Care product compositions with improved olfactory properties

Abstract

The present invention relates to a care product composition with improved olfactory properties. The composition comprises: at least one composition for home care; and at least one solid microcapsule having an average diameter of 1-30 [mu] m, said solid microcapsule comprising: a core consisting of a composition C1 comprising at least one perfume, said composition C1 being in the form of an emulsion, and a solid shell of a cross-linked polymer completely wrapping said core at the periphery of said core, the solid shell comprises a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive functional group, the solid shell having a thickness of 0.1-20 [mu] m. The composition disclosed by the invention can emit lasting and pleasant fragrance.

Description

[0001] This application is a divisional application of a Chinese patent application filed on January 22, 2020, with application number 202080010555.8 and invention name “Care Product Composition with Improved Olfactory Properties”. Technical Field

[0002] The subject of the present invention relates to compositions, in particular for stain removal, household care cleaning, comprising microcapsules and having improved olfactory properties. Background Art

[0003] Scent is currently one of the leading factors in purchasing cleaning products such as household cleaners. The sensory attribute that consumers appreciate is a pleasant, fresh scent that is emitted in a continuous and long-lasting manner.

[0004] Achieving this level of olfactory performance is a real technical challenge for players in this field. First, fragrances are volatile substances that evaporate quickly in the cleaning product bottle before emitting a pleasant smell when used. Secondly, it is certain that since fragrances are mostly hydrophobic substances and since cleaning products also contain surfactants, they will hardly adhere to the surface. Therefore, most of the fragrances contained in cleaning products will disappear due to evaporation or removal by surfactants, and will not adhere to the surface to leave a fragrance.

[0005] To overcome this problem, a major innovation emerged in 2000, namely the fragrance microcapsules. The benefits of encapsulating fragrances in microcapsules with a polymer shell are manifold. First, the polymer shell allows limiting the fragrance evaporation rate. In addition, the affinity of the polymer shell for the constituent material of the surface to be treated enables the microcapsules and therefore the fragrance to attach to it. Finally, the microcapsules provide a lasting fragrance effect by gradually diffusing the fragrance they contain or by gradually rupturing upon mechanical contact with the surface to gradually release the fragrance.

[0006] Microcapsules thus allow improving the olfactory properties of cleaning products while reducing the amount of fragrance contained in these products, thus reducing their cost. However, manufacturers are now facing increasingly stringent environmental restrictions and seek to make their products biodegradable. Current microcapsules are derived from non-biodegradable plastics, which is a major obstacle to the current dynamics.

[0007] Microcapsules mainly used in cleaning products are formed by the interfacial polymerization of formaldehyde-based compounds and melamine-based compounds. The ingredients of these cleaning products are detailed in US patent applications US2013 / 0203642, US 7119057, WO 2015 / 031418, US2015 / 025231 and US2016 / 177241. These capsules show adequate performance in preventing the evaporation of fragrance and lasting fragrance, but are not biodegradable.

[0008] Biodegradable alternatives have been developed, for example, non-polymeric matrix microcapsules containing cellulose, polycaprolactone or polyvinylpyrrolidone, as described in patent application CN106614564 or US2015 / 265541. However, these microcapsules are highly porous and the properties they can provide to prevent the evaporation of the fragrance and the release of the aroma are insufficient.

[0009] Therefore, there is a need in the art for biodegradable microcapsules while improving the properties of long-lasting fragrance. Summary of the invention

[0010] It is therefore an object of the present invention to provide a composition, in particular for household cleaning, which comprises biodegradable microcapsules and allows the emission of a long-lasting, pleasant fragrance.

[0011] Another object of the present invention is to provide a cleaning product which emits a pleasant, long-lasting fragrance and exhibits less perfume evaporation than current products containing microcapsules.

[0012] Another object of the present invention is to provide a biodegradable cleaning product which emits a pleasant, long-lasting pleasant scent.

[0013] Therefore, the present invention relates to a composition comprising:

[0014] - at least one composition for home care; and

[0015] - at least one solid microcapsule with an average diameter of 1 to 30 μm, the solid microcapsule comprising:

[0016] - a core consisting of a composition C1 comprising at least one fragrance; and

[0017] - a solid shell of a cross-linked polymer which completely surrounds the core at the periphery of the core, the solid shell comprising a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups,

[0018] Wherein, the thickness of the solid shell is 0.1 to 20 μm, preferably 0.2 to 8 μm, and more preferably 0.2 to 5 μm.

[0019] The present invention relates to a composition comprising:

[0020] - at least one composition for home care; and

[0021] - at least one solid microcapsule with an average diameter of 1 to 30 μm, the solid microcapsule comprising:

[0022] - a core consisting of a composition C1 comprising at least one fragrance, said composition C1 being in the form of an emulsion; and

[0023] - a solid shell of a crosslinked polymer which completely surrounds the core at the periphery of the core, the solid shell comprising a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups,

[0024] Wherein, the thickness of the solid shell is 0.1 to 20 μm, preferably 0.2 to 8 μm, and more preferably 0.2 to 5 μm.

[0025] Surprisingly, the present inventors have determined that by combining the formulation of a home care cleaning product, such as surface cleaners well known in the prior art, with microcapsules of a crosslinked polymer, such as a crosslinked polyester, a crosslinked polyepoxide or a crosslinked polyurethane, the resulting home cleaning product has the following properties:

[0026] -It emits a pleasant, long-lasting fragrance;

[0027] - it exhibits less evaporation of fragrance compared to prior art products containing microcapsules; and

[0028] -It is biodegradable.

[0029] For the composition of the present invention, a composition typically used for household cleaning but not comprising the microcapsules described in detail below is combined with biodegradable microcapsules having a core comprising a perfume.

[0030] In the present invention, the microcapsules do not contain a household cleaning composition. In particular, the core of the microcapsules used in the present invention does not include a surface cleaning composition or any detergent product.

[0031] The present invention particularly encompasses the use of biodegradable microcapsules having a perfume-containing core to improve the olfactory properties of household cleaning product compositions.

[0032] In this application, the terms "microcapsule" and "capsule" are used in different ways.

[0033] Household cleaning compositions

[0034] As stated above, the compositions of the present invention comprise household cleaning compositions.

[0035] These household cleaning compositions are selected from compositions known in the prior art for household care and cleaning, for example, detergents; glass cleaners; neutral all-purpose cleaners; bathroom cleaners; cleaning agents; rinse agents; dishwashing agents; kitchen cleaners; oven cleaners; dishwasher cleaners; floor cleaners and detergents; window cleaners; ceramic cleaners; toilet bowl cleaners; rug and carpet cleaners and shampoos; stain repellents; furniture polishes; products and waxes for polishing glass, wood, plastics, marble, granite, tiles, etc.; automobile body polishing products; leather treatments; vinyl treatments and air filters.

[0036] Preferably, these compositions do not comprise (micro)capsules.

[0037] In particular, compositions for household cleaning are cleaning compositions, especially liquid cleaning compositions for use on surfaces.

[0038] Compositions for household cleaning may include surfactant compounds, especially nonionic surfactant compounds.

[0039] The choice of surfactant compound (surfactant) and the amount thereof to be used will depend upon the intended use of the household cleaning composition.

[0040] The total content of surfactant also depends on the final intended use and can reach 60% by weight. Typically, the household cleaning composition used in the present invention comprises at least 2% by weight of surfactant, preferably 2% to 6%, especially 15% to 40%, preferably 25% to 35%, relative to the total weight of the composition.

[0041] In one embodiment, the household cleaning composition used in the present invention comprises at least one surfactant, in particular selected from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof, in particular as described in detail in the following literature: for example, "Surface Active Agents and Detergents", Volumes I and II, edited by Schwartz, Perry and Berch.

[0042] In one embodiment, the household cleaning composition used in the present invention comprises at least one anionic surfactant, in particular selected from linear alkylbenzene sulfonates, in particular with an alkyl chain length of C8 to C 16Preferably, the content of these surfactants is 0 to 40% by weight, in particular 1 to 25% by weight, preferably 2 to 15% by weight, relative to the total weight of the composition.

[0043] As anionic surfactants, mention may also be made of alkaline salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms, sulfuric acid half-ester salts of fatty alcohols having 12 to 18 carbon atoms, and sulfated products of the above-mentioned nonionic surfactants with a low degree of ethoxylation; primary and secondary alkyl sulfates, in particular primary branched and statistically C8 to C 15 Alkyl sulfate; C 10 ~C 18 Secondary (2,3) alkyl sulfates; alkyl ether sulfates; sulfated fatty alcohol ethoxylates (FAE), preferably alkyl alkoxy sulfates; C 10 ~C 18 Alkyl alkoxy carboxylates; medium chain branched alkyl sulfates; medium chain branched alkoxy sulfates; modified alkyl benzene sulfonates; methyl ester sulfonates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates. Sodium salts are generally preferred.

