Detergent composition with improved olfactory properties

Abstract

The present invention relates to a detergent composition having improved olfactory properties. The present invention relates to a composition for washing and / or caring for laundry, comprising: at least one composition for washing and / or caring for laundry, 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 and a solid shell of a cross-linked polymer, and a solid outer shell completely wrapping the core at the periphery of the core, the solid outer shell comprising a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive functional group, the at least one reactive functional group is selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioalkene, maleate, epoxy group, siloxane, amine, lactone, phosphate and carboxylate functional groups, and the solid shell has a thickness of 0.1-20 [mu] m.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of January 22, 2020, an application number of 202080010558.1, and an invention title of "Detergent Composition with Improved Olfactory Properties". Technical Field

[0002] The present invention relates to a composition, in particular a composition for detergents or for washing and / or caring for laundry, which comprises microcapsules and has improved olfactory properties. Background Art

[0003] Today, odor is one of the factors in laundry care products such as detergents and fabric softeners. The sensory characteristic that consumers like is that their clothes have a pleasant and fresh smell that lasts for a long time.

[0004] This level of olfactory performance is a real technical challenge for those in the field. In fact, on the one hand, fragrances are volatile substances and tend to evaporate rapidly in the detergent or fabric softener bottle before they can impart a pleasant smell to the laundry. On the other hand, it should be noted that fragrances are mostly hydrophobic and have a very low adhesion to laundry due to the presence of surfactants in laundry care products. Therefore, the fragrances contained in detergents or fabric softeners are largely lost due to evaporation or due to the washing process, and never adhere to the laundry and make it fragrant.

[0005] A major innovation in the twenty-first century to solve this problem is fragrance microcapsules. The polymer coating surrounding the fragrance in the microcapsules has multiple benefits. First, the polymer coating makes it possible to limit the evaporation rate of the fragrance. In addition, the affinity of the polymer coating for the materials constituting the fabric fibers allows the microcapsules to attach themselves to these fibers, thereby attaching the fragrance to the laundry. Finally, the microcapsules provide a long-lasting fragrance to the fabric because when the fabric is used, the microcapsules gradually break due to mechanical action, thereby gradually releasing the fragrance.

[0006] Therefore, microcapsules can improve the olfactory performance of detergents and fabric softeners while reducing the amount of fragrance contained in these products, thereby reducing their cost. However, in the face of increasingly strict environmental restrictions, manufacturers are now seeking to make their products biodegradable. Known microcapsules made of non-biodegradable microplastics are a major obstacle in this regard.

[0007] The main microcapsules for detergents and fabric softeners are produced by interfacial emulsion polymerization of formaldehyde-based compounds and melamine-based compounds. Such compositions for fabric washing and / or care products are described in detail, inter alia, in the following patent applications: US2013 / 0203642, US7119057, WO2015 / 031418, US2015 / 025231 and US2016 / 177241. These capsules have sufficient performance in protecting fragrances from evaporation and providing long-lasting fragrance, but they are not biodegradable.

[0008] Biodegradable alternatives have been developed, such as, for example, non-polymerized cellulose matrix microcapsules, polycaprolactone matrix microcapsules or polyvinylpyrrolidone matrix microcapsules, as described in particular in patent applications CN106614564 or US2015 / 265541. However, these microcapsules are very porous and their ability to protect against fragrance evaporation and fragrance on fabrics is insufficient.

[0009] Accordingly, there is a need in the art for biodegradable microcapsules while further improving their ability to provide fabrics with a long-lasting fragrance. Summary of the Invention

[0010] Accordingly, an object of the present invention is to provide a composition, in particular a composition for washing and / or caring for fabrics, which composition comprises biodegradable microcapsules and is capable of providing fabrics with a long-lasting pleasant odor.

[0011] Another object of the present invention is to provide a detergent product which provides fabrics with a long-lasting pleasant odor and shows less fragrance evaporation compared to currently available products containing microcapsules.

[0012] Another object of the present invention is to provide a biodegradable detergent product and to provide fabrics with a long-lasting pleasant odor.

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

[0014] - at least one composition for washing and / or caring for fabrics, and

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

[0016] - a core composed of a composition C1 containing at least one fragrance, and

[0017] - A solid crosslinked polymer coating that completely wraps the core around the periphery of the core, wherein the solid coating comprises a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, epoxy group, siloxane, amine, lactone, phosphate ester, and carboxylate moieties,

[0018] wherein the thickness of the solid coating is 0.1 - 20 μm, preferably 0.2 - 8 μm, more preferably 0.2 - 5 μm.

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

[0020] - At least one composition for washing and / or caring for fabrics, and

[0021] - At least one solid microcapsule having an average diameter of 1 - 30 μm, the solid microcapsule comprising:

[0022] - A core composed of a composition C1 containing at least one fragrance, wherein the composition C1 is in the form of an emulsion, and

[0023] - A solid crosslinked polymer coating that completely wraps the core around the periphery of the core, wherein the solid coating comprises a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester, and carboxylate moieties,

[0024] wherein the thickness of the solid coating is 0.1 - 20 μm, preferably 0.2 - 8 μm, more preferably 0.2 - 5 μm.

[0025] Surprisingly, the inventors have found that by associating the formulation of a detergent product (e.g., a detergent or fabric softener well-known in the prior art) with microcapsules made of a crosslinked polymer (e.g., crosslinked polyester, crosslinked polyepoxide, or crosslinked polyurethane), the resulting detergent product will have the following properties:

[0026] - It provides a long-lasting pleasant odor to the fabric;

[0027] - It shows less fragrance evaporation compared to products containing prior art microcapsules, and

[0028] - It is biodegradable.

[0029] The composition according to the invention combines a composition for washing and / or caring for fabrics which does not contain microcapsules (discussed in detail below) with biodegradable microcapsules having a core containing a fragrance.

[0030] According to the invention, the microcapsules do not contain a composition for washing and / or caring for fabrics. Specifically, the core of the microcapsules used according to the invention does not contain any fabric softener, detergent or any other such product.

[0031] Specifically, the invention includes the use of biodegradable microcapsules having a core containing a fragrance to improve the olfactory properties of fabric washing and / or caring compositions (e.g., detergents and fabric softeners).

[0032] Within the meaning of this application, "microcapsules" and "capsules" are synonyms.

[0033] Fabric washing and / or caring composition

[0034] As described above, the composition of the invention includes a composition for washing and / or caring for fabrics.

[0035] These fabric washing and / or caring compositions are selected from known compositions for the cleaning and maintenance of fabrics, but also for bleaching, wrinkle removal, softening, facilitating ironing or preventing wear or pilling.

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

[0037] Specifically, the composition for washing and / or caring for fabrics is a detergent composition, especially a detergent composition in liquid, powder or tablet form. Preferably, the fabric washing and / or caring composition according to the invention is a detergent composition, especially a primary detergent (fabric cleaning) composition or a fabric softener composition added to the rinse water, especially as described in the following patent applications: EP 1954793, WO2016 / 003699, US9284261 or WO2015 / 150124.

[0038] The primary washing composition may include a fabric softener, and the fabric softener added to the rinse water may include a surfactant, especially a nonionic surfactant compound.

[0039] The choice of surfactant compound and the amount present depend on the intended use of the detergent composition. In a composition for washing fabrics, as is well known to those skilled in the art, various surfactant systems can be selected to adapt to, for example, different types of fabrics or washing machines.

[0040] The total amount of surfactant contained will also depend on the intended end use and can be up to 60% by weight, for example, in a composition for hand-washing fabrics. In a composition for machine-washing fabrics, an amount of 5-40% by weight is usually suitable. Generally, relative to the total weight of the composition, the fabric washing and / or care composition used according to the invention contains at least 2% by weight of surfactant, preferably 2-60% by weight, especially 15-40% by weight and preferably 25-35% by weight.

[0041] Detergent compositions suitable for use in most automatic washing machines usually contain a soap-free anionic surfactant or a non-ionic surfactant, or a combination of the two in any suitable proportion, optionally containing soap.

[0042] In one embodiment, the fabric washing and / or care composition used according to the invention contains at least one surfactant, especially a surfactant selected from anionic, cationic, non-ionic, amphoteric and zwitterionic surfactants and mixtures thereof, especially as described in detail in the following documents: for example, "Surface Active Agents and Detergents", volumes I and II, edited by Schwartz, Perry and Berch ('Surfaces active[sic]Agents and Detergents', volumes I and II, Schwartz, Perry, and Berch).

