 g) at room temperature to obtain an oil phase. This oil phase was dispersed in a solution of L-lysine (2.50 g) in water (94.05 g) with an Ultra Turrax T25 (S 25 N - 10G) at 24,000 rpm for 1 minute. A solution of EDA (0.48 g) in water (5.00 g) was added dropwise over 5 min. The reaction mixture was stirred at 250 rpm at 30° C. for 4 h on an orbital shaker (IKA KS 3000) to give a white dispersion.

[0279] Microcapsule 7 was prepared according to the protocol for microcapsule 6, except that the EDA solution was replaced by a solution of cystamine dihydrochloride (1.8 g) in an aqueous solution of guanidine carbonate (30% by weight, 5.00 g).

[0280] Preparation of microcapsules 8-11 using polyhydric alcohol 3 (3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol) Microcapsule 8: TMCl (0.89 g) was dissolved in benzyl benzoate (2.59 g) in a round bottom flask. Polyhydric alcohol 3 (0.55 g) was dissolved in benzyl benzoate (2.51 g) and this solution was added to the first solution and stirred at 60° C. for 1 hour (solution A). Sodium caseinate (1.94 g) was dispersed in fragrance 2 (24.92 g). A second solution of TMCl (1.76 g) in benzyl benzoate (2.49 g) was prepared and added to the fragrance dispersion, after which solution A was added to this dispersion to obtain the oil phase. This oil phase was dispersed in a solution of L-lysine (2.57 g) in water (94.39 g) for 5 minutes at 24,000 rpm using an Ultra Turrax T25 (S 25 N - 10G). A solution of EDA (0.24 g) in water (5.30 g) was added dropwise over 5 min. The reaction mixture was stirred at 250 rpm at 30° C. for 4 h on an orbital shaker (IKA KS 3000) to give a white dispersion.

[0281] Microcapsule 9: In a round bottom flask, TMCl (2.63 g) was dissolved in benzyl benzoate (2.53 g). Polyhydric alcohol 3 (0.22 g) was dissolved in acetone (2.64 g) and this solution was added to the first solution and stirred at 60° C. for 1 hour (solution A). Sodium caseinate (1.03 g) was dispersed in benzyl benzoate (5.03 g, solution B). Solutions A and B were added to perfume 2 (25.6 g) to obtain an oil phase. This oil phase was dispersed in a solution of L-lysine (2.56 g) in water (94.27 g) at 24,000 rpm with an Ultra Turrax T25 (S 25 N - 10G) for 5 minutes. A solution of EDA (0.73 g) in water (5.15 g) was added dropwise over 5 minutes. The reaction mixture was stirred at 30° C. and 250 rpm for 4 hours in an orbital shaker (IKA KS 3000), yielding a white dispersion.

[0282] Microcapsule 10 was prepared following the protocol for Microcapsule 8, but using 0.31 g of polyhydric alcohol 3.

[0283] Microcapsule 11: In a round bottom flask, TMCl (2.68 g) was dissolved in benzyl benzoate (2.62 g). Polyhydric alcohol 3 (0.34 g) was dissolved in acetone (2.66 g) and this solution was added to the first solution and stirred at 60° C. for 1 h (solution A). Sodium caseinate (0.98 g) was dispersed in benzyl benzoate (5.09 g, solution B) at 60° C. for 30 min. Solutions A and B were added to perfume 2 (24.6 g) to obtain an oil phase. This oil phase was dispersed in a solution of L-lysine (2.49 g) and EDA (0.75 g) in water (95.65 g) with an Ultra Turrax T25 (S 25 N - 10G) at 24,000 rpm for 5 min. The reaction mixture was stirred at 30° C. and 250 rpm for 4 hours in an orbital shaker (IKA KS 3000), yielding a white dispersion.