[0044] In one embodiment, the household cleaning compositions used in the present invention comprise at least one nonionic surfactant.

[0045] As nonionic surfactants, for example, there may be mentioned alkyl glucosides and / or ethoxylates or propoxylates of primary and secondary alcohols, especially C8 to C20 ethoxylated fatty alcohols containing an average of 1 to 20 mol of ethylene oxide per mole of alcohol, and C10 to C15 primary and secondary alcohol ethoxylated fatty alcohols; C6 to C12 alkoxylates of alkyl alkylphenols, wherein the alkoxylate repeating units are a mixture of ethyleneoxy and propyleneoxy units; C12 to C18 alcohol condensates and C6 to C12 alkylphenol condensates with ethylene oxide / propylene oxide block alkylpolyamine ethoxylates; alkyl polysaccharides; amides of polyhydroxy fatty acids; and alkoxylated ester surfactants such as fatty methyl ester ethoxylates (MEEs).

[0046] As nonionic surfactants, mention may also be made of, for example, non-ethoxylated nonionic surfactants, for example, alkyl polyglycosides; ethoxylation and / or propoxylation products of glycerol monoethers and polyhydroxyamides (glucamide); N-alkylamines, vicinal glycols, fatty acid esters and fatty amides.

[0047] The content of the surfactant in the composition may be 0 to 40 wt %, preferably 1 to 25 wt %, and more preferably 2 to 15 wt %, relative to the total weight of the composition.

[0048] In one embodiment, the household cleaning composition used in the present invention comprises at least one amphoteric surfactant.

[0049] As amphoteric surfactants, there may be mentioned, for example, derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines; or quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds such as derivatives of betaines, including alkyl dimethyl betaine and cocodimethylamidopropyl betaine, C8 to C18 amine oxides and sulfonyl and hydroxybetaines (for example, N-alkyl-N,N-dimethylamino-1-propanesulfonate, the alkyl group of which may be C8 to C18 or C10 to C14); water-soluble amine oxides, for example, C10 to C18 alkyl dimethyl amine oxide or C8 to C12 alkoxy ethyl dihydroxy ethyl amine oxide.

[0050] In one embodiment, the household cleaning composition used in the present invention comprises at least one stabilizer, the primary purpose of the at least one stabilizer being to suspend and stabilize the microcapsules.

[0051] As stabilizers, mention may be made of any known ingredient capable of suspending particles and / or adjusting the rheology of a liquid composition, in particular crystalline materials containing hydroxyl groups, polyacrylates, polycarboxylates, salts of alkali metals, salts of alkaline earth metals, ammonium salts, alkanolamine salts, C12 to C20 fatty alcohols, derivatives of dibenzylidene polyol acetate (DBPA), cationic polymers comprising a first structural unit derived from methacrylamide and a second structural unit derived from diallyldimethylammonium chloride, and combinations thereof. C8 to C22 linear alcohols, C10 to C20 linear alcohols or mixtures thereof alkoxylated with 10 to 20 moles of ethylene oxide may also be used. Other stabilizers include antiflocculating polymers as described in patent applications EP 0415698 and EP 0458599. Advantageously, the nonionic stabilizer is a C8 to C222 linear alcohol alkoxylated with 10 to 20 moles of ethylene oxide. Gums and other polysaccharides may also be advantageously used, for example, gellan gum, carrageenan, xanthan gum, polyvinyl alcohol and its derivatives, cellulose and its derivatives (including cellulose ethers and cellulose esters) and tamarind gum (including, for example, xylan polymers), guar gum, locust bean gum. Finally, fatty acids and fatty waxes may be mentioned, for example, C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof, and castor oil and its derivatives. Preferably, saturated fatty acids are used, especially C16 to C18 hardened tallow fatty acids. Preferably, the fatty acids are non-saponified, more preferably, the fatty acids are free, for example, oleic acid, lauric acid or tallow fatty acids.

[0052] The stabilizer may be included in the composition in an amount of 0.1 to 10 wt %, particularly 0.5 to 5 wt %, and preferably 1 to 4 wt %, relative to the total weight of the composition.

[0053] In one embodiment, the household cleaning composition used in the present invention comprises at least one inorganic additive to improve the stain removal performance of the product, for example, sodium carbonate, optionally in combination with seed crystals of calcium carbonate; crystalline and amorphous aluminosilicates such as zeolites; inorganic phosphates and polyphosphates such as sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate.

[0054] Preferably, the content of the inorganic additive is 5 to 40 wt % relative to the total weight of the composition.

[0055] In one embodiment, the household cleaning composition used in the present invention comprises at least one organic detergent additive, for example, polycarboxylic acids, in particular citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malonic acid (malaric acid), fumaric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid; polyphosphonic acids, in particular aminotriacid (methylenephosphonic acid), ethylenediamine tetrabasic compounds (methylenephosphonic acid) and polymeric acids such as dextrin (polymer), polymeric acrylic acid, methacrylic acid, maleic acid and polymer mixtures thereof. All the acids mentioned are usually used in the form of their water-soluble salts, in particular their alkaline salts.

[0056] Preferably, the content of the organic detergent additive is 0.5 to 25 wt%, preferably 1 to 10 wt%, relative to the total weight of the composition.

[0057] In one embodiment, the household cleaning composition used in the present invention comprises at least one organic detergent additive of the polycarboxylic acid monomer type, for example, citrate esters; gluconate esters; disuccinateoxy esters; glyceryl monosuccinate, glyceryl disuccinate and glyceryl trisuccinate; carboxymethyloxysuccinate; carboxymethyloxymalonate; disilicate diester; hydroxyethyliminodiacetate; alkyl and alkenyl malonates; salts of succinic acid and sulfonated fatty acids.

[0058] Preferably, the content of the organic detergent additive is 5 to 30 wt%, preferably 10 to 25 wt%, relative to the total weight of the composition.

[0059] In one embodiment, the household cleaning composition used in the present invention comprises at least one peroxygen bleach compound, for example, an inorganic persulfate or an organic peroxyacid capable of generating hydrogen peroxide in aqueous solution. Suitable peroxy bleach compounds include organic peroxides (e.g., urea peroxide) and inorganic persulfates (e.g., perborates, percarbonates, perphosphates, silicates and alkali metal persulfates). Particular mention is made of sodium perborate monohydrate and tetrahydrate; as well as sodium percarbonate, phthalimidoperoxycaproic acid, peroxybenzoic acid, hypochlorite, peracetic acid, diperoxyazelaic acid, diperoxydodecanedioic acid and an oxidase system or a salt of diperoxydodecanedioic acid.

[0060] Preferably, the peroxygen bleaching compound is present in an amount of 0.1 to 35% by weight, preferably 0.5 to 25% by weight, relative to the total weight of the composition.

[0061] In one embodiment, the household cleaning composition used in the present invention comprises at least one bleach activator or precursor, which can be used together with the bleaching compound to improve the bleaching effect at low washing temperatures, for example, a complex of a catalytic metal, a precursor of a peroxycarboxylic acid, more specifically a precursor of peracetic acid and a precursor of peroxynonanoic acid, for example, N,N,N',N'-tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (SNOBS), octanoic acid caprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, benzoylpentylcyclohexanolactam, dodecylbenzyl methyl acrylate. In addition, peroxy acids can also be used, for example, iminoperoxycarboxylic acid peracid, phthalimidoperoxycaproic acid (PAP).

[0062] Preferably, the content of the bleach activator or precursor is 0.1 to 8% by weight, preferably 0.5 to 5% by weight, relative to the total weight of the composition.

[0063] In one embodiment, the household cleaning composition used in the present invention comprises at least one bleach stabilizer (transition metal chelator), for example, ethylenediaminetetraacetic acid (EDTA), polyphosphates such as Dequest (registered trademark) and non-phosphate stabilizers such as EDDS (ethylenediamine disuccinic acid).

[0064] In one embodiment, the household cleaning composition used in the present invention comprises at least one enzyme, for example, proteases (especially subtilisin), cutinases, amylases, pullulanases, hemicellulases, cellulases, hemicellulases, mannanases, pectinase, tannases, xylanases, xanthanases, β-glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases, lipases and peroxidases and mixtures thereof. Active enzyme substances obtained from the following fungi or bacteria are particularly suitable: for example, Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, blue green humus bacteria, endophytic humus bacteria, pseudoalcaligenes or Pseudomonas cepacia. The optional enzymes can be adsorbed on a matrix material and / or incorporated into an encapsulating material to prevent early inactivation.

[0065] Preferably, the enzyme is contained in an amount of about 0.1 to 3.0 wt % relative to the total weight of the composition.