[0043] In one embodiment, the fabric washing and / or care composition used according to the invention contains at least one anionic surfactant, especially an anionic surfactant selected from linear alkylbenzene sulfonates, especially linear alkylbenzene sulfonates having an alkyl chain length of C8-C16. Preferably, relative to the total weight of the composition, the surfactant content is 0-40 wt%, especially 1-25 wt%, more preferably 2-15 wt%.

[0044] Further examples of anionic surfactants include saturated or unsaturated basic fatty acid salts having 12-18 carbon atoms, sulfuric acid fatty alcohol semiesters salts having 12-18 carbon atoms, and sulfated products of the aforementioned non-ionic surfactants having a low degree of ethoxylation; primary and secondary alkyl sulfates, especially branched statistical primary C8-C15 alkyl sulfates; secondary C10-C18(2,3) alkyl sulfates; alkyl ether sulfates; sulfated fatty alcohol ethoxylates (FAE), preferably alkyl alkyl alkoxysulfates; C10-C18 alkyl alkyl alkoxycarboxylates; medium-chain branched alkyl sulfates; medium-chain branched alkyl alkoxysulfates; modified sodium alkylbenzenesulfonates; methyl ester sulfonates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and fatty acid sulfonates. Usually sodium salts are preferred.

[0045] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one nonionic surfactant.

[0046] Examples of nonionic surfactants include alkyl glycoside ethoxylates or propoxylates and / or primary and secondary alcohols, especially C8-C20 ethoxylated aliphatic alcohols and C10-C15 ethoxylated aliphatic primary alcohols having an average of 1-20 mol of ethylene oxide per mole of alcohol; C6-C12 alkylphenol alkoxylates, wherein the alkoxylate motif is a mixture of ethyleneoxy and propoxy units; C12-C18 alcohol and C6-C12 alkylphenol condensates condensed with alkyl polyamine ethoxylates having ethylene oxide / propylene oxide sequences; alkyl polysaccharides; polyhydroxy fatty acid amides; and alkoxylated ester surfactants such as fatty acid methyl ester ethoxylates (MEE).

[0047] Examples of nonionic surfactants also include non-ethoxylated nonionic surfactants such as alkyl glycosides, glycerol monoethers and polyhydroxyamides (gluconamides), ethoxylated and / or propoxylated products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides.

[0048] Relative to the total weight of the composition, the content of such surfactants in these compositions can be 0-40 wt%, preferably 1-25 wt%, more preferably 2-15 wt%.

[0049] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one amphoteric surfactant.

[0050] Examples of amphoteric surfactants include secondary and tertiary amine derivatives, secondary and tertiary heterocyclic amine derivatives, or quaternary ammonium derivatives, quaternary phosphonium derivatives or derivatives of tertiary sulfonate compounds such as betaines, including alkyl dimethyl betaines and coconut dimethylamidopropyl betaines, C8-C18 amine oxides, and thio and hydroxy betaines, for example, N-alkyl-N,N-dimethylamino-1-propane sulfonates, wherein one alkyl can be a C8-C18 or C10-C14 alkyl; water-soluble amine oxides, for example C10-C18 alkyl dimethyl amine oxides or C8-C12 alkoxyethyl dihydroxyethyl oxides.

[0051] In one embodiment, if the fabric washing and / or care composition is a fabric softener, the composition comprises at least one cationic softening compound for softening fabrics.

[0052] Examples of cationic softening compounds include cationic surfactants, such as quaternary ammonium salts, which have a water solubility in demineralized water at 20 °C of less than 1×10 -3 wt%, and contain a single long alkyl or alkenyl chain with an average length greater than or equal to C20; preferably, compounds containing a polar head group and two alkyl or alkenyl chains with an average chain length greater than or equal to C14. Preferably, these compounds have two long alkyl or alkenyl chains, each with an average length greater than or equal to C16. Preferably, at least 50% of the alkyl or alkenyl groups have a chain length of C18 or greater. Preferably, the long-chain alkyl or alkenyl groups are mainly linear. For example, distearyldimethylammonium chloride and bis(hydrogenated tallow alkyl)dimethylammonium, bis(sulfonyloxyethyl)dimethylammonium and / or its tallow analogues, triethanolamine (TEA quaternary) derivatives such as tallow N-methyl-N,N,N-triethanolamine diester or quaternary tallow ammonium chloride diester, or tallow methyl sulfate diester. Other examples include quaternium-18, chlorodimethylhydroxyethyl dodecylammonium, benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalkon B (C2-2 meta, para-dichlorobenzyl dimethylalkyl chloride), benzalkonium chloride, (2-hydroxyethyl)ammonium chloride, cetyltrimethylammonium bromide (N-hexadecyl-N,N-trimethylammonium bromide), phenethylammonium chloride, dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-hexadecylpyridinium chloride, benzalkonium chloride with C8-C22 alkyl residues, methyl-N-(2-hydroxyethyl)-N,N-bis(acyloxyethyl)methyl sulfate, bis(palmitoyl)ethylhydroxyethylmethyl sulfate or (2-hydroxyethyl)methyl-N,N-bis(acyloxyethyl)-N-methyl sulfate, and cationic polyamines.

[0053] Relative to the total weight of the composition, the content of such cationic softening compounds in these compositions can be 0.5 - 35 wt%, preferably 1 - 30 wt%, more preferably 3 - 25 wt%.

[0054] In one embodiment, if the fabric washing and / or care composition is a fabric softening composition, the composition contains at least one biodegradable cationic fabric softening compound, such as biodegradable quaternary ammonium-based materials, etc. 1,2-bis(hydrogenated sulfonyloxy)-3-trimethylpropane ammonium chloride, as described in US Patent Application US4137180. Preferably, these materials contain a small amount of the corresponding monoester, for example, hydrogenated sulfonyloxy-2-hydroxy-3-trimethylpropane ammonium chloride.

[0055] Examples of cationic fabric softening compounds also include alkylpyridinium salts, substituted imidazoline species, primary amines, secondary amines and tertiary amines, and condensation products of fatty acids and alkyl polyamines.

[0056] Based on the total weight of the composition, the content of such cationic compounds in these compositions can be 0.5 to 35 wt%, preferably 1 to 30 wt%, more preferably 3 to 25 wt%.

[0057] In one embodiment, if the fabric washing and / or care composition is a fabric softening composition, the composition comprises at least one water-soluble cationic fabric softening compound, as described in patent application GB2039556.

[0058] In one embodiment, if the fabric washing and / or care composition is a fabric softening composition, the composition comprises at least one non-ionic fabric softening compound, for example, lanolin and its derivatives, lecithin and other phospholipids.

[0059] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one stabilizer, especially for stabilizing the microcapsules.

[0060] Examples of stabilizers include any known components capable of suspending particles and / or regulating the rheology of liquid compositions, especially crystalline materials containing hydroxyl groups, polyacrylates, polycarboxylates, alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts, C12 - C20 fatty alcohols, dibenzylidene polyol (DBPA) acetate derivatives, cationic polymers comprising a first structural motif derived from methacrylamide and a second structural motif derived from diallyldimethylammonium chloride, and combinations thereof. Linear C8 - C22 alcohols alkoxylated with 10 - 20 mol of ethylene oxide, C10 - C20 alcohols, and mixtures thereof can also be used. Other stabilizers include, for example, the anti-flocculating polymers described in EP0415698 and EP0458599. Advantageously, the non-ionic stabilizer is a C8 - C22 straight-chain alcohol alkoxylated with 10 - 20 mol of ethylene oxide. Gums and other polysaccharides can 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, examples also include fatty acids and fatty waxes, for example, C8 - C24 mono-carboxylic acid alkyl or alkenyl acids and their polymers, castor oil and its derivatives. Preferably, saturated fatty acids are used, especially hydrogenated C16 - C18 tallow fatty acids. Preferably, the fatty acids are unsaponifiable, and more preferably, the fatty acids are free, for example, oleic acid, lauric acid, or tallow fatty acid.

[0061] Based on the total weight of the composition, the content of such stabilizers in these compositions can be 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 1 to 4 wt%.

[0062] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one inorganic additive that improves the washing performance of the product, for example, sodium carbonate, optionally in combination with a crystallization germ of calcium carbonate; amorphous crystalline aluminosilicates, such as zeolites, inorganic phosphates and polyphosphates such as sodium orthophosphate, pyrophosphate and tripolyphosphate.

[0063] Preferably, the content of such inorganic additives is 5 to 40 wt% relative to the total weight of the composition.