[0284] Preparation of microcapsules 12 to 14 using polyhydric alcohol 8 (2,2'-(1,4-phenylenebis(oxazolidine-2,3-diyl))bis(ethan-1-ol)) Microcapsule 12: In a round-bottom flask, a solution of TMCl (0.88 g) in benzyl benzoate (2.50 g) was added to a dispersion of bovine serum albumin (BSA, 0.95 g) in benzyl benzoate (5.00 g) over 10 minutes at 60°C. In another round-bottom flask, a solution of polyhydric alcohol 8 (1.54 g) in acetone (5.00 g) was added to a solution of TMCl (0.88 g) in benzyl benzoate (2.50 g) and the reaction mixture was stirred for several minutes. This solution and dispersion were added to perfume 2 (25.14 g) at room temperature to obtain an oil phase. This oil phase was dispersed in a solution of L-lysine (2.50 g) in water (94.05 g) with an Ultra Turrax T25 (S 25 N - 10G) at 24,000 rpm for 1 minute. A solution of EDA (0.48 g) in water (5.00 g) was added dropwise over 5 min. The reaction mixture was stirred at 250 rpm at 30° C. for 4 h on an orbital shaker (IKA KS 3000) to give a white dispersion.

[0285] Microcapsule 13 was prepared according to the protocol for microcapsule 12, but replacing the EDA solution with a solution of cystamine dihydrochloride (1.8 g) in an aqueous solution of guanidine carbonate (30% by weight, 5.00 g).

[0286] Microcapsule 14 was prepared following the protocol for Microcapsule 12, except that the EDA solution was replaced with a solution of diethylenetriamine (0.83 g) in water (5.00 g).

[0287] Preparation of microcapsules 15 using polyhydric alcohol 1 (bis(2-hydroxyethyl) disulfide) in water and polyhydric alcohol 3 (3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol) in oil In a round-bottom flask, TMCl (2.65 g) was dissolved in benzyl benzoate (5.00 g). Polyhydric alcohol 3 (1.14 g) was dissolved in acetone (2.60 g). This solution was added to the first solution and stirred at 60° C. for 1 hour. This solution was added to fragrance 2 (25 g) to obtain an oil phase. This oil phase was dispersed in an aqueous solution of gum arabic (Senegal, 1% by weight, 95.22 g) with an Ultra Turrax T25 (S 25 N - 10G) at 24,000 rpm for 5 minutes. A solution of polyhydric alcohol 1 (0.78 g) in water (5.00 g) was added dropwise over 5 minutes. The pH of the emulsion was controlled at a value of 4.0 by adding an aqueous solution of sodium bicarbonate (5% by weight, 70.77 g). The reaction mixture was stirred at 90° C. for 4 hours to obtain a white dispersion.

[0288] Polyhydric alcohol 4: Preparation of microcapsules 16-18 using 2,2'-(disulfanediylbis(methylene))bis(2-methylpropane-1,3-diol) Sodium caseinate (2 g) was dispersed in perfume 2 (25 g) in a beaker. The dispersion was stirred at 60° C. for 1 h. TMCl (1.74 g) was dissolved in benzyl benzoate (5.14 g) in a round-bottom flask. Polyhydric alcohol 4 (0.68 g) was dissolved in acetone (2.49 g) at 40° C. This solution was added to the first solution and stirred at RT for 1 h. This solution was added to perfume 2 dispersion (25 g) to obtain an oil phase. This oil phase was dispersed in a solution of L-lysine (2.56 g) in water (95 g) with an Ultra Turrax T25 (S 25 N - 10G) at 24,000 rpm for 5 min. A solution of ethylenediamine (0.12 g) in water (5.00 g) was added dropwise over 5 min. The reaction mixture was stirred at 30° C. for 4 h to obtain a white dispersion.

[0289] Microcapsule 17 was prepared following the protocol for Microcapsule 16, but using 0.44 g of polyhydric alcohol 4 and 0.17 g of ethylenediamine.

[0290] Microcapsule 18 was prepared following the protocol for Microcapsule 16, but using 0.28 g of polyhydric alcohol 4 and 0.20 g of ethylenediamine.