[0066] In one embodiment, the household cleaning composition used in the present invention comprises at least one powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate copolymer or an acrylate / maleic acid copolymer or sodium silicate.

[0067] Preferably, the content of the powder structurant is 1 to 5 wt % relative to the total weight of the composition.

[0068] The household cleaning composition used in the present invention may further contain other additives, for example, a soil-releasing polymer; an inorganic salt such as sodium sulfate or sodium hydroxide; a colorant; and a decoupling polymer.

[0069] In one embodiment, the household cleaning composition comprises at least one free fragrance, i.e., a non-encapsulated fragrance. The fragrance is well known to those skilled in the art and includes, for example, the fragrances mentioned in the following documents: S. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969); S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ, 1960); the fragrances in the list of the International Fragrance Association (IFRA) (http: / / www.ifraorg.org / en / ingredients) and the "Flavor and Fragrance Materials", 1991 (Allured Publishing Co. Wheaton, III. USA) published in 1991.

[0070] Preferably, the content of the free fragrance is 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.3 to 2% by weight, relative to the total weight of the composition.

[0071] In one embodiment, the household cleaning composition used in the present invention comprises at least one defoaming agent such as silicone oil or paraffin.

[0072] Preferably, the content of the defoaming agent is 0.05 to 4% by weight, preferably 0.1 to 3% by weight, and especially 0.2 to 1% by weight, relative to the total weight of the composition.

[0073] In one embodiment, the household cleaning composition used in the present invention comprises at least one degreasing agent or anti-redeposition agent such as nonionic cellulose ether, for example, methylcellulose; carboxymethylcellulose; methylhydroxypropylcellulose; polymers of phthalic acid and / or terephthalic acid, especially ethylene terephthalate polymers and / or polyethylene terephthalate or derivatives thereof with anionic and / or nonionic modification, and preferably in an amount of 0 to 5% by weight relative to the total weight of the composition.

[0074] In one embodiment, the household cleaning composition used in the present invention comprises at least one fluorescent whitening agent, which may include any compound having fluorescence, including compounds that absorb and re-emit ultraviolet light in the form of visible "blue" light. The whitening agent includes: derivatives of stilbene, 4,4'-diaminostyrene derivatives, biphenyl derivatives, stilbene biphenyl derivatives, derivatives of five-membered heterocycles (such as triazoles, pyrazoline, oxazole, imine diazole) or six-membered heterocycles (such as coumarin, naphthylamide, s-triazine).

[0075] Preferably, the content of the fluorescent whitening agent is 0 to 0.4 wt %, especially 0.1 to 0.3 wt %, relative to the total weight of the composition.

[0076] In one embodiment, the household cleaning composition used in the present invention comprises at least one non-aqueous solvent, for example, a monohydric alcohol or a polyhydric alcohol, an alkanolamine or a glycol ether, provided that they are miscible with water within a specified concentration. Preferably, the solvent is selected from ethanol, n-propanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, methylpropylene glycol, glycerol, diethylene glycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol, ethylene glycol and ethylene glycol, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol ether, tert-butyl ether, dioctyl ether and mixtures thereof.

[0077] Preferably, the content of the non-aqueous solvent is 0 to 25% by weight, preferably 1 to 20% by weight, and especially 2 to 15% by weight, relative to the total weight of the composition.

[0078] In one embodiment, the household cleaning compositions used in the present invention comprise water.

[0079] Solid microcapsules

[0080] As mentioned above, the composition of the present invention comprises at least one solid microcapsule as described above.

[0081] Preferably, the composition of the invention comprises several solid microcapsules, ie a series or collection of solid microcapsules which are all identical or different.

[0082] Due to the solid nature of the cross-linked polymer shell, the microcapsules of the present invention are referred to as solid microcapsules.

[0083] In one embodiment, the solid microcapsules of the present invention comprise a liquid (non-solid) core.

[0084] The microcapsules used in the present invention have biodegradable properties, given the selection of specific monomers and polymers.

[0085] Biodegradability is defined herein as the ability to degrade in the natural environment, for example, as defined in the OECD guidelines: OECD 301 (immediate biodegradability), i.e. OECD 301A (disappearance of dissolved organic carbon (DOC)); OECD 301B (CO2 evolution test), OECD 301C (modified MITI test (I)); OECD 301D (closed bottle test); OECD 301E (modified OECD screening); OECD 301F (pressure respirometry) or OECD 304A (intrinsic biodegradability in soil), OECD 306 (biodegradability in seawater) and OECD 310 (immediate biodegradability in sealed containers - CO2 (headspace test)).

[0086] The microcapsules of the present invention are characterized in that they have a core comprising at least one fragrance which is different from a household cleaning composition.

[0087] In the present invention, the household cleaning composition and the solid microcapsules (a series or collection of solid microcapsules) are different entities.

[0088] In one embodiment, the composition of the invention comprises a collection of solid microcapsules, each of which is a solid microcapsule as defined above, and wherein the standard deviation of the diameter size distribution of the microcapsules is less than 50%, in particular less than 25% or less than 1 μm.

[0089] The size distribution of the solid microcapsules can be measured, for example, by image analysis techniques under an optical microscope or light scattering techniques using a Mastersizer 3000 (Malvern Instruments) equipped with a Hydro-SV measuring unit.

[0090] Composition C1

[0091] As indicated above, preferably composition C1 is in the form of an emulsion and therefore comprises a continuous phase and a dispersed phase.

[0092] In one embodiment, the composition C1 as defined above in the core of the solid microcapsule comprises at least 20% by weight of fragrance relative to the total weight of the composition C1; preferably, 25-60% by weight, more preferably 30-50% by weight relative to the total weight of the composition C1.

[0093] In one embodiment, composition C1 further comprises at least one gelling agent.

[0094] The gelling agent can be selected from water-soluble or water-dispersible polymers, especially water-based polymers, preferably selected from the group consisting of the following substances:

[0095] - cellulose derivatives, for example cellulose ethers: methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose;

[0096] - polyacrylates (also called carbomers), for example polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(hydroxyethyl methacrylate) (pHEMA), poly(N-2-hydroxypropyl methacrylate) (pHPMA);

[0097] - polyacrylamides, for example poly(N-isopropylacrylamide) (PNIPAM);

[0098] - Polyvinylpyrrolidone (PVP) and its derivatives;

[0099] - Polyvinyl alcohol (PVA) and its derivatives;

[0100] - poly(ethylene glycol), poly(propylene glycol) and derivatives thereof, for example, poly(ethylene glycol) acrylates / methacrylates, poly(ethylene glycol) diacrylates / dimethacrylates, polypropylene carbonate;

[0101] - polysaccharides, for example, carrageenan, locust bean gum or tara gum, dextran, xanthan gum, chitosan, agarose, hyaluronic acid, gellan gum, guar gum, gum arabic, baicalensis gum, didan gum, oat gum, karaya gum, ghatti gum, kolan gum, pectin, konjac gum, starch;

[0102] - protein derivatives, for example, gelatin, collagen, fibrin, polylysine, albumin, casein;

[0103] - Polyurethane and its derivatives.

[0104] The gelling agent may also be selected from solid particulates that can act as gelling agents when dispersed in water, such as clays, silicas, and silicates.

[0105] As solid particles that can be used as gelling agents in composition C1, mention may be made of clays and silicates that belong in particular to the class of phyllosilicates (also called sheet silicates). As examples of silicates that can be used in the present invention, mention may be made of bentonite, laponite, attapulgite, sepiolite, montmorillonite, saponite, ulexite, nontronite, kaolinite, talc, sepiolite, chalk. Synthetic fumed silica may also be used. The above-mentioned clays, silicates and silicas may advantageously be modified by organic molecules, for example, polyethers, ethoxylated amides, quaternary ammonium salts, long-chain diamines, long-chain esters, polyethylene glycols, polypropylene glycols.

[0106] Preferably, the gelling agent is selected from cellulose derivatives, polyacrylates, derivatives of poly(ethylene glycol) and synthetic silica.

[0107] In one embodiment, composition C1 comprises 0.1 to 30 wt % of a gelling agent, preferably 0.5 to 20 wt %, more preferably 0.5 to 10 wt %.

[0108] In one embodiment, composition C1 comprises 30 to 70% by weight of water, preferably 35 to 65% by weight, more preferably 35 to 60% by weight.

[0109] In one embodiment, the composition C1 also comprises at least one surfactant, which is particularly selected from anionic, cationic, amphoteric and nonionic surfactants. As surfactants, block oxyethylene / oxypropylene polymers, for example, poloxamer; sorbitol fatty acid esters and oxyethylated derivatives thereof, for example, sorbitol monostearate, sorbitol monopalmitate, oxyethylated sorbitan stearate, palmitate and oleate; polyethylene glycol derivatives and mixtures of glycerides of caprylic acid and capric acid (monoglycerides, diglycerides, triglycerides); alkyl glycosides, especially alkyl polyglucosides such as octyl / octyl glucoside or lauryl glucoside.