[0064] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one organic detergent additive such as polycarboxylic acids, especially citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid (malaric acid), fumaric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, especially methylglycine diacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and polyaspartic acid; polyphosphonic acids, especially aminotris(methylenephosphonic) acid, ethylenediaminetetra(methylenephosphonic) compounds; and polymeric acids, such as (poly)dextrin, polyacrylic acid, methacrylic acid, maleic acid and their polymer mixtures. All of the above acids are usually used in the form of their water-soluble salts, especially their basic salts.

[0065] Preferably, the amount of the organic detergent additive is 0.5 to 25 wt%, preferably 1 to 10 wt% relative to the total weight of the composition.

[0066] In one embodiment, the fabric washing and / or care composition used according to the present invention includes at least one monomeric polycarboxylic acid type organic detergent additive, such as citrate, gluconate, oxalosuccinate, glycerol monosuccinate, glycerol disuccinate and glycerol trisuccinate, carboxymethyloxysuccinate, carboxymethyloxypropanedioate, disilicates, hydroxyethyliminodiacetate, alkyl and alkenyl malonates and succinates, and sulfonated fatty acid salts.

[0067] 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.

[0068] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one peroxide bleaching compound capable of generating hydrogen peroxide in an aqueous solution, for example, an inorganic peroxysalt or an organic peroxyacid. Suitable peroxide bleaching compounds include organic peroxides (e.g., urea peroxide) and inorganic peroxysalts (e.g., alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, alkali metal persilicates, and alkali metal persulfates). Examples thereof include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, phthalimidoperoxycaproic acid, peroxybenzoic acid, hypohalite, peracetic acid, diperoxynonanoic acid, diperoxydodecanedioic acid, and an oxidase system or diperoxydiketone salts.

[0069] Preferably, relative to the total weight of the composition, the content of the hydrogen peroxide bleaching compound is 0.1 to 35 wt%, preferably 0.5 to 25 wt%.

[0070] In one embodiment, the fabric washing and / or care composition used according to the present invention includes 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, catalytic metal complexes, peroxycarboxylic acid precursors, more specifically, peracetic acid precursors and pernonanoic acid precursors, such as N,N,N',N'-tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (SNOBS), octanoyl caprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, benzoylvalerolactone, and methyl dodecylbenzyl acrylate. Similarly, peroxyacids can be used, such as iminoperoxycarboxylic peracid and phthalimidoperoxycaproic acid (PAP).

[0071] Preferably, relative to the total weight of the composition, the content of the bleach activator or precursor is 0.1 to 8 wt%, preferably 0.5 to 5 wt%.

[0072] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one bleach stabilizer (transition metal chelator) such as ethylenediaminetetraacetate (EDTA), polyphosphates such as Dequest(TM), and non-phosphate stabilizers such as EDDS (ethylenediaminedisuccinic acid).

[0073] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one enzyme, for example, proteases (especially subtilisin), cutinase, amylase, pullulanase, hemicellulase, cellulase, hemicellulase, mannanase, pectinase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase, lipase and peroxidase and mixtures thereof. Active enzyme substances obtained from the following fungi or bacteria are particularly suitable: for example, Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia. Optionally used enzymes may be adsorbed on a carrier substance and / or incorporated into an encapsulating substance to prevent premature inactivation.

[0074] Preferably, relative to the total weight of the composition, the content of such enzymes is about 0.1 wt% to about 3.0 wt%.

[0075] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one powder structuring agent, for example, fatty acids (or fatty acid soaps), sugars, acrylates or acrylate / maleic acid copolymers or sodium silicate.

[0076] Preferably, relative to the total weight of the composition, the content of the powder structuring agent is 1 to 5 wt%.

[0077] The fabric washing and / or care composition used according to the present invention may further comprise other additives such as soil release polymers, inorganic salts such as sodium sulfate or sodium hydroxide; colorants; and decoupling polymers.

[0078] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one free perfume, i.e., a non-encapsulated perfume. The perfumes are well-known to those skilled in the art and particularly include, for example, the perfumes mentioned in the following documents: S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J., 1969); S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960); the perfumes in the International Fragrance Association (IFRA) list (http: / / www.ifraorg.org / en / ingredients) and "Flavor and Fragrance Materials" published in 1991 (Allured Publishing Co., Wheaton, III., USA).

[0079] Preferably, relative to the total weight of the composition, the content of the free perfume is 0.1 to 5% by weight, preferably 0.2 to 3% by weight.

[0080] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one defoaming agent such as silicone oil or paraffin.

[0081] Preferably, relative to the total weight of the composition, the content of the defoaming agent is 0.05 to 4 wt%, preferably 0.1 to 3 wt%, more preferably 0.2 to 1 wt%.

[0082] In one embodiment, the fabric washing and / or care composition used according to the present invention includes at least one degreasing agent or anti-redeposition agent such as non-ionic cellulose ethers, for example, methyl cellulose; carboxymethyl cellulose; methyl hydroxypropyl cellulose; polymers of phthalic acid and / or terephthalic acid, especially ethylene terephthalate and / or polyethylene terephthalate polymers, or their anionic and / or non-ionic modified derivatives, and preferably, relative to the total weight of the composition, its content is 0 to 5% by weight.

[0083] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one color transfer inhibitor or anti-discoloration agent, for example, derivatives of polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridinium chloride, copolymers of vinylpyrrolidone and vinylimidazole polyethylene glycol and mixtures thereof. Preferably, the content thereof is 0 to 2 wt% relative to the total weight of the composition.

[0084] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one optical brightening agent, which may include any compound having fluorescence, including compounds that absorb ultraviolet light and re-emit light in the form of "blue" visible light. Such optical brightening agents include: stilbene, 4,4'-diaminostilbene, biphenyl, stilbene biphenyl derivatives, five-membered heterocycles (such as triazole, pyrazoline, oxazole, imidazole) or six-membered heterocycles (such as coumarin, naphthamide, s-triazine).

[0085] Preferably, the content of the optical brightening agent is 0 to 0.4 wt%, preferably 0.1 to 0.3 wt% relative to the total weight of the composition.

[0086] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises at least one non-aqueous solvent, for example, monohydric alcohols or polyhydric alcohols, alkanolamines or ethylene glycol ethers, 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, methyl propylene glycol, glycerol, diethylene glycol, propyl diethylene glycol, butyl diethylene glycol, 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, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol ether, tert-butyl ether, dioctyl ether and mixtures thereof.

[0087] Preferably, the content of such non-aqueous solvent is 0 to 25 wt%, preferably 1 to 20 wt%, more preferably 2 to 15 wt% relative to the total weight of the composition.

[0088] In one embodiment, the fabric washing and / or care composition used according to the present invention comprises water.

[0089] Solid microcapsules

[0090] As described above, the composition according to the present invention comprises at least one solid microcapsule as defined above.

[0091] Preferably, the composition according to the invention comprises a number of solid microcapsules, i.e. a series or a group of solid microcapsules, all of which are identical or different.

[0092] The microcapsules according to the invention are called "solid microcapsules" because of the solid nature of the crosslinked polymer envelope.

[0093] In one embodiment, the solid microcapsules according to the invention comprise a liquid (non-solid) core.

[0094] Considering the selection of specific monomers and polymers, the microcapsules used according to the invention are biodegradable.

[0095] Biodegradability is defined herein as the ability to degrade in a natural environment, for example, as defined in the OECD guidelines: OECD 301 (ready biodegradability), i.e. OECD 301A (dissolved organic carbon (DOC) disappearance); OECD 301B (CO 2 evolution test), OECD 301C (modified MITI test (I)); OECD 301D (closed bottle test); OECD 301E (modified OECD screening); OECD 301F (manometric respirometry) or OECD 304A (inherent biodegradability in soil), OECD 306 (biodegradability in sea water) and OECD 310 (ready biodegradability in sealed containers - CO 2 (headspace test)).

[0096] The microcapsules of the invention are characterized in that they have a core containing at least one fragrance, which is different from the fabric washing and / or care composition.

[0097] According to the invention, the above-mentioned fabric washing and / or care composition and the solid microcapsules (series or group of solid microcapsules) are different entities.

[0098] In one embodiment, the composition according to the invention comprises solid microcapsules, wherein each solid microcapsule is as defined above, and wherein the standard deviation of the microcapsule diameter distribution is less than 50% or less than 1.