[0291] Example 4 Preparation of cleavable polyisocyanates from cleavable polyhydric alcohols of formula (I) and preparation of core-shell type microcapsules thereof Preparation of cleavable polyisocyanates 1-5 Preparation of (((((benzene-1,3,5-triyltris(oxy))tris(carbonyl))tris(oxy))tris(propane-3,1-diyl))tris(sulfanediyl))tris(ethane-2,1-diyl)tris(3-(isocyanatomethyl)benzylcarbamate) (Polyisocyanate 1) 1,3-Bis(isocyanatomethyl)benzene (1.55 mL, 9.90 mmol) and tin(II) 2-ethylhexanoate (0.09 g, 0.011 mmol) were introduced into a 50 mL round-bottom three-neck flask under nitrogen to give a colorless solution. Benzene-1,3,5-triyltris(3-((2-hydroxyethyl)thio)propyl)tricarbonate (polyhydric alcohol 32, 2.04 g, 3.33 mmol) in ethyl acetate (4.4 mL) was added dropwise over 5 minutes. The reaction mixture was stirred at 50 °C for 3 hours, after which the medium was slowly cooled to room temperature under stirring before use.

[0292] [ka]

[0293] Preparation of 2-ethyl-2-(1-(3-(isocyanatomethyl)phenyl)-3,10-dioxo-4,11-dioxa-7-thia-2-azadodecan-12-yl)propane-1,3-diylbis(3-((2-(((3-(isocyanatomethyl)benzyl)carbamoyl)oxy)ethyl)thio)propanoate) (Polyisocyanate 2) 1,3-Bis(isocyanatomethyl)benzene (1.4 mL, 8.9 mmol) and tin(II) 2-ethylhexanoate (0.09 g, 0.34 mmol) in ethyl acetate were introduced into a 50 mL round-bottom three-neck flask to give a colorless solution. A solution of 2-ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((2-hydroxyethyl)thio)propanoate) (polyhydric alcohol 21, 1.54 g, 2.89 mmol) in ethyl acetate (3.1 mL) was added dropwise. The reaction mixture was stirred at 50° C. for 3 hours and then cooled slowly to room temperature under stirring.

[0294] [ka]

[0295] Preparation of 2-ethyl-2-(1-(5-isocyanato-1,3,3-trimethylcyclohexyl)-3,10-dioxo-4,11-dioxa-7-thia-2-azadodecan-12-yl)propane-1,3-diylbis(3-((2-((((5-isocyanato-1,3,3-trimethylcyclohexyl)methyl)carbamoyl)oxy)ethyl)thio)propanoate) (Polyisocyanate 3) 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (3.1 mL, 14.63 mmol) and tin(II) 2-ethylhexanoate (0.09 g, 0.011 mmol) were introduced into a 50 mL round-bottom three-neck flask to give a colorless solution. The reaction mixture was stirred at 50° C. for 5 minutes. 2-Ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((2-hydroxyethyl)thio)propanoate) (polyhydric alcohol 21, 2.53 g, 4.77 mmol) in ethyl acetate (6.3 mL) was added dropwise over 5 minutes. The reaction mixture was stirred at 50° C. for 3 hours and the reaction product was used without further purification.

[0296] [ka]

[0297] Preparation of (((((benzene-1,3,5-triyltris(oxy))tris(carbonyl))tris(oxy))tris(propane-3,1-diyl))tris(sulfanediyl))tris(ethane-2,1-diyl)tris(((5-isocyanato-1,3,3-trimethylcyclohexyl)methyl)carbamate) (polyisocyanate 4) 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (2.15 mL, 10.15 mmol) and tin(II) 2-ethylhexanoate (0.09 g, 0.011 mmol) were added to a 50 mL round-bottom three-neck flask under nitrogen to give a colorless solution. Benzene-1,3,5-triyltris(3-((2-hydroxyethyl)thio)propyl)tricarbonate (polyhydric alcohol 32, 2.02 g, 3.30 mmol) in ethyl acetate (3 mL) was added dropwise over 5 min. The reaction mixture was stirred at 50 °C for 3 h and then cooled slowly to room temperature under stirring.

[0298] [ka]

[0299] Preparation of bis(3-((2-(((3-(isocyanatomethyl)benzyl)carbamoyl)oxy)ethyl)thio)propyl)2-((2-(((3-(isocyanatomethyl)benzyl)carbamoyl)oxy)ethyl)thio)succinate (polyisocyanate 5) 1,3-Bis(isocyanatomethyl)benzene (1.4 mL, 8.94 mmol) and tin(II) 2-ethylhexanoate (0.09 g, 2.90 mmol) were placed in a 25 mL round-bottom three-neck flask to give a colorless solution. A solution of bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate (polyhydric alcohol 33, 1.25 g, 2.90 mmol) in ethyl acetate (0.28 mL) was added dropwise. The reaction mixture was stirred at 50° C. for 3 h and then cooled to room temperature under stirring.