[0110] In one embodiment, composition C1 also contains at least one hydrophobicity corrector of the essence. These agents are hydrophobic materials with a cLogP greater than 4, preferably greater than 6, and have good compatibility with the essence used. Among these agents, mention may be made of oils such as monoglycerides, diglycerides and triglycerides, for example, capric / caprylic triglycerides; fatty acid esters of oligomers of polyglycerol, polyethylene glycol, propylene glycol and polybutylene glycol; nonionic fatty alcohol alkoxylates, for example, isopropyl myristate, diethyl phthalate, dibutyl phthalate, diisodecyl adipate; mineral oil; silicone oils, for example, polydimethylsiloxane and polydimethylcyclosiloxane; diethyl phthalate; polyalphaolefins; castor oil.

[0111] Preferably, composition C1 is in the form of a nanoemulsion, wherein the continuous phase is a hydrogel. Preferably, the average diameter of the droplets of the nanoemulsion is from 50 nm to 5 μm, preferably from 100 nm to 3 μm, more preferably from 100 nm to 1 μm.

[0112] Preferably, composition C1 is in the form of an emulsion in which the continuous phase is a hydrogel.

[0113] Preferably, the average diameter of the droplets of the emulsion is from 50 nm to 5 μm, more preferably from 100 nm to 3 μm, further preferably from 100 nm to 1 μm.

[0114] spices

[0115] As mentioned above, composition C1 comprises at least one fragrance.

[0116] For example, the composition C1 according to the invention may comprise a single fragrance (single fragrance) or a mixture of several fragrances (or a mixture of several essences).

[0117] Among the fragrances, particular mention may be made of any type of fragrance or flavor, which terms may be used synonymously herein. These fragrances or flavors are well known to the person skilled in the art and include in particular those mentioned, for example, in S. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969); S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ, 1960); the fragrances in the list of the International Fragrance Association (IFRA) (http: / / www.ifraorg.org / en / ingredients) and "Flavor and Fragrance Materials", 1991 (Allured Publishing Co. Wheaton, III. USA).

[0118] The flavors used in the present invention may include natural products, for example, extracts, essential oils, absolutes, resinoids, resins, concretes, etc.; and synthetic basic substances, for example, hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, alicyclic and heterocyclic compounds.

[0119] In one embodiment, the fragrance comprises less than 10 wt%, even less than 7.5 wt%, of compounds with a cLogP of less than 2.1, relative to the total weight of the fragrance. In one embodiment, the fragrance does not comprise any compound with a cLogP of less than 2.1.

[0120] Solid shell

[0121] In one embodiment, the above-mentioned solid microcapsules comprise a solid shell consisting entirely of a cross-linked polymer as defined above.

[0122] The solid shell is formed by a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups.

[0123] In the present invention, the term "monomer" or "polymer" means any basic unit suitable for forming a solid material by polymerization (alone or in combination with other monomers or polymers). The term "polymer" also includes oligomers.

[0124] In one embodiment, the crosslinked polymer is obtained by polymerization of monomers or polymers selected from the group consisting of aliphatic or aromatic esters or polyesters, urethanes or polyurethanes, anhydrides or polyanhydrides, sugars or polysaccharides, ethers or polyethers, amides or polyamides, and carbonates or polycarbonates, and the monomers or polymers also have at least one reactive functional group selected from the group consisting of acrylates, methacrylates, vinyl ethers, N-vinyl ethers, vinyl esters, thioenes, maleates, epoxy groups, siloxanes, amines, lactones, phosphates, and carboxylates.

[0125] Among the examples of the monomers or polymers, the following compounds and mixtures thereof may be mentioned but are not limited thereto:

[0126] - aliphatic or aromatic esters and polyesters, including in particular polyglycolide (PGA), polylactic acid (PLA), polylactide-co-glycolide (PLGA), poly(vicinal esters) such as polycaprolactone (PCL), polydioxanone, poly(ethylene succinate), poly(butylene succinate) (PBS), poly(ethylene adipate), poly(butylene adipate), polyethylene sebacate, polybutylene sebacate, polyvalerolactone (PVL), polydecalactone, polyhydroxyvalerate, poly-β-malic acid, poly-3-hydroxybutyrate (PHB), poly-3-hydroxybutyrate-co-3-hydroxyvalerate (P-3HB-3HV), poly-3-hydroxybutyrate-co-4 ... butyrate (P-3HB-4HB), poly-3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate (P-3HB-3HV-4HB), poly(3-hydroxyvalerate), poly(3-hydroxypropionate), poly(3-hydroxyhexanoate), poly(3-hydroxyoctanoate), poly(3-hydroxydecanoate), poly(3-hydroxyundecanoate), poly(3-hydroxydodecanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate). esters), poly(2-hydroxybutyrate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(4-hydroxybutyrate), poly(4-hydroxybutyrate-co-2-hydroxybutyrate), poly(4-hydroxypropionate), poly(4-hydroxyvalerate), poly(5-hydroxybutyrate), poly(5-hydroxyvalerate), poly(6-hydroxyhexanoate), poly(alkylene esters), poly(dicarboxylates), poly(butylene adipate), poly(butylene adipate-co-terephthalate), poly(butylene carbonate), poly(butylene pimarate) , poly(butylene succinate-co-adipate), poly(butylene succinate-co-carbonate), poly(butylene sebacate), poly(butylene sebacate-co-terephthalate), poly(butylene succinate-co-terephthalate), poly(butylene succinate-co-lactate), poly(cyclohexene carbonate), poly(dioxanone), poly(ethylene azelaate), poly(ethylene carbonate), poly(ethylene sebacate), poly(ethylene furanoate), poly(ethylene oxalate), poly(ethylene succinate), poly(ethylene succinate-co-adipate), poly(ethylene sebacate), poly(ethylene succinate-co-terephthalate), poly(ethylene linoleate),poly(hexamethylene sebacate), poly(glycolide-co-caprolactone), poly(lactide-co-ε-caprolactone), polymandelotide, poly(B-malic acid), poly(b-lactide), poly(propylene succinate), poly(tetramethylene adipate-co-terephthalate), poly(tetramethylene carbonate), poly(trimethyl carbonate), poly(tetramethylene succinate)-co-(tetramethylene carbonate), poly(trimethyl adipate), poly(dimethylene adipate-co-dieterephthalate), poly(tetramethylene adipate), poly(ethylene glycol tetramethyl ester), poly(butylene succinate), poly(valerolactone), and further having at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiol, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups;

[0127] - anhydrides or polyanhydride family, for example, derived from polysebacic acid, polyadipic acid, polyterephthalic acid, poly(bis(p-carboxyphenoxy)alkanoic acid; or more generally from the family of polyanhydrides, such as described in Advanced Drug Delivery Reviews 54 (2002) 889-910, which also have at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiol, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups;

[0128] - the family of carbohydrates and polysaccharides, including in particular carrageenan; dextran; cyclodextrins (e.g., hyaluronic acid); agarose; chitosan; chitin; sodium alginate; starch; cellulose and its derivatives, such as, for example, methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose, which also have at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiol, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups;

[0129] - ether and polyether families, including in particular polyethylene glycols, further having at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiol, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups; and

[0130] - the family of amides and polyamides, especially including poly(ester amides) or polyterephthalamides, further having at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups;

[0131] - polyurethane series, especially including the reaction products of polyols and polyisocyanates, the reaction products also having at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups. Among the above polyols, mention may be made of 1,4-butanediol, 1,2-propylene glycol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, methylpropylene glycol, bisphenol A, polyoxypropylene glycol, polybutadiene glycol, oxytetramethylene glycol, ethylene glycol adipate glycol, polyethylene adipate glycol propylene glycol, polydiethylene glycol adipate glycol, polydiethylene glycol adipate-diethylene glycol ester glycol, pentaerythritol, glycerol, trimethylolpropane, triethylolpropane or oxyglycerol. Among the abovementioned polyisocyanates, mention may be made of derivatives of hexamethylene diisocyanate, derivatives of methylene dicyclohexyl diisocyanate or derivatives of isophorone diisocyanate.

[0132] In a preferred embodiment, the cross-linked polymer is selected from the group consisting of cross-linked polyesters, cross-linked polyepoxides and cross-linked polyurethanes.

[0133] Preferably, the crosslinked polymer shell of the solid microcapsules is obtained by polymerization of a composition C2 comprising at least one monomer or polymer having at least one reactive functional group as defined above, at least one crosslinking agent and optionally at least one crosslinking photoinitiator or catalyst.