[0099] The size distribution of the solid microcapsules can be measured, for example, by image analysis techniques under an optical microscope or by light scattering techniques using a Mastersizer 3000 (Malvern Instruments) equipped with a Hydro-SV measurement unit.

[0100] Composition C1

[0101] As described above, composition C1 is preferably in the form of an emulsion and thus comprises a continuous phase and a dispersed phase.

[0102] In one embodiment, relative to the total weight of composition C1, the composition of the core of the above solid microcapsules in composition C1 comprises at least 20 wt% of the fragrance, and relative to the total weight of composition C1, preferably 25 - 60 wt%, more preferably 30 - 50 wt%.

[0103] In one embodiment, composition C1 further comprises at least one gelling agent.

[0104] The gelling agent may be selected from water-soluble or water-dispersible polymers, especially aqueous polymers, and is preferably selected from the group consisting of:

[0105] - Cellulose derivatives, such as, cellulose ethers: methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose;

[0106] - Polyacrylates (also known as carbomers), such as, polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(hydroxyethyl methacrylate) (pHEMA), poly(N-2-hydroxypropyl methacrylate) (pHPMA);

[0107] - Polyacrylamides, such as, poly(N-isopropylacrylamide) (PNIPAM);

[0108] - Polyvinylpyrrolidone (PVP) and its derivatives;

[0109] - Polyvinyl alcohol (PVA) and its derivatives;

[0110] - Poly(ethylene glycol), poly(propylene glycol) and their derivatives, such as, poly(ethylene glycol) acrylate / methacrylate, poly(ethylene glycol) diacrylate / dimethacrylate, poly(propylene carbonate);

[0111] - Polysaccharides, such as, carrageenan, locust bean gum or tara gum, dextran, xanthan gum, chitosan, agarose, hyaluronic acid, gellan gum, guar gum, gum arabic, scutellaria gum, didan gum, oat gum, karaya gum, gatti gum, curdlan gum, pectin, konjac gum, starch;

[0112] - Protein derivatives, such as, gelatin, collagen, fibrin, polylysine, albumin, casein;

[0113] - Polyurethanes and their derivatives.

[0114] The gelling agent may also be selected from solid particulate matters that can be used as gelling agents when dispersed in water, such as clays, silica, and silicates.

[0115] As solid particles that can be used as gelling agents in Composition C1, mention may be made in particular of clays and silicates belonging to the class of phyllosilicates (also known 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, sodalite, nontronite, kaolinite, talc, sepiolite, chalkstone. Fumed silica can also be used. The above-mentioned clays, silicates, and silica can be advantageously modified by organic molecules, such as polyethers, ethoxylated amides, quaternary ammonium salts, long-chain diamines, long-chain esters, polyethylene glycols, and polypropylene glycols.

[0116] Preferably, the gelling agent is selected from cellulose derivatives, polyacrylates, derivatives of poly(ethylene glycol), and synthetic silica.

[0117] In one embodiment, Composition C1 contains 0.1 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, more preferably 0.5 wt% to 10 wt% of the gelling agent.

[0118] In one embodiment, Composition C1 contains 30 to 70 wt% of water, preferably 35 to 65 wt% of water, more preferably 35 to 60 wt% of water.

[0119] In one embodiment, Composition C1 further contains at least one surfactant, which is particularly selected from anionic, cationic, amphoteric, and nonionic surfactants. As surfactants, mention may be made of oxyethylated / oxypropylated block polymers, such as Poloxamer; sorbitan fatty acid esters and their oxyethylated derivatives, such as sorbitan monostearate, sorbitan monopalmitate, oxyethylated sorbitan stearate, palmitate, and oleate; polyethylene glycol derivatives and mixtures of glycerol esters of caprylic and capric acids (monoglycerides, diglycerides, triglycerides); alkyl glycosides, especially alkyl polyglucosides such as octyl / octyl glucoside or lauryl glucoside.

[0120] In one embodiment, composition C1 further comprises at least one hydrophobic corrector for the perfume. These reagents are hydrophobic materials with a cLogP greater than 4, preferably greater than 6, and have good compatibility with the perfume used. Examples of these reagents can include oils of monoglycerides, diglycerides and triglycerides, such as triglyceride caprylate / caprate; fatty acid esters of oligomers of polyglycerol, polyethylene glycol, propylene glycol and polybutylene glycol; nonionic fatty alcohol alkoxylates, such as isopropyl myristate, diethyl phthalate, dibutyl phthalate, diisodecyl adipate; mineral oil; silicone oils, such as polydimethylsiloxane and polydimethylcyclosiloxane; diethyl phthalate; polyalpha-olefins; castor oil.

[0121] 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 50 nm to 5 μm, preferably 100 nm to 3 μm, more preferably 100 nm to 1 μm.

[0122] Preferably, composition C1 is in the form of an emulsion, wherein the continuous phase is a hydrogel.

[0123] Preferably, the average diameter of the droplets of the emulsion is 50 nm to 5 μm, preferably 100 nm to 3 μm, more preferably 100 nm to 1 μm.

[0124] The inventors have found that a decisive parameter for limiting the evaporation of the flavoring agent in the microcapsules is the stability of the emulsion of composition C1 over time, i.e., the particle size distribution changes very little over time.

[0125] To achieve this stability, it is particularly advantageous to add a gelling agent as it can slow down the aggregation of the droplets of the emulsion.

[0126] Perfume

[0127] As described above, composition C1 comprises at least one perfume.

[0128] Thus, composition C1 according to the present invention can comprise a single perfume (or fragrance) or a mixture of several perfumes (or fragrances).

[0129] Examples of fragrances include all types of fragrances or flavorings; these terms are used synonymously herein. These fragrances or flavorings are well known to those skilled in the art and particularly include, for example, those mentioned in the following documents: S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J., 1969); S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960); fragrances in the International Fragrance Association (IFRA) list (http: / / www.ifraorg.org / en / ingredients) and "Flavor and Fragrance Materials" published in 1991 (Allured Publishing Co., Wheaton, III, USA).

[0130] The flavorings used in the present invention may include natural products such as extracts, essential oils, absolutes, resinoids, resins, concretes, etc.; and synthetic basic substances such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, alicyclic and heterocyclic compounds.

[0131] In one embodiment, relative to the total weight of the fragrance, the fragrance contains less than 10 wt% or less than 7.5 wt% of any compound having a ClogP below 2.1. In one embodiment, the fragrance does not contain a compound having a ClogP below 2.1.

[0132] Solid coating

[0133] In one embodiment, the aforementioned solid microcapsules comprise a solid coating consisting entirely of a crosslinked polymer as defined above.

[0134] The above solid coating comprises a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties.

[0135] Within the meaning of the present invention, the terms "monomer" or "polymer" include any basic unit suitable for forming a solid material by polymerization, whether alone or in combination with other monomers or polymers. The term "polymer" also includes oligomers.

[0136] In one embodiment, the crosslinked polymer is obtained by polymerization of monomers or polymers selected from: aliphatic or aromatic esters or polyesters, urethanes or polyurethanes, acid anhydrides or polyanhydrides, sugars or polysaccharides, ethers or polyethers, amides or polyamides, and carbonates or polycarbonates, said monomers or polymers further having at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy, siloxane, amine, lactone, phosphate ester, and carboxylate moieties.

[0137] Examples of such monomers or polymers include, but are not limited to, the following compounds and mixtures thereof:

[0138] - aliphatic or aromatic esters and polyesters, especially including polyglycolide (PGA), polylactic acid (PLA), poly(lactide-co-glycolide) (PLGA), poly(orthoesters) such as polycaprolactone (PCL), poly(p-dioxanone), poly(ethylene succinate), poly(butylene succinate) (PBS), poly(ethylene adipate), poly(butylene adipate), poly(ethylene sebacate), poly(butylene sebacate), polyvalerolactone (PVL), polydodecalactone, polyhydroxyvalerate, poly-β-poly(malic acid), poly-3-hydroxybutyrate (PHB), poly-3-hydroxybutyrate-co-3-hydroxyvalerate (P-3HB-3HV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate (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-hydroxyhexanoate), 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(alkanol alkylene esters), poly(dicarboxylic acid alkylene esters), poly(butylene adipate), poly(butylene adipate-co-terephthalate), poly(butylene carbonate), poly(butylene abietate), 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(p-dioxanone), poly(ethylene azelate), poly(ethylene carbonate), poly(ethylene sebacate), poly(ethylene furoate), 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), polydioxanone, poly(β-malonic acid), poly(β-lactide), poly(propylene succinate), poly(tetramethylene adipate-co-terephthalate), poly(tetramethylene carbonate), poly(trimethylene carbonate), poly(tetramethylene succinate)-co-(tetramethylene carbonate), poly(trimethylene adipate), poly(dimethylene adipate-co-diterephthalate), poly(tetramethylene adipate), poly(tetramethylene glycol tetra-methyl ester), poly(butylene succinate), poly(valerolactone), which further has at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester and carboxylate moiety;