[0300] [ka]

[0301] Preparation of microcapsules 19 and 20 of the present invention using a cleavable polyisocyanate containing a cleavable polyhydric alcohol of formula (I) Preparation of microcapsules 19 from polyisocyanate 4 Polyisocyanate 4 (4.64 g) was mixed with perfume oil (Fragrance 1, 20.01 g) in a 150 mL beaker to obtain a yellow solution. The mixture was stirred for 5 min. A solution of PVOH 18-88 (supplied by Aldrich, Switzerland) in water (1% by weight, 46.31 g) was added to the mixture. The reaction mixture was stirred at 17,500 rpm for 3 min with an Ultra Turrax (S25N 10G) to produce an emulsion. The droplet size was controlled by optical microscopy (pH=4.79). The reaction mixture was poured into a 250 mL reactor and stirred at 350 rpm at room temperature for 1 h. The temperature was then increased to 70° C. over 1 h and finally stirred at 350 rpm at 70° C. for 2 h (pH=5.68). The pH was adjusted to 8.8 with aqueous sodium hydroxide.

[0302] Production of microcapsules 20 from polyisocyanate 3 Microcapsules 20 were prepared following the protocol described for microcapsules 19, but from polyisocyanate 3 (5.32 g) in perfume oil.

[0303] Example 5 Fragrance leakage in fabric softener applications The storage stability of the capsules was evaluated in a fabric softener formulation (see composition in Table 2). The capsule dispersion was diluted with fabric softener (29.73 g) to a final concentration of 0.20% perfume 2 by weight. The fabric softener was stored at 37° C. for up to 1 month. The amount of perfume leaked from the capsules was then measured by solvent extraction with isooctane (10 mL) under stirring.

[0304] [Table 5]

[0305] Stability Assessment Protocol Fabric softener base containing microcapsules (2 g) was introduced into a 20 mL vial. The sample was diluted with water (2 mL) and the viscosity was reduced using a Socorex 10 mL bottle-top dispenser. The sample was shaken for 5 minutes using a Turbulat Shaker set at 40 rpm. To the vial (10 mL) was added isooctane containing 1,4-dibromobenzene as an internal standard at a precisely known concentration of approximately 90 ng / μL. The sample was shaken at 40 rpm for 45 minutes to extract the free perfume and then centrifuged at 3.0 G for 10 minutes to separate the two phases. The solvent phase was collected, dried over MgSO4 and subjected to GC analysis.

[0306] [Table 6]

[0307] Thus, the microcapsules according to the present invention show good stability in fabric softeners.

[0308] Example 6 Liquid detergent composition Microcapsules 1 to 20 of the present invention were dispersed in the liquid detergent base described in Table 4 to give an encapsulated perfume oil concentration of 0.22%.

[0309] [Table 7]

[0310] Example 7 Rinse-off conditioner Microcapsules 1 to 20 of the present invention are dispersed in a rinse-off conditioner base shown in Table 5 to give an encapsulated perfume oil concentration of 0.5%.

[0311] [Table 8]

[0312] Example 8 Shampoo Composition Microcapsules 1 to 20 of the present invention are weighed and mixed into a shampoo composition to add a fragrance equivalent to 0.2%.

[0313] [Table 9-1] [Table 9-2]

[0314] Example 9 Antiperspirant roll-on emulsion composition Microcapsules 1 to 20 of the present invention are weighed and mixed into the antiperspirant roll-on emulsion composition, thereby adding a fragrance equivalent to 0.2%.

[0315] [Table 10]

[0316] Part A and Part B are heated separately to 75°C, Part A is added to Part B under stirring and the mixture is homogenized for 10 minutes, the mixture is then cooled under stirring and Part C is added slowly when the mixture reaches 45°C and Part D is added slowly when the mixture reaches 35°C while stirring, the mixture is then cooled to room temperature.

[0317] Example 10 Shower gel composition Microcapsules 1 to 20 of the present invention are weighed and mixed into the following composition to add a fragrance equivalent to 0.2%.