[0134] "Crosslinking agent" refers to a compound having at least one or two reactive functional groups that is capable of crosslinking monomers or polymers or a mixture of monomers and polymers when polymerized.

[0135] The crosslinking agent may be selected from molecules having at least two identical or different functional groups selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiol, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups.

[0136] As crosslinking agents, mention is made in particular of:

[0137] - diacrylates, for example 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,10-decanediol dimethacrylate, bis(2-methacryloxyethyl) N,N′-1,9-nonanedicarbamate, 1,4-butanediol diacrylate, 1,5-pentanediol dimethacrylate, allyl methacrylate, N,N′-diol methylenebisacrylamide, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, tetraethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, N,N-diallylacrylamide or glycidyl methacrylate;

[0138] - multifunctional acrylates, for example, pentaerythritol pentaacrylate, 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane trimethacrylate, ethylenediaminetetramethacrylate, pentaerythritol triacrylate or pentaerythritol tetraacrylate; and

[0139] - an acrylate which also has another reactive functional group, for example, propargyl methacrylate, N-acryloxysuccinimide, N-(2-hydroxypropyl)methacrylamide, N-(tert-butoxycarbonyl-aminopropyl)methacrylamide, monoacryloxyethyl phosphate, acrylic anhydride, 2-(tert-butylamino)ethyl methacrylate, N,N-diallylacrylamide or glycidyl methacrylate.

[0140] "Photoinitiator" refers to a compound that is capable of cleaving upon exposure to light radiation.

[0141] The photoinitiators that can be used in the present invention are known in the prior art and are described, for example, in the following documents: “Les photoinitiateurs dans la réticulation des revêtements”, G. Li Bassi, Double Liaison-Chimie des Peintures, Issue 361, November 1985, pp. 34-41; “Applications industrielles de la polymérisation photoinduite”, Henri Strub, L'Actualité Chimique, February 2000, pp. 5-13; and “Photopolymères: considérations théoriques et réaction de prise”, Marc, JM Badie, Double Liaison-Chimie des Peintures, Issues 435-436, 1992, pp. 28-34.

[0142] These photoinitiators include:

[0143] -α-Hydroxyketones, for example, 2-hydroxy-2-methyl-1-phenyl-1-propanone, which is marketed by BASF under the trade name 1173 and 4265, 184, 2959 and 500 and CYTEC CPK sales;

[0144] -α-aminoketones, in particular 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-, which is marketed by BASF under the trade name 907 and 369 sales;

[0145] - aromatic ketones, for example, marketed under the name TRIETHYLENE by LAMBERTI Aromatic ketones sold by TZT; or by LAMBERTI under the trade name Thioxanthone sold by ITX, as well as quinones. Most of these aromatic ketones require the presence of hydrogen donor compounds such as tertiary amines (especially alkanolamines). Particular mention may be made of the product sold by LAMBERTI under the trade name Tertiary amines sold by EDB.

[0146] -α-dicarbonyl derivatives, the most representative of which are produced by BASF under the trade name Benzyl dimethyl ketal sold under the trade name 651. KB1 sells other commercial products; and

[0147] - acylphosphine oxides, for example, available from BASF under the trade name 819, 1700 and 1800; 4265; TPO and TPO-L is sold as bisacylphosphine oxide (BAPO).

[0148] Among the photoinitiators, mention may also be made of aromatic ketones such as benzophenone, phenylglyoxylic esters such as the methyl ester of phenylglyoxylic acid, oxime esters such as [1-(4-phenylsulfonylbenzoyl)heptanimino]benzoate, sulfonates, iodonium salts and oxime sulfonates.

[0149] Preparation of microcapsules

[0150] In one embodiment, the solid microcapsules are obtained by a method comprising the steps of:

[0151] a) adding, under stirring, the composition C1 as described above to the polymerized composition C2, the compositions C1 and C2 being immiscible with each other,

[0152] The viscosity of composition C2 at 25° C. is 500 to 100,000 mPa·s, and is preferably greater than the viscosity of composition C1. Composition C2 comprises:

[0153] - at least one monomer or polymer having at least one reactive functional group as defined above,

[0154] - at least one cross-linking agent, and

[0155] - optionally at least one crosslinking photoinitiator or catalyst,

[0156] An emulsion (E1) is then obtained comprising droplets of composition C1 dispersed in composition C2;

[0157] b) adding the emulsion (E1) to the composition C3 under stirring, the compositions C2 and C3 being immiscible with each other,

[0158] The viscosity of composition C3 at 25° C. is 500 to 100,000 mPa·s, and is preferably greater than the viscosity of emulsion (E1).

[0159] A double emulsion (E2) is then obtained comprising droplets dispersed in the composition C3;

[0160] c) applying shear to the emulsion (E2),

[0161] A double emulsion (E3) is then obtained comprising droplets of controlled size dispersed in the composition C3; and

[0162] d) polymerizing composition C2, whereupon solid microcapsules dispersed in composition C3 are obtained.

[0163] The method comprises forming a double emulsion consisting of droplets containing at least one fragrance enclosed by a crosslinkable liquid phase. These double droplets are prepared to be monodisperse in size before being converted into rigid capsules by crosslinking or polymerization. The preparation comprises the following four steps.

[0164] In one embodiment, the method of the invention comprises a preliminary step of preparing composition C1 in the form of an emulsion before step a) above.

[0165] In this step, the fragrance-containing composition c1 is added to the hydrophilic composition c2, this step being carried out under stirring in order to emulsify the mixture of composition c1, which means that composition c1 is generally under mechanical stirring when adding the fragrance-containing composition c1.

[0166] In this step, the fragrance-containing composition c1 is at a temperature between 0° C. and 100° C., preferably between 10° C. and 80° C. and more preferably between 15° C. and 60° C. In this step, the hydrophilic composition c2 is at a temperature between 0° C. and 100° C., preferably between 10° C. and 80° C. and more preferably between 15° C. and 60° C.

[0167] To carry out this step, any type of stirrer commonly used for forming emulsions may be used, for example, a mechanical blade stirrer, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser or a high-speed homogenizer.

[0168] In one embodiment, the hydrophilic composition c2 comprises a gelling agent.

[0169] In another embodiment, once the composition C1 containing fragrance is emulsified in the hydrophilic composition c2, the gelling agent is added to the composition C1. In this embodiment, to add the gelling agent to the composition C1, any type of stirrer for homogenizing a solution can be used, for example, a stirrer using mechanical blades at a slow speed.

[0170] Step a) of the process of the invention comprises the preparation of a first emulsion (E1).

[0171] The first emulsion is a dispersion of droplets of composition C1 (containing at least one fragrance) dispersed in a polymer composition C2 immiscible with C1, obtained by adding C1 dropwise to C2 under stirring.

[0172] In step a), composition C1 is added to the crosslinkable polymerizable composition C2, this step being carried out under stirring in order to emulsify the mixture of compositions C1 and C2, which means that composition C2 is generally mechanically stirred while composition C1 is being added.

[0173] The addition of composition C1 to composition C2 is generally carried out dropwise.

[0174] In step a), composition C1 is at a temperature of 0° C. to 100° C., preferably 10° C. to 80° C., more preferably 15° C. to 60° C. In step a), composition C2 is at a temperature of 0° C. to 100° C., preferably 10° C. to 80° C., and more preferably 15° C. to 60° C.

[0175] Under the addition conditions of step a), compositions C1 and C2 are immiscible, which means that the amount (by weight) of composition C1 that can be dissolved in composition C2 is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total weight of composition C2; and the amount (by weight) of composition C2 that can be dissolved in composition C1 is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total weight of composition C1.

[0176] Thus, when composition C1 is brought into contact with composition C2 under stirring, it is dispersed in the form of droplets known as single drops.

[0177] The immiscibility between compositions C1 and C2 also allows preventing the migration of active ingredients from composition C1 into composition C2.

[0178] Composition C2 is stirred to form an emulsion comprising droplets of composition C1 dispersed in composition C2. Such an emulsion is also referred to as a "single emulsion" or a C2-in-C1 emulsion.

[0179] For carrying out step a), any type of stirrer commonly used for forming emulsions may be used, for example, a mechanical blade stirrer, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser or a high-speed homogenizer.

[0180] Composition C2 is intended to form the future solid shell of the microcapsules.

[0181] The volume fraction of C1 in C2 can be varied between 0.1 and 0.6 to control the thickness of the capsule shell obtained when the method is completed.

[0182] In one embodiment, the ratio between the volume of composition C1 and the volume of composition C2 varies between 1: 10 and 10: 1. Preferably, this ratio is between 1:3 and 5:1, more preferably between 1:3 and 3:1.

[0183] Preferably, the viscosity of composition C2 at 25° C. is 1000 to 50000 mPa·s, more preferably 2000 to 25000 mPa·s, for example, 3000 to 15000 mPa·s.