[0139] - Acid anhydride or polyanhydride family, for example, derived from polysebacic acid, polyadipic acid, polyterephthalic acid, poly(bis(p-carboxyphenoxy) alkanoic acid); or more broadly derived from the polyanhydride family, for example, as described in Advanced Drug Delivery Reviews 54 (2002) pages 889 - 910, which further has at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester and carboxylate moiety;

[0140] - Carbohydrates and polysaccharide family, especially including carrageenan; dextran; cyclodextrin (e.g., hyaluronic acid); agarose; chitosan; chitin; sodium alginate; starch; cellulose and its derivatives, for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or methyl hydroxypropyl cellulose, which further has at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester and carboxylate moiety;

[0141] - Ether and polyether family, especially including polyethylene glycol, which further has at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester and carboxylate moiety; and

[0142] -Amides and polyamide families, especially including poly(ester amides) or poly(terephthalamides), also have at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester and carboxylate moieties;

[0143] -Polyurethane series, especially including reaction products of polyols and polyisocyanates, and the reaction products also include at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester and carboxylate moieties. Examples of the above polyols include 1,4-butanediol, 1,2-propanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, methylpropanediol, bisphenol A, polyoxypropylene glycol, polybutadiene glycol, oxytetramethylene glycol, ethylene glycol adipate glycol, polyethylen adipate propanediol, polyadipic acid diethylene glycol glycol, polyadipic acid diethylene glycol - diethylene glycol ester ester glycol, pentaerythritol, glycerol, trimethylolpropane, triethylolpropane or oxypropanetriol. Examples of the above polyisocyanates include hexamethylene diisocyanate derivatives, methylene dicyclohexyl diisocyanate derivatives or isophorone diisocyanate derivatives.

[0144] In a preferred embodiment, the crosslinked polymer is selected from crosslinked polyesters, crosslinked polyepoxides and crosslinked polyurethanes.

[0145] Preferably, the crosslinked polymer of the coating of the solid microcapsules is obtained from polymerization composition C2, which includes at least one monomer or polymer having at least one reactive moiety as described above, at least one crosslinking agent and optionally at least one crosslinking photoinitiator or catalyst.

[0146] "Crosslinking agent" refers to a compound that can crosslink at least two reactive moieties of monomers or polymers or a mixture of monomers and polymers during polymerization.

[0147] The crosslinking agent can be selected from molecules having at least two identical or different moieties selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester, carboxylate moieties.

[0148] Examples of the crosslinking agent especially include:

[0149] - Diacrylates, such as 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 - methacryloyloxyethyl) N,N'-1,9 - nonanedicarboxylate, 1,4 - butanediol diacrylate, 1,5 - pentanediol dimethacrylate, allyl methacrylate, N,N’ - diol methylene bisacrylamide, 2,2 - bis[4-(2 - hydroxy - 3 - methacryloyloxypropoxy)phenyl]propane, tetraethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, N,N - diallylacrylamide or glycidyl methacrylate;

[0150] - Polyfunctional acrylates, such as pentaerythritol pentaacrylate, 1,1,1 - trimethylolpropane triacrylate, 1,1,1 - trimethylolpropane trimethacrylate, ethylenediamine tetramethacrylate, pentaerythritol triacrylate or pentaerythritol tetraacrylate; and

[0151] - Acrylates having another reactive moiety, such as propargyl methacrylate, N - acryloxysuccinimide, N-(2 - hydroxypropyl)methacrylamide, N-(tert - butoxycarbonyl - aminopropyl)methacrylamide, monoacryloyloxyethyl phosphate, acrylic anhydride, 2-(tert - butylamino)ethyl methacrylate, N,N - diallylacrylamide or glycidyl methacrylate.

[0152] "Photoinitiator" refers to a compound that can be cleaved under the action of light radiation.

[0153] Photoinitiators that can be used according to the present invention are known in the prior art and are described, for example, in the following document: "Les photoinitiateurs dans la réticulation des ”, G. Li Bassi, Double Liaison–Chimie des Peintures, No. 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, J. M. Abadie, Double Liaison–Chimie des Peintures, Nos. 435-436, 1992, pp. 28-34.

[0154] These photoinitiators include:

[0155] - α-hydroxy ketones, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone, which is sold by BASF under the trade names 1173 and 4265, 184, 2959 and 500, and by CYTEC under CPK;

[0156] - α-amino ketones, especially 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, for example, those sold by BASF under the trade names 907 and 369;

[0157] - aromatic ketones, such as the aromatic ketone sold by LAMBERTI under the trade name TZT; or thioxanthone sold by LAMBERTI under the trade name ITX, and quinones. Most of these aromatic ketones require the presence of a hydrogen donor compound such as a tertiary amine (especially an alkanolamine). The tertiary amine sold by LAMBERTI under the trade name EDB can be specifically mentioned.

[0158] - α-dicarbonyl derivatives, the most representative of which is benzyl dimethyl ketal sold by BASF under the trade name 651. Other commercial products are sold by LAMBERTI under the trade name KB1; and

[0159] - acylphosphine oxides, such as those sold by BASF under the trade name 819, 1700, and 1800; 4265; TPO and bisacylphosphine oxide (BAPO) sold as TPO-L.

[0160] Other examples of photoinitiators include aromatic ketones such as benzophenone, phenylglyoxylates such as methyl phenylglyoxylate, oxime esters such as [1-(4-phenylsulfonylbenzoyl)heptylimino]benzoate, sulfonates, iodonium salts, and oxime sulfonates.

[0161] Preparation of Microcapsules

[0162] In one embodiment, solid microcapsules are obtained by a method comprising the following steps:

[0163] a) Adding composition C1 as described above to a polymer composition C2 with stirring, wherein compositions C1 and C2 are immiscible,

[0164] wherein the viscosity of composition C2 at 25 °C is 500 - 100000 mPa·s and is preferably greater than the viscosity of composition C1,

[0165] wherein said composition C2 comprises:

[0166] - at least one monomer or polymer having at least one reactive moiety as described above,

[0167] - at least one crosslinking agent, and

[0168] - optionally at least one crosslinking photoinitiator or catalyst,

[0169] to obtain an emulsion (E1) comprising droplets of composition C1 dispersed in composition C2;

[0170] b) Adding the emulsion (E1) to composition C3 with stirring, wherein compositions C2 and C3 are immiscible,

[0171] wherein the viscosity of composition C3 at 25 °C is 500 - 100000 mPa·s and is preferably greater than the viscosity of the emulsion (E1),

[0172] to obtain a double emulsion (E2) comprising droplets dispersed in composition C3;

[0173] c) Applying shear stress to the emulsion (E2),

[0174] to obtain a double emulsion (E3) comprising droplets of controlled size dispersed in composition C3; and

[0175] d) Polymerizing the composition C2,

[0176] Obtain solid microcapsules dispersed in composition C3.

[0177] The above method includes forming a double emulsion composed of droplets containing at least one fragrance, which is surrounded by a crosslinkable liquid phase. These double droplets are made monodisperse in size before being transformed into rigid capsules by crosslinking or polymerization. The preparation includes four steps, which will be described in detail below.

[0178] In one embodiment, the method according to the present invention includes a preliminary step of preparing composition C1 in the form of an emulsion before the aforementioned step a).

[0179] In this step, composition c1 containing the fragrance is added to hydrophilic composition c2, and this step is carried out under stirring, which means that when adding composition c1 containing the fragrance, composition c1 is usually mechanically stirred to emulsify the mixture of composition c1.

[0180] During this step, composition c1 containing the fragrance is at a temperature between 0 and 100 °C, preferably between 10 and 80 °C, more preferably between 15 and 60 °C. During this step, hydrophilic composition c2 is at a temperature between 0 and 100 °C, preferably between 10 and 80 °C, more preferably between 15 and 60 °C.

[0181] To carry out this step, any type of stirrer commonly used for forming emulsions can be used, such as 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.

[0182] In one embodiment, hydrophilic composition c2 contains a gelling agent.