[0318] [Table 11]

Claims

1. A method for producing a core-shell microcapsule slurry, the method comprising the steps of: a) adding at least one multifunctional monomer to a hydrophobic material to form an oil phase; b) preparing a dispersed phase that is immiscible with the oil phase; c) adding the oil phase to the dispersed phase to form a two-phase dispersion; d) optionally adding reactants to the dispersion obtained in step c); e) carrying out a hardening step to form core-shell microcapsules in the form of a slurry; Including, In step a) and / or step b), a stabilizer is added, In step a) and / or step b) and / or step c) and / or step d), at least one cleavable polyhydric alcohol is added, The cleavable polyhydric alcohol is a compound selected from the group consisting of: disulfides selected from the group consisting of 2,2'-disulfanediylbis(ethan-1-ol), 2,2'-disulfanediylbis(propane-1,3-diol), 3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol, 2,2'-(disulfanediylbis(methylene))bis(2-methylpropane-1,3-diol) or 2,2'-(disulfanediylbis(methylene))bis(2-ethylpropane-1,3-diol), bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 3,3'-disulfanediyl dipropionate, tetrakis(2-hydroxyethyl) 2,2'-disulfanediyl disuccinate, and / or oxazolidines selected from the group consisting of: (3-(2-hydroxyethyl)oxazolidine-2,2-diyl)dimethanol, oxazolidine-2,2,4-triyltrimethanol, 2,2'-(ethane-1,2-diylbis(2-methyloxazolidine-2,3-diyl))bis(ethan-1-ol), (ethane-1,2-diylbis(2-methyloxazolidine-2,4,4-triyl))tetramethano 2,2'-(1,4-phenylenebis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(furan-2,5-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(cyclohexane-1,4-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4,12-diyl)bis(ethan-1-ol), (1,4-phenylenebis(oxazolidine-2,4,4-triyl))tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,3,11,11-tetrayl)tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (3,11-dimethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (1,4-phenylenebis(4-ethyloxazolidine-2,4-diyl))dimethanol, (3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, 2,2'-(3,11-bis(hydroxymethyl)-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4,12-diyl)bis(ethan-1-ol), and / or 1,4-adducts selected from the group consisting of 2-hydroxyethyl 3-((2-hydroxyethyl)thio)propanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 3-((3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)thio)-2-methylpropanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl(S)-3-((2,3-dihydroxypropyl)thio)propanoate, 2-ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((2-hydroxyethyl)thio)propanoate), 4-Hydroxybutyl 3-((1,3-dihydroxypropan-2-yl)amino)propanoate, bis(2-hydroxyethyl) 3,3'-(butylazanediyl)dipropionate, bis(2-hydroxyethyl) 3,3'-((4-hydroxybutyl)azanediyl)dipropionate, bis(2-hydroxyethyl) 3,3'-(piperazine-1,4-diyl)dipropionate, tetrakis(2-hydroxyethyl) 3,3',3'',3'''-(propane-1,3-diylbis(azanetriyl))tetrapropionate, bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate That is, the method.

2. 2. The method of claim 1, wherein the multifunctional monomer is selected from the group consisting of at least one polyisocyanate, polyanhydride, polyacyl chloride, polyepoxide, polyacrylate monomer, polymethacrylate, and polyalkoxysilane, and mixtures thereof.

3. 3. The method of claim 1 or 2, wherein the reactant is selected from the group consisting of nitrogen nucleophilic compounds, sulfur nucleophilic compounds, enol carbon nucleophilic compounds, oxygen nucleophilic compounds, phosphorus nucleophilic compounds, and mixtures thereof.

4. The reactants include xylylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, L-lysine, L-lysine ethyl ester, O,O'-bis(2-aminopropyl)polypropylene glycol block-polyethylene glycol block-polypropylene glycol, ethylenediamine, 1,3-diamino-2-hydroxypropane, diethylenetriamine, spermine, spermidine, cystamine, cystine, cystine dialkyl esters, aminoguanidine bicarbonate, N,N'-diethylethylenediamine, polyamidoamine (PAMAM), chitosan, 3-aminopropyltriethoxysilane, L-arginine 4. The method of claim 3, wherein the aryl group is selected from the group consisting of 1,3-diaminopropane, N-ethylguanidine sulfate, 1,6-diaminohexane, guanidine salts, N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, guanazole, 2-amino-1,3-propanediol, ethanolamine, tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, tris[2-(methylamino)ethyl]amine, 1-(2-aminoethyl)piperazine, triethylenetetramine, triethanolamine, dipotassium phthalate, disodium succinate, dithiothreitol, and mixtures thereof.