[0184] Preferably, the viscosity of composition C2 is greater than the viscosity of composition C1.

[0185] Viscosity was measured using Hake Rheostress TM The measurements were performed using a 600 rheometer equipped with a cone with a diameter of 60 mm and an angle of 2 degrees; the temperature control unit was set at 25°C. The viscosity value was 10s -1 The shear rate is read.

[0186] In this embodiment, the destabilization kinetics of the emulsion (E1) droplets are significantly low, which allows the shell of the microcapsules to polymerize in step d) before the emulsion destabilizes. Once the polymerization is complete, thermodynamic stabilization is provided. Therefore, the relatively high viscosity of the composition C2 ensures the stability of the emulsion (E1) obtained after step a).

[0187] Preferably, the interfacial tensions between compositions C1 and C2 are low. Typically, these interfacial tensions vary between 0 mN / m and 50 mN / m, preferably between 0 mN / m and 20 mN / m.

[0188] The low interfacial tension between compositions C1 and C2 also advantageously allows ensuring the stability of the emulsion (E1) obtained after step a).

[0189] Composition C2 comprises at least one monomer or polymer (as defined above), at least one crosslinking agent (as defined above) and optionally at least one crosslinking photoinitiator or catalyst (as defined above), making the composition crosslinkable.

[0190] In one embodiment, composition C2 comprises from 50 to 99% by weight of monomers or polymers (as defined above) or mixtures of monomers and polymers (as defined above), relative to the total weight of composition C2.

[0191] In one embodiment, composition C2 comprises from 1 to 20% by weight of a crosslinker or a mixture of crosslinkers as defined above, relative to the total weight of composition C2.

[0192] In one embodiment, composition C2 comprises from 0.1 to 5% by weight of a photoinitiator or a mixture of photoinitiators (as defined above), relative to the total weight of composition C2.

[0193] In one embodiment, composition C2 comprises 0.001 to 20 wt % of a crosslinking agent relative to the total weight of the composition.

[0194] In one embodiment, composition C2 may also contain additional monomers or polymers capable of improving the properties of the microcapsule shell and / or imparting new properties to the microcapsule shell.

[0195] Among these additional monomers or polymers, mention may be made of monomers or polymers having groups sensitive to pH, temperature, UV or IR.

[0196] These additional monomers or polymers can induce the rupture of the solid microcapsule upon stimulation (eg by pH, temperature, UV or IR) and thus release its contents.

[0197] These additional monomers or polymers may be selected from monomers or polymers carrying at least one of the following groups:

[0198] - pH sensitive groups, for example, primary, secondary or tertiary amines; carboxylic acids; phosphate, sulfate, nitrate or carbonate groups;

[0199] - UV-sensitive or UV-cleavable groups (or photochromic groups), for example, azobenzene, spiropyran, 2-diazo-1,2-naphthoquinone, o-nitrobenzyl, thiol or 6-nitro-veratryloxycarbonyl, for example, poly(ethylene oxide)-block-poly(2-nitrobenzyl methacrylate) and other block copolymers, for example, in particular those described in Liu et al., Polymer Chemistry 2013, 4, 3431-3443;

[0200] - IR-sensitive or IR-cleavable groups, for example, o-nitrobenzyl or 2-diazo-1,2-naphthoquinone, for example, the polymers described in Liu et al., Polymer Chemistry 2013, 4, 3431-3443;

[0201] - hydrolysis-sensitive groups, for example, polylactic acid, polyglycolic acid, poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxybutyrate, chitosan, dextran, agarose, cellulose and derivatives of these compounds; and

[0202] - Temperature-sensitive groups, for example, poly(N-isopropylacrylamide).

[0203] Step b) of the process of the invention comprises the preparation of a second emulsion (E2).

[0204] The second emulsion is a dispersion of droplets of the first emulsion in a composition C3 that is immiscible with C2, and is obtained by adding the emulsion (E1) dropwise to C3 under stirring.

[0205] In step b), the emulsion (E1 ) is at a temperature between 15°C and 60°C. In step b), the composition C3 is at a temperature between 15°C and 60°C.

[0206] Under the addition conditions of step b), compositions C2 and C3 are immiscible, which means that the amount (by weight) of composition C2 that can be dissolved in composition C3 is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total weight of composition C3; and the amount (by weight) of composition C3 that can be dissolved in composition C2 is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total weight of composition C2.

[0207] Thus, when emulsion (E1) comes into contact with composition C3 under stirring, it is dispersed in the form of droplets known as double droplets, and the dispersion of these droplets of emulsion (E1) in the continuous phase C3 is known as emulsion (E2).

[0208] Typically, the double droplet formed in step b) corresponds to a single droplet of composition C1 as described above, surrounded by a shell of composition C2 which completely encapsulates said single droplet.

[0209] The double droplets formed in step b) may also comprise at least two single droplets of composition C1 surrounded by a shell of composition C2 which completely encapsulates the single droplets.

[0210] The double droplet thus comprises a core consisting of one or more single droplets of composition C1 and a layer of composition C2 surrounding the core.

[0211] The obtained emulsion (E2) is usually a polydisperse double emulsion (C1-in-C2-in-C3 emulsion or C1 / C2 / C3 emulsion), which means that the double droplets do not have different size distributions in the emulsion (E2).

[0212] The immiscibility between compositions C2 and C3 prevents mixing between the layers of composition C2 and composition C3, thus ensuring the stability of the emulsion (E2).

[0213] The immiscibility between compositions C2 and C3 also prevents the migration of water-soluble substances of composition C1 from the core of the droplet to composition C3.

[0214] For carrying out step b), any type of stirrer commonly used for forming emulsions may be used, for example a mechanical blade stirrer, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser or a high-speed homogenizer.

[0215] In one embodiment, the viscosity of composition C3 at 25°C is greater than the viscosity of emulsion (E1) at 25°C.

[0216] In the present invention, the viscosity of composition C3 at 25°C is 500 to 100,000 mPa·s.

[0217] Preferably, the viscosity of composition C3 at 25 ℃ is 3000-100000 mPa·s, more preferably 5000-8000 mPa·s, for example 7000-70000 mPa·s.

[0218] In this embodiment, given the very high viscosity of the continuous phase formed by the composition C3, the destabilization kinetics of the double droplets of the emulsion (E2) are significantly slow relative to the length of time of the process of the invention, thus providing a kinetic stabilization of the emulsion (E2) and then of the emulsion (E3) until the polymerization of the capsule shell is complete. Once polymerized, the capsules are thermodynamically stable.

[0219] The very high viscosity of composition C3 therefore ensures the stability of the emulsion (E2) obtained after step b).

[0220] The low surface tension between C3 and the first emulsion and the high viscosity of the system advantageously allow to ensure the kinetic stability of the double emulsion (E2), preventing its dephasing throughout the production process.

[0221] Preferably, the interfacial tension between compositions C2 and C3 is low. The low interfacial tension between compositions C2 and C3 also advantageously allows ensuring the stability of the emulsion (E2) obtained after step b).

[0222] The volume fraction of the first emulsion in C3 can be 0.05-0.5 to improve the production yield and change the average diameter of the capsules. At the end of this step, the particle size distribution in the second emulsion is relatively wide.

[0223] In one embodiment, the ratio between the volume of emulsion (E1) and the volume of composition C3 is from 1:10 to 10: 1. Preferably, the ratio is from 1:9 to 3:1, preferably from 1:9 to 1:1.

[0224] In one embodiment, composition C3 further comprises at least one branched polymer (preferably with a molecular weight greater than 5000 g·mol -1 ) and / or molecular weight greater than 5000 g·mol-1 at least one polymer and / or solid particles such as silicates.

[0225] In one embodiment, composition C3 comprises at least one branched polymer, preferably with a molecular weight greater than 5000 g·mol -1 , more preferably 10000 to 500000 g·mol -1 , for example, 50,000 to 300,000 g·mol -1 .

[0226] "Branched polymer" refers to a polymer having at least one branching point between its two end groups, a branching point being a point on the chain to which a side chain (also called a branch or pendant chain) is attached.

[0227] Among the branched polymers, mention may be made, for example, of graft polymers, comb or star polymers or dendrimers.

[0228] In one embodiment, composition C3 comprises at least one -1 , preferably 10000 to 500000 g·mol -1 , for example, 50,000 to 300,000 g·mol -1 of polymers.