[0183] In another embodiment, once composition C1 containing the fragrance is emulsified in hydrophilic composition c2, a gelling agent is added to composition C1. In this embodiment, to add the gelling agent to composition C1, any type of stirrer used for homogenizing the solution can be used, such as a mechanical blade stirrer at a low rotation speed.

[0184] Step a) of the method according to the present invention includes preparing a first emulsion (E1).

[0185] The first emulsion consists of a dispersion of droplets of composition C1 (containing at least one fragrance) in polymer composition C2, and is formed by adding C1 dropwise to C2 under stirring, and the polymer composition C2 is not miscible with C1.

[0186] In step a), composition C1 is added to crosslinkable polymer composition C2, and this step is carried out under stirring, which means that composition C2 is usually mechanically stirred when adding composition C1 so as to emulsify the mixture of compositions C1 and C2.

[0187] The addition of composition C1 to composition C2 is usually carried out drop by drop.

[0188] During step a), composition C1 is at a temperature between 0 and 100, preferably between 10 and 80, more preferably between 15 and 60. During step a), composition C2 is at a temperature between 0 and 100, preferably between 10 and 80, more preferably between 15 and 60.

[0189] 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.

[0190] Therefore, when composition C1 contacts composition C2 under stirring, the latter is dispersed in the form of drops ("single drops").

[0191] The immiscibility of compositions C1 and C2 also makes it possible to avoid the migration of the active ingredient of composition C1 into composition C2.

[0192] Composition C2 is stirred to form an emulsion containing droplets of composition C1 dispersed in composition C2. Such an emulsion is also called a "simple emulsion", or a C1-in-C2 emulsion.

[0193] To carry out step a), any type of stirrer commonly used for forming emulsions can be used, such as 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.

[0194] Composition C2 will ultimately form the solid film of the microcapsules.

[0195] The volume fraction of C1 in C2 can vary between 0.1 and 0.6 to control the coating thickness of the capsules produced by this method.

[0196] In one embodiment, the volume ratio of composition C1 to composition C2 varies between 1:10 and 10:1. Preferably, this volume ratio is between 1:3 and 5:1, more preferably between 1:3 and 3:1.

[0197] Preferably, the viscosity of composition C2 at 25 °C is between 1000 mPa·s and 50000 mPa·s, more preferably between 2000 mPa·s and 25000 mPa·s, for example, between 3000 mPa·s and 15000 mPa·s.

[0198] Preferably, the viscosity of composition C2 is greater than the viscosity of composition C1.

[0199] The viscosity is measured using a Haake Rheostress TM 600 rheometer equipped with a cone having a diameter of 60 mm and an angle of 2 degrees; the temperature control unit is set at 25 °C. The viscosity value is read at a shear rate of 10 s -1 .

[0200] In this embodiment, the destabilization kinetics of the emulsion (E1) droplets are significantly low, which allows the encapsulation of the microcapsules to polymerize in step d) before the emulsion destabilizes. Once the polymerization is complete, it provides thermodynamic stability. Thus, the relatively high viscosity of composition C2 ensures the stability of the emulsion (E1) obtained after step a).

[0201] Preferably, the interfacial tension between compositions C1 and C2 is low. Generally, these interfacial tensions vary between 0 mN / m and 50 mN / m, preferably between 0 mN / m and 20 mN / m.

[0202] The low interfacial tension between compositions C1 and C2 also advantageously allows ensuring the stability of the emulsion (E1) obtained after step a).

[0203] 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) such that the composition is crosslinkable.

[0204] In one embodiment, relative to the total weight of composition C2, composition C2 comprises 50 to 99 wt% of the monomer or polymer as defined above or a mixture of monomers or polymers as defined above.

[0205] In one embodiment, relative to the total weight of composition C2, composition C2 comprises 1 to 20 wt% of the crosslinking agent or mixture of crosslinking agents as defined above.

[0206] In one embodiment, relative to the total weight of composition C2, composition C2 comprises 0.1 to 5 wt% of the photoinitiator or mixture of photoinitiators as defined above.

[0207] In one embodiment, the composition C2 contains 0.001 to 20 wt% of a crosslinking agent, relative to the total weight of the composition.

[0208] In one embodiment, the composition C2 may further comprise additional monomers or polymers capable of improving the properties of the microcapsule envelope and / or imparting new properties to the microcapsule envelope.

[0209] Examples of these additional monomers or polymers include monomers or polymers having groups sensitive to pH, temperature, UV or IR.

[0210] These additional monomers or polymers can induce the rupture of solid microcapsules upon stimulation (e.g., by pH, temperature, UV or IR) and thus release their contents.

[0211] These additional monomers or polymers can be selected from monomers or polymers carrying at least one of the following groups:

[0212] - pH-sensitive groups, such as primary amines, secondary amines or tertiary amines; carboxylic acids; phosphate esters, sulfates, nitrates or carbonate groups;

[0213] - UV-sensitive or UV-cleavable groups (or photochromic groups), such as azobenzene, spiropyran, 2-diazo-1,2-naphthoquinone, o-nitrobenzyl, thiols or 6-nitro-veratryloxycarbonyl, e.g., poly(ethylene oxide)-block-poly(2-nitrobenzyl methacrylate) and other block copolymers, e.g., especially the block copolymers described in: Liu et al., Polymer Chemistry 2013, 4, 3431-3443;

[0214] - IR-sensitive or IR-cleavable groups, such as o-nitrobenzyl or 2-diazo-1,2-naphthoquinone, e.g., the polymers described in Liu et al., Polymer Chemistry 2013, 4, 3431-3443;

[0215] - Hydrolysis-sensitive groups, such as polylactic acid, polyglycolic acid, poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxybutyrate, chitosan, dextran, agarose, cellulose and derivatives of these compounds; and

[0216] - Temperature-sensitive groups, such as poly(N-isopropylacrylamide).

[0217] Step b) of the method according to the invention comprises preparing a second emulsion (E2).

[0218] The second emulsion consists of a dispersion of the first emulsion droplets in a composition C3 that is immiscible with C2, and this composition is produced by dropwise adding the emulsion (E1) to C3 under stirring.

[0219] 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.

[0220] Under the addition conditions of step b), the compositions C2 and C3 are immiscible, which means that, relative to the total weight of the composition C3, the amount (by weight) of the composition C2 soluble in the composition C3 is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%; and relative to the total weight of the composition C2, the amount (by weight) of the composition C3 soluble in the composition C2 is less than or equal to 5%, preferably less than 1%, more preferably less than 0.5%.

[0221] Thus, when the emulsion (E1) comes into contact with the composition C3 by stirring, the latter is dispersed in the form of droplets ("double droplets"); the dispersion of these emulsion droplets (E1) in the continuous phase C3 is called the emulsion (E2).

[0222] Typically, the double droplets formed in step b) correspond to the single droplets of the composition C1 as described above, surrounded by an envelope of the composition C2 that completely encloses the single droplet.

[0223] The double droplets formed in step b) can also include at least two single droplets of the composition C1, with the single droplets surrounded by an envelope of the composition C2 that completely encloses the single droplets.

[0224] Thus, the said double droplets include a core composed of one or more single droplets of the composition C1 and a layer of the composition C2 surrounding the core.

[0225] The resulting emulsion (E2) is generally a double polydisperse emulsion (C1-in-C2-in-C3 or C1 / C2 / C3 emulsion), which means that the double droplets do not have a clear particle size distribution in the emulsion (E2).

[0226] The fact that the compositions C2 and C3 are immiscible makes it possible to avoid the mixing of the layers of the compositions C2 and C3 and also ensures the stability of the emulsion (E2).

[0227] The fact that the compositions C2 and C3 are immiscible also prevents the water-soluble substances of the composition C1 from migrating from the droplet core to the composition C3.

[0228] For performing step b), any type of stirrer commonly used for forming emulsions can 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.

[0229] In one embodiment, the viscosity of composition C3 at 25 °C is greater than the viscosity of emulsion (E1) at 25 °C.

[0230] According to the present invention, the viscosity of composition C3 at 25 °C is 500 to 100,000 mPa·s.

[0231] Preferably, the viscosity of composition C3 at 25 °C is 3,000 to 100,000 mPa·s, more preferably 5,000 to 80,000 mPa·s, for example, 7,000 to 70,000 mPa·s.

[0232] In this embodiment, in view of the very high viscosity of the continuous phase formed by composition C3, the destabilization rate of the double-droplet emulsion (E2) is rather slow relative to the duration of the method according to the present invention. Therefore, the kinetic stability of emulsions (E2) and (E3) is allowed until the capsule envelope is completely polymerized. Once polymerized, the capsule is thermodynamically stable.