5. 5. The method of claim 1, wherein the stabilizer is selected from the group consisting of gum arabic, modified starch, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, anionic polysaccharides, acrylamide copolymers, inorganic particles, proteins, and mixtures thereof.

6. A core-shell type microcapsule, comprising: an oily core comprising a hydrophobic material; a shell comprising a reaction product of a polyfunctional monomer and a cleavable polyhydric alcohol; wherein the cleavable polyhydric alcohol is a compound selected from the group consisting of: disulfides selected from the group consisting of 2,2'-disulfanediylbis(ethan-1-ol), 2,2'-disulfanediylbis(propane-1,3-diol), 3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol, 2,2'-(disulfanediylbis(methylene))bis(2-methylpropane-1,3-diol) or 2,2'-(disulfanediylbis(methylene))bis(2-ethylpropane-1,3-diol), bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 3,3'-disulfanediyl dipropionate, tetrakis(2-hydroxyethyl) 2,2'-disulfanediyl disuccinate, and / or oxazolidines selected from the group consisting of: (3-(2-hydroxyethyl)oxazolidine-2,2-diyl)dimethanol, oxazolidine-2,2,4-triyltrimethanol, 2,2'-(ethane-1,2-diylbis(2-methyloxazolidine-2,3-diyl))bis(ethan-1-ol), (ethane-1,2-diylbis(2-methyloxazolidine-2,4,4-triyl))tetramethano 2,2'-(1,4-phenylenebis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(furan-2,5-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(cyclohexane-1,4-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2'-(1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4,12-diyl)bis(ethan-1-ol), (1,4-phenylenebis(oxazolidine-2,4,4-triyl))tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,3,11,11-tetrayl)tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (3,11-dimethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (1,4-phenylenebis(4-ethyloxazolidine-2,4-diyl))dimethanol, (3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, 2,2'-(3,11-bis(hydroxymethyl)-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4,12-diyl)bis(ethan-1-ol), and / or 1,4-adducts selected from the group consisting of 2-hydroxyethyl 3-((2-hydroxyethyl)thio)propanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 3-((3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)thio)-2-methylpropanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl(S)-3-((2,3-dihydroxypropyl)thio)propanoate, 2-ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl)propane-1,3-diylbis(3-((2-hydroxyethyl)thio)propanoate), 4-Hydroxybutyl 3-((1,3-dihydroxypropan-2-yl)amino)propanoate, bis(2-hydroxyethyl) 3,3'-(butylazanediyl)dipropionate, bis(2-hydroxyethyl) 3,3'-((4-hydroxybutyl)azanediyl)dipropionate, bis(2-hydroxyethyl) 3,3'-(piperazine-1,4-diyl)dipropionate, tetrakis(2-hydroxyethyl) 3,3',3'',3'''-(propane-1,3-diylbis(azanetriyl))tetrapropionate, bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate These are core-shell microcapsules.

7. 7. The core-shell microcapsule of claim 6, wherein the multifunctional monomer is selected from the group consisting of at least one polyisocyanate, polyanhydride, polyacyl chloride, polyepoxide, polyacrylate monomer, polymethacrylate, and polyalkoxysilane, and mixtures thereof.

8. (i) a perfume microcapsule according to claim 6, wherein the hydrophobic material comprises a perfume; (ii) at least one ingredient selected from the group consisting of a perfume carrier and a perfume base; (iii) optionally at least one flavor adjuvant; A fragrance composition comprising:

9. - a personal care active base, - a microcapsule according to claim 7 or a fragrance composition according to claim 8 and in the form of a personal care composition.

10. - a home or fabric care active base, - a microcapsule according to claim 7 or a fragrance composition according to claim 8 and in the form of a home care composition or a fabric care composition.

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