[0229] As polymers that can be used in composition C3, the following compounds can be cited and used alone or as a mixture thereof:

[0230] - cellulose derivatives, for example, cellulose ethers: methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose;

[0231] - polyacrylates (also known as carbomers), for example polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyhydroxyethyl methacrylate (pHEMA), polymethacrylate N-2-hydroxypropyl methacrylate (pHPMA);

[0232] - polyacrylamides, for example poly(N-isopropylacrylamide) (PNIPAM);

[0233] - Polyvinylpyrrolidone (PVP) and its derivatives;

[0234] - Polyvinyl alcohol (PVA) and its derivatives;

[0235] - polyethylene glycol, polypropylene glycol and their derivatives, for example, poly(ethylene glycol) acrylate / methacrylate, poly(ethylene glycol) diacrylate / dimethacrylate, polypropylene carbonate;

[0236] - polysaccharides, for example, carrageenan, locust bean gum or tara gum, dextran, xanthan gum, chitosan, agarose, hyaluronic acid, gellan gum, guar gum, gum arabic, baicalensis gum, didan gum, oat gum, karaya gum, ghatti gum, kolan gum, pectin, konjac gum, starch;

[0237] - protein derivatives, for example, gelatin, collagen, fibrin, polylysine, albumin, casein;

[0238] - silicone derivatives, for example polydimethylsiloxane (also called dimethylsiloxane), alkylsiloxanes, arylsiloxanes, alkylarylsiloxanes, polyethylene glycol dimethicone, propylene glycol dimethicone;

[0239] - waxes, for example, diester waxes (alkanediol diesters, hydroxycarboxylic acid diesters), triester waxes (triacylglycerol; triesters of alkane-1,2-diol, ω-hydroxycarboxylic acid and fatty acid; esters of hydroxymalonic acid, fatty acid and alcohol; triesters of hydroxy fatty acid, fatty acid and fatty alcohol; triesters of fatty acid, hydroxy fatty acid and diol) and polyester waxes (polyesters of fatty acid). Fatty acid esters that can be used as waxes in the present invention are, for example, cetyl palmitate, cetyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, cetyl stearate, stearyl stearate, myristyl stearate, cetyl myristate, isocetyl stearate, trimyristin, tripalmitin, monostearin or palmitin and cetyl palmitate;

[0240] - fatty acids which can be used as waxes are, for example, cerotic acid, palmitic acid, stearic acid, dihydroxystearic acid, behenic acid, tetracosanoic acid, arachidic acid, myristic acid, lauric acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tridecanoic acid, pentacosanoic acid, heptadecanoic acid, octacosanoic acid or nonacosanoic acid;

[0241] - fatty acid salts, in particular fatty acid aluminum salts, for example, aluminum stearate, hydroxyaluminum bis(2-ethylhexanoate);

[0242] - Isomerized jojoba oil;

[0243] - Hydrogenated sunflower oil;

[0244] - Hydrogenated coconut oil;

[0245] - Hydrogenated lanolin oil;

[0246] - castor oil and its derivatives, in particular modified hydrogenated castor oil or compounds obtained by esterification of castor oil with fatty alcohols;

[0247] - Polyurethane and its derivatives;

[0248] - styrene polymers such as styrene-butadiene; and

[0249] - Polyolefins such as polyisobutylene.

[0250] In one embodiment, composition C3 comprises solid particles such as clay, silica and silicates.

[0251] As solid particles that can be used in composition C3, mention may be made of clays and silicates that belong in particular to the class of phyllosilicates (also referred to as sheet silicates). As examples of silicates that can be used in the present invention, mention may be made of bentonite, laponite, attapulgite, sepiolite, montmorillonite, saponite, ulexite, nontronite, kaolinite, talc, sepiolite, chalk. It is also possible to use gas-phase synthesized silicon dioxide. The above-mentioned clays, silicates and silicas can advantageously be modified by organic molecules, for example, polyethers, ethoxylated amides, quaternary ammonium salts, long-chain diamines, long-chain esters, polyethylene glycols, polypropylene glycols.

[0252] These particles may be used alone or in combination.

[0253] In one embodiment, composition C3 comprises at least one -1 Any mixture of the above compounds can be used.

[0254] Step c) of the process of the invention comprises refining the droplet size of the second emulsion (E2).

[0255] This step may comprise applying a controlled uniform shear to the emulsion (E2), the applied shear rate being between 10 s -1 and 100000s -1 between.

[0256] In one embodiment, the polydisperse double droplets obtained in step b) are size refined by subjecting them to a shearing capable of fragmenting them into new double droplets of controlled, uniform diameter. Preferably, the fragmentation step is carried out using a Couette type high shear unit, according to the method described in patent application EP15306428.2.

[0257] In one embodiment, in step c), the second emulsion (E2) obtained after step b), consisting of polydisperse double droplets dispersed in a continuous phase, is subjected to shear in a mixer applying a controlled uniform shear.

[0258] Therefore, in this embodiment, step c) comprises applying a controlled uniform shear to the emulsion (E2), wherein the applied shear rate is between 1000 s -1 and 100000s -1 between.

[0259] In this embodiment, in a mixer, the shear rate is said to be controlled and uniform when the shear rate reaches the same maximum value for all parts of the emulsion at a given time (which can vary from one point of the emulsion to another), regardless of the length of time. The precise configuration of the mixer is not essential to the present invention, provided that the entire emulsion is subjected to the same maximum shear when output from the device. A mixer suitable for carrying out step c) is specifically described in document US 5938581.

[0260] Controlled uniform shearing can be achieved when the second emulsion circulates through a unit formed by:

[0261] - Two concentric rotating cylinders (also called Couette-type mixer);

[0262] - two parallel rotating discs; or

[0263] - Two parallel oscillating plates.

[0264] In this embodiment, the shear rate applied to the second emulsion is 1000s -1 and 100000s -1 Between, preferably in the 1000s -1 and 50000s -1 Between, preferably in the 2000s -1 and 20000s -1 between.

[0265] In this embodiment, in step c), the second emulsion is input into a mixer and subjected to shearing, which results in the formation of a third emulsion. The third emulsion (E3) is chemically identical to the second emulsion (E2), but consists of monodisperse double droplets, whereas emulsion (E2) consists of polydisperse double droplets. The third emulsion (E3) typically consists of a dispersion of double droplets, the dispersion of double droplets comprising a core consisting of one or more droplets of composition C1 and a layer of composition C2 encapsulating the core, the double droplets being dispersed in composition C3.

[0266] The difference between the second and third emulsions lies in the size variation of the twin droplets: through the above-mentioned breakup mechanism, the size of the second emulsion droplets is polydisperse, while the size of the third emulsion droplets is monodisperse.

[0267] Preferably, in this embodiment, the second emulsion is added continuously to the mixer, which means that the amount of double emulsion (E2) input into the mixer is the same as the amount of third emulsion (E3) output from the mixer.

[0268] Since the size of the emulsion droplets (E3) corresponds substantially to the size of the solid microcapsule droplets after polymerization, the size of the microcapsules and the thickness of the shell can be adjusted by adjusting the shear rate in step c), and the decrease in droplet size is strongly correlated with the increase in shear rate. This allows the final size of the microcapsules to be adjusted by changing the shear rate applied in step c).

[0269] In a preferred embodiment, the mixer used in step c) is a Couette type mixer, comprising two concentric cylindrical barrels with an inner diameter of R o The outer cylinder has an outer diameter of R i The inner cylinder is fixed and the outer cylinder rotates at an angular velocity ω.

[0270] A Couette type mixer suitable for use in the process of the present invention can be supplied by TSR France.

[0271] In one embodiment, the angular velocity ω of the inner rotating cylinder of the Couette mixer is greater than or equal to 30 rad·s -1 .

[0272] For example, the angular velocity ω of the drum in a Couette mixer is about 70 rad·s -1 .

[0273] The size of the outer fixed cylinder of the Couette mixer can be used to adjust the space between the inner rotating cylinder and the outer fixed cylinder (d = R o -R i ).

[0274] In one embodiment, the space between two concentric cylinders of the Couette mixer (d = R o -R i ) is 50 to 1000 μm, preferably 100 to 500 μm, for example, 200 to 400 μm.

[0275] For example, the distance d between two concentric cylinders is 100 μm.

[0276] In this embodiment, in step c), the second emulsion is usually input into the mixer by a pump and guided into the space between two concentric cylinders, the outer cylinder is fixed and the inner cylinder rotates at an angular velocity ω.

[0277] When the double emulsion is located between two cylindrical barrels, the shear rate applied to the emulsion is given by:

[0278]

[0279] in:

[0280] -ω is the angular velocity of the inner rotating cylinder;

[0281] -R o To fix the inner diameter of the outer cylindrical barrel; and

[0282] -R i is the outer diameter of the inner rotating cylinder.

[0283] In another embodiment, when the viscosity of composition C3 at 25° C. is greater than 2000 mPa·s, step C) comprises applying to the emulsion (E2) less than 1000 s -1 The shear rate.

[0284] In this embodiment, the breaking step c) can be carried out using any type of mixer commonly used for forming emulsions in a speed of less than 1000 s. -1 In this case, ie under the conditions described in patent application FR 1661787, the viscosity of composition C3 is greater than 2000 mPa·s.