[0233] Therefore, the very high viscosity of composition C3 ensures the stability of the emulsion (E2) obtained in step b).

[0234] The low surface tension between composition C3 and the first emulsion and the high viscosity of the system contribute to ensuring the kinetic stability of the double emulsion (E2), thereby preventing it from demixing during the production method.

[0235] Preferably, the interfacial tension between compositions C2 and C3 is low. The low interfacial tension between compositions C2 and C3 also advantageously enables the stability of the emulsion (E2) obtained in step b) to be ensured.

[0236] The volume fraction of the first emulsion in C3 can vary between 0.05 and 0.5 in order to increase production performance on the one hand and change the average diameter of the capsules on the other hand. At the end of this step, the particle size distribution of the second emulsion is relatively wide.

[0237] In one embodiment, the ratio of the volume of emulsion (E1) to the volume of composition C3 varies between 1:10 and 10:1. Preferably, this ratio is 1:9 to 3:1, more preferably 1:9 to 1:1.

[0238] In one embodiment, composition C3 further comprises at least one branched polymer (preferably having a molecular weight greater than 5000 g·mol -1(molecular weight) and / or at least one polymer (having a molecular weight greater than 5000 g·mol -1 (molecular weight) and / or solid particles such as silicates.

[0239] In one embodiment, composition C3 comprises at least one branched polymer, preferably having a molecular weight greater than 5000 g·mol -1 , preferably 10,000 - 500,000 g·mol -1 , such as 50,000 - 300,000 g·mol -1 (molecular weight).

[0240] “Branched polymer” means a polymer having at least one branching point between its two end groups; a “branching point” is a point on the chain at which a side chain (also called a “dangling chain”) is attached.

[0241] Examples of branched polymers include graft polymers, comb polymers, star polymers or dendrimers.

[0242] In one embodiment, composition C3 comprises at least one branched polymer having a molecular weight greater than 5000 g·mol -1 , preferably 10,000 - 500,000 g·mol -1 , such as 50,000 - 300,000 g·mol -1 .

[0243] Examples of polymers that can be used in composition C3 include the following compounds used alone or in admixture with each other:

[0244] - Cellulose derivatives, e.g., cellulose ethers: methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or methyl hydroxypropyl cellulose;

[0245] - Polyacrylates (also known as carbomers), e.g., polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(2-hydroxyethyl methacrylate) (pHEMA), poly(N - 2 - hydroxypropyl methacrylamide) (phpma);

[0246] - Polyacrylamides, e.g., poly(N - isopropylacrylamide) (PNIPAM);

[0247] - Polyvinylpyrrolidone (PVP) and its derivatives;

[0248] - Polyvinyl alcohol (PVA) and its derivatives;

[0249] - Polyethylene glycol, polypropylene glycol and their derivatives, for example, poly(ethylene glycol) acrylate / methacrylate, poly(ethylene glycol) diacrylate / dimethacrylate, polypropylene carbonate;

[0250] - Polysaccharides, for example, carrageenan, locust bean gum or tara gum, dextran, xanthan gum, chitosan, agarose, hyaluronic acid, gellan gum, guar gum, gum arabic, scutellaria gum, didan gum, oat gum, karaya gum, gatti gum, curdlan gum, pectin, konjac gum, starch;

[0251] - Protein derivatives, for example, gelatin, collagen, fibrin, polylysine, albumin, casein;

[0252] - Silicone derivatives, for example, polydimethylsiloxane (also known as dimethylsiloxane), alkylsiloxane, arylsiloxane, alkylarylsiloxane, polyethylene glycol dimethylsiloxane, propylene glycol dimethylsiloxane;

[0253] - Waxes, for example, diester waxes (alkanediol diesters, hydroxycarboxylic acid diesters), triester waxes (triglycerides; alkan-1,2-diol, ω-hydroxycarboxylic acid and fatty acid triesters; hydroxypropanedioic acid, fatty acid and alcohol esters; hydroxy fatty acid, fatty acid and fatty alcohol triesters; fatty acid, hydroxy fatty acid and diol triesters) and polyester waxes (fatty acid polyesters). Examples of fatty acid esters that can be used as waxes in the present invention include cetyl palmitate, cetyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, cetyl stearate, stearyl stearate, stearyl myristate, cetyl myristate, isocetyl stearate, trimyristin, tripalmitin, glycerol monostearate or glyceryl palmitate and cetyl palmitate;

[0254] - Fatty acids that can be used as waxes are, for example, cerotic acid, palmitic acid, stearic acid, dihydroxystearic acid, behenic acid, lignoceric acid, arachidic acid, myristic acid, lauric acid, tridecylic acid, pentadecylic acid, heptadecylic acid, nonadecylic acid, heneicosylic acid, tridecylic acid, pentacosylic acid, heptacosylic acid, octacosylic acid or nonacosylic acid;

[0255] - Fatty acid salts, especially aluminum fatty acid salts, for example, aluminum stearate, aluminum hydroxybis(2-ethylhexanoate);

[0256] - Isomerized jojoba oil;

[0257] - Hydrogenated sunflower oil;

[0258] - Hydrogenated coconut oil;

[0259] - Hydrogenated lanolin oil;

[0260] - Castor oil and its derivatives, especially modified hydrogenated castor oil or compounds obtained by esterification of castor oil with fatty alcohols;

[0261] - Polyurethanes and their derivatives;

[0262] - Styrene polymers such as styrene - butadiene; and

[0263] - Polyolefins such as polyisobutene.

[0264] In one embodiment, composition C3 comprises solid particles such as clay, silica, and silicates.

[0265] Examples of solid particles that can be used in composition C3 include clay and silicates, especially clays and silicates of the phyllosilicate (also known as sheet silicate) category. Examples of silicates that can be used in the present invention include bentonite, laponite, attapulgite, sepiolite, montmorillonite, saponite, sodalite, nontronite, kaolinite, talc, sepiolite, and chalkstone. Fumed silica can also be used. The above - mentioned clays, silicates, and silica can be advantageously modified by organic molecules, for example, polyethers, ethoxylated amides, quaternary ammonium salts, long - chain diamines, long - chain esters, polyethylene glycols, and polypropylene glycols.

[0266] These particles can be used alone or in combination.

[0267] In one embodiment, composition C3 comprises at least one polymer having a molecular weight greater than 5000 g·mol -1 and solid particles. Any mixture of the above - mentioned compounds can be used.

[0268] Step c) of the method of the present invention comprises adjusting the droplet size of the second emulsion (E2).

[0269] This step can include applying a controlled and uniform shear stress to the emulsion (E2), with the applied shear rate being between 10 s -1 and 100000 s -1 .

[0270] In one embodiment, the polydisperse double droplets obtained in step b) are size - adjusted, thereby subjecting them to a shear stress capable of fragmenting them into new double droplets of a controlled and uniform diameter. Preferably, the shear step is carried out using a Couette - type high - shear unit according to the method described in patent application EP15306428.2.

[0271] In one embodiment, in step c), the second emulsion (E2) obtained from step b) consists of polydisperse double droplets dispersed in a continuous phase and is subjected to shear in a mixer with controlled and uniform shear.

[0272] Thus, in the present embodiment, step c) includes applying a controlled and uniform shear to the emulsion (E2), and the applied shear rate is between 1000 s -1 and 100000 s -1 .

[0273] In the present embodiment, in a mixer, 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), the shear rate is said to be controlled and uniform, regardless of the time length. The exact configuration of the mixer is not necessary in the present invention, provided that when output from the device, the entire emulsion is subjected to the same maximum shear. A mixer suitable for performing step c) is specifically described in the document US 5938581.

[0274] Controlled and uniform shear can be performed when the second emulsion circulates in a unit formed by:

[0275] - Two concentric rotating cylinders (also called a Couette type mixer);

[0276] - Two parallel rotating disks; or

[0277] - Two parallel oscillating plates.

[0278] In the present embodiment, the shear rate applied to the second emulsion is between 1000 s -1 and 100000 s -1 , preferably between 1000 s -1 and 50000 s -1 , more preferably between 2000 s -1 and 20000 s -1 .

[0279] In the present embodiment, in step c), the second emulsion is input into a mixer and subjected to shear, which results in a shear stress for forming a third emulsion. The third emulsion (E3) is chemically the same as the second emulsion (E2), but consists of monodisperse double droplets, while the emulsion (E2) consists of polydisperse double droplets. The third emulsion (E3) typically consists of a dispersion of double droplets, the dispersion of double droplets includes a core composed of one or more droplets of composition C1 and a layer of composition C2 wrapping the core, and the double droplets are dispersed in composition C3.

[0280] The difference between the second emulsion and the third emulsion lies in the size variation of the double droplets: due to the above-mentioned fragmentation mechanism, the size of the second emulsion droplets is polydisperse, while the size of the third emulsion droplets is monodisperse.

[0281] Preferably, in the present embodiment, the second emulsion is continuously added to the mixer, which means that the amount of the double emulsion (E2) input at the mixer inlet is the same as the amount of the third emulsion (E3) output at the mixer outlet.

[0282] Since the size of the emulsion droplets (E3) substantially corresponds to the size of the solid microcapsule droplets after polymerization, the size of the microcapsules and the thickness of the coating can be adjusted by adjusting the shear rate in step c). There is a strong correlation between the decrease in droplet size and 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).

[0283] In a preferred embodiment, the mixer used in step c) is a Couette-type mixer, which includes two concentric cylinders, an outer cylinder with an inner diameter of R o and an inner cylinder with an outer diameter of R i . The outer cylinder is fixed, and the inner cylinder rotates at an angular velocity ω.

[0284] The Couette-type mixer suitable for the method of the present invention can be provided by T.S.R. France.

[0285] In one embodiment, the angular velocity ω of the inner rotating cylinder of the Couette-type mixer is greater than or equal to 30 rad·s -1 .

[0286] For example, the angular velocity ω of the inner rotating cylinder of the Couette-type mixer is about 70 rad·s -1 .

[0287] The size of the outer fixed cylinder of the Couette-type mixer can be used to adjust the space between the inner rotating cylinder and the outer fixed cylinder (d = R o - R i ).

[0288] In one embodiment, the space (d = R o - R i ) between the two concentric cylinders of the Couette-type mixer is 50 - 1000 μm, preferably 100 - 500 μm, for example, 200 - 400 μm.

[0289] For example, the distance d between the two concentric cylinders is 100 μm.

[0290] In the present embodiment, in step c), the second emulsion is usually input into the mixer by a pump and is guided into the space between the two concentric cylinders. The outer cylinder is fixed, and the inner cylinder rotates at an angular velocity ω.

[0291] When the double emulsion is located between two cylindrical barrels, the shear rate applied to said emulsion is given by the following formula:

[0292]

[0293] Where:

[0294] - ω is the angular velocity of the inner rotating cylindrical barrel;

[0295] - R o is the inner diameter of the fixed outer cylindrical barrel; and

[0296] - R i is the outer diameter of the inner rotating cylindrical barrel.

[0297] In another embodiment, when the viscosity of composition C3 at 25 °C is greater than 2000 mPa·s, step C) includes applying a shear rate of less than 1000 s -1 to the emulsion (E2).

[0298] In this embodiment, the fragmentation step c) can be carried out using any type of mixer commonly used for forming emulsions at a shear rate of less than 1000 s -1 In this case, under the conditions described in patent application FR 1661787, the viscosity of composition C3 is greater than 2000 mPa·s.

[0299] The geometric characteristics of the double droplets formed at the end of this step will determine the geometric characteristics of the future capsules.

[0300] In this embodiment, in step c), an emulsion (E2) composed of polydisperse droplets dispersed in a continuous phase is subjected to shear stress, for example, in a mixer, at a low shear rate of less than 1000 s -1 .

[0301] In this embodiment, for example, the shear rate applied in step c) is 10 s -1 ~1000 s -1 .

[0302] Preferably, the shear rate applied in step c) is strictly less than 1000 s -1 .

[0303] In this embodiment, only by applying a high shear stress to the emulsion droplets (E2) can the droplets of emulsion (E2) be effectively broken into fine monodisperse emulsion droplets (E3).

[0304] The shear stress σ applied to the droplets of emulsion (E2) is defined as the tangential force per unit droplet surface area, which is generated by the macroscopic shear applied to the emulsion under stirring in step d).

[0305] The shear stress σ (expressed in Pa), the viscosity η of composition C3 (expressed in Pa·s), and the shear rate γ (expressed in s -1 -1) applied to the emulsion (E2) (under stirring in step d) are related by the following equation:

[0306] σ = ηγ

[0307] Thus, in this embodiment, the high viscosity of composition C3 allows a very high shear stress to be applied to the droplets of the emulsion (E2) in the mixer, even when the shear rate is low and the shear is non-uniform.

[0308] To carry out step c) in this embodiment, any type of stirrer can generally be used to form the emulsion, 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.

[0309] In a preferred embodiment, a simple emulsifier such as a mechanical blade stirrer or a static emulsifier is used to carry out step c). Indeed, this is possible because this embodiment does not require controlled shear or shear greater than 1000 s -1 -1.

[0310] Step d) of the method of the present invention includes crosslinking and thereby forming the coating of the solid microcapsules according to the present invention.

[0311] This step allows the desired retention properties of the capsules to be achieved by clearly preventing any instability mechanisms such as coalescence or ripening and ensures their thermodynamic stability.

[0312] In one embodiment, when composition C2 contains a photoinitiator, step d) is a photopolymerization step, which includes exposing the emulsion (E3) to a light source suitable for initiating the photopolymerization of composition C2, in particular to a UV light source preferably emitting in the wavelength range between 100 nm and 400 nm, and especially for a time of less than 15 minutes.

[0313] In this embodiment, step d) includes subjecting the emulsion (E3) to photopolymerization, which will allow the photopolymerization of composition C2. This step will allow microcapsules encapsulating a water-soluble substance (as defined above) to be obtained.

[0314] In one embodiment, step d) includes exposing the emulsion (E3) to a light source suitable for initiating the photopolymerization of composition C2.

[0315] Preferably, the light source is an ultraviolet light source.

[0316] In one embodiment, the UV light source emits in the wavelength range between 100 nm and 400 nm.

[0317] In one embodiment, the emulsion (E3) is exposed to a light source for less than 15 minutes, preferably 5 to 10 minutes.

[0318] In step d), the envelopes of the double droplets composed of the photocrosslinkable composition C2 are crosslinked and thus transformed into viscoelastic polymer envelopes that encapsulate and protect the water-soluble substance against release without mechanical triggering.

[0319] In another embodiment, when the composition C2 does not contain a photoinitiator, step d) is a polymerization step without exposure to a light source, and the duration of this polymerization step d) is preferably 8 to 100 hours and / or this step d) is carried out at a temperature between 20 °C and 80 °C.

[0320] In this embodiment, the polymerization is initiated, for example, by exposure to heat (thermal initiation) or by simple contact between the monomer, polymer, and crosslinker or by a catalyst. The polymerization time is generally greater than several hours.

[0321] Preferably, the polymerization step d) of the composition C2 is carried out at a temperature of 20 °C to 80 °C for 8 to 100 hours.

[0322] The composition obtained after step d) includes solid microcapsules dispersed in the composition C3, which can be used at any time and without any additional post-treatment steps for the capsules.

[0323] The thickness of the envelope of the microcapsules thus obtained is generally 0.1 to 20 μm, preferably 0.2 to 8 μm, more preferably 0.2 to 5 μm.

[0324] In one embodiment, the solid microcapsules obtained after step d) do not contain a surfactant.

[0325] An advantage of the method according to the invention is that no surfactant is required in any of the steps described. Thus, the method according to the invention allows for a reduction in the presence of additives that may alter the properties of the final product obtained after the release of the fragrance.

[0326] The invention also relates to the use of the composition as defined above for washing and / or caring for fabrics.

[0327] The invention also relates to the use of the microcapsules as defined above to improve the olfactory and / or sensory properties of a washing and / or care composition.

[0328] The invention also relates to the use of the microcapsules as described above to reduce or prevent the evaporation of the fragrance provided by the microcapsules.

[0329] Unless otherwise specified, "between... and...", "from... to...", and "in the range from... to..." shall be construed in an inclusive sense.

[0330] The following examples illustrate the invention without limiting its scope of protection. Example

[0331] Example 1: Preparation of microcapsules

[0332] All stirring steps were carried out using a mechanical stirrer (Ika Eurostar 20) equipped with a serrated stirring paddle.

[0333] Preparation of composition C1

[0334] [Table 1]

[0335]

[0336] The components of phase A were stirred together at 300 rpm until homogenized. To prepare phase B, Tween 80 was gradually added to distilled water and stirred at