[0285] The geometrical features of the twin droplets formed at the end of this step will determine the geometrical features of the future capsule.

[0286] In this embodiment, in step c), the emulsion (E2) consisting of polydisperse droplets dispersed in the continuous phase is stirred, for example, in a mixer at a speed of less than 1000 s. -1 The low shear rate is subjected to shear.

[0287] In this embodiment, for example, the shear rate applied in step c) is 10 s -1 ~1000s -1 .

[0288] Preferably, the shear rate applied in step c) is strictly below 1000 s -1 .

[0289] In this embodiment, if a high shear stress is applied to the emulsion droplets (E2), the droplets of the emulsion (E2) can only be effectively broken into fine monodisperse emulsion droplets (E3).

[0290] The shear stress σ applied to the emulsion droplets (E2) is defined as the tangential force per unit droplet surface area resulting from the macroshear applied to the emulsion under stirring in step d).

[0291] The shear stress σ (expressed in Pa), the viscosity η of the composition C3 (expressed in Pa·s) and the shear rate γ (expressed in s) applied to the emulsion (E2) (under stirring in step d) are -1 ) is related by the following equation:

[0292] σ=ηγ

[0293] Thus, in this embodiment, the high viscosity of composition C3 allows very high shear stresses to be applied to the droplets of emulsion (E2) in the mixer, even if the shear rate is low and the shear is non-uniform.

[0294] To carry out step c) in this embodiment, generally any type of agitator can be used to form an emulsion, for example, a mechanical blade agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high pressure homogenizer, a colloid mill, a high shear disperser or a high speed homogenizer.

[0295] In a preferred embodiment, step c) is performed using a simple emulsifier such as a mechanical blade stirrer or a static emulsifier. This is possible because this embodiment does not require controlled shear or more than 1000 s -1 of shear.

[0296] Step d) of the process according to the invention comprises the crosslinking and thereby the formation of the shell of the solid microcapsules according to the invention.

[0297] This step allows achieving the expected retention properties of the capsules and ensures their thermodynamic stability by explicitly preventing any destabilization mechanisms such as agglomeration or ripening.

[0298] In one embodiment, when composition C2 comprises a photoinitiator, step d) is a photopolymerization step, whereby the emulsion (E3) is exposed to a light source capable of initiating photopolymerization of composition C2, in particular to a UV light source emitting preferably in a wavelength range between 100 nm and 400 nm, and in particular for a period of less than 15 minutes.

[0299] In this embodiment, step d) consists in subjecting the emulsion (E3) to photopolymerization, which will allow photopolymerization of the composition C2. This step will allow obtaining microcapsules encapsulating the water-soluble substance (as defined above).

[0300] In one embodiment, step d) comprises exposing the emulsion (E3) to a light source capable of initiating photopolymerization of the composition C2.

[0301] Preferably, the light source is an ultraviolet light source.

[0302] In one embodiment, the UV light source emits in a wavelength range between 100 nm and 400 nm.

[0303] In one embodiment, the emulsion (E3) is exposed to the light source for less than 15 minutes, preferably 5 to 10 minutes.

[0304] In step d), the shell of the above-mentioned double droplet consisting of the photocrosslinkable composition C2 is crosslinked and thereby transformed into a viscoelastic polymer shell which encapsulates and protects the water-soluble substance from release without mechanical triggering.

[0305] In another embodiment, when composition C2 does not contain a photoinitiator, step d) is a polymerization step without exposure to a light source, the length of the polymerization step d) is preferably 8 to 100 hours and / or the step d) is carried out at a temperature between 20°C and 80°C.

[0306] In this embodiment, polymerization is initiated, for example, by exposure to heat (thermal initiation) or by simple contact between monomer, polymer and crosslinker or by a catalyst. The polymerization time is typically greater than several hours.

[0307] Preferably, the polymerization step d) of composition C2 is carried out at a temperature ranging from 20°C to 80°C for a period ranging from 8 to 100 hours.

[0308] The composition obtained after step d) comprises solid microcapsules dispersed in composition C3 and is ready for use and can be used without subjecting the capsules to any additional post-treatment steps.

[0309] The thickness of the shell of the microcapsule thus obtained is usually 0.1 to 20 μm, preferably 0.2 to 8 μm, more preferably 0.2 to 5 μm.

[0310] In one embodiment, the solid microcapsules obtained after step d) are free of surfactant.

[0311] An advantage of the process of the invention is that no surfactant is required in any of the steps described. The process of the invention thus allows reducing the presence of additives that could modify the properties of the final product obtained after the release of the fragrance.

[0312] The invention also relates to the use of a composition as defined above for household cleaning.

[0313] The present invention also relates to the use of microcapsules as defined above for improving the olfactory and / or sensory properties of household cleaning compositions.

[0314] The invention also relates to the use of microcapsules as described above to reduce or even prevent the evaporation of the fragrance provided by the microcapsules.

[0315] Unless otherwise specified, “between and,” “from to,” and “in the range from to” are to be interpreted as inclusive limitations.

[0316] The following examples illustrate the invention without limiting its scope of protection.

Claims

1. A composition comprising: - at least one home care composition, and - at least one solid microcapsule with an average diameter of 1 to 30 μm, the solid microcapsule comprising: a core consisting of a composition C1 comprising at least one fragrance, said composition C1 being in the form of an emulsion, and a solid shell of a crosslinked polymer, which completely surrounds the core at the periphery thereof, said solid shell comprising a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive functional group selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups, Wherein, the thickness of the solid shell is 0.1-20 μm.

2. The composition according to claim 1, comprising a collection of solid microcapsules, each of which is a solid microcapsule as claimed in claim 1, and a standard deviation of a diameter size distribution of the microcapsules is less than 50% or less than 1 μm.

3. The composition according to claim 1 or 2, wherein The composition C1 of the core of the solid microcapsule comprises at least 20% by weight of fragrance relative to the total weight of the composition C1.

4. The composition according to any one of claims 1 to 3, wherein The composition C1 also comprises at least one aqueous gelling agent, preferably chosen from cellulose derivatives, polyacrylates, polyacrylamides, polyvinyl pyrrolidone and its derivatives, polyvinyl alcohol and its derivatives, poly(ethylene glycol), poly(propylene glycol) and its derivatives, polysaccharides, protein derivatives, polyurethanes and their derivatives, clays and silicates.

5. The composition according to claim 4, wherein The composition C1 is in the form of an emulsion comprising a continuous phase in the form of a hydrogel.

6. The composition according to any one of claims 1 to 5, wherein The crosslinked polymer is obtained by polymerizing a monomer or a polymer selected from aliphatic or aromatic esters or polyesters, carbamates or polyurethanes, anhydrides or polyanhydrides, sugars or polysaccharides, ethers or polyethers, amides or polyamides and carbonates or polycarbonates, and the monomer or polymer also has at least one reactive functional group selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate functional groups.

7. The composition according to any one of claims 1 to 6, wherein The cross-linked polymer is selected from the group consisting of cross-linked polyesters, cross-linked polyepoxides and cross-linked polyurethanes.

8. The composition according to any one of claims 1 to 7, wherein The crosslinked polymer of the shell of the solid microcapsule is obtained by polymerization of composition C2, which comprises at least one monomer or polymer having at least one reactive functional group as described in claim 1, at least one crosslinking agent and optionally at least one crosslinking photoinitiator or catalyst.

9. The composition according to any one of claims 1 to 8, wherein The solid microcapsules are obtained by a method comprising the following steps: a) adding, under stirring, the composition C1 as claimed in any one of claims 1 to 5 to the polymerized composition C2, the compositions C1 and C2 being immiscible with each other, The viscosity of composition C2 at 25° C. is 500 to 100,000 mPa·s, and is preferably greater than the viscosity of composition C1. Composition C2 comprises: - at least one monomer or polymer having at least one reactive functional group as claimed in claim 1, - at least one cross-linking agent, and - optionally at least one crosslinking photoinitiator or catalyst, An emulsion (E1) is then obtained comprising droplets of composition C1 dispersed in composition C2; b) adding the emulsion (E1) to the composition C3 under stirring, the compositions C2 and C3 being immiscible with each other, The viscosity of composition C3 at 25°5 is 500 to 100000 mPa·s, and is preferably greater than the viscosity of emulsion (E1), A double emulsion (E2) is then obtained comprising droplets dispersed in the composition C3; c) applying shear to the emulsion (E2), A double emulsion (E3) is then obtained comprising droplets of controlled size dispersed in the composition C3; and d) polymerizing composition C2, whereupon solid microcapsules dispersed in composition C3 are obtained.

10. Use of the composition according to any one of claims 1 to 9 for household care cleaning.

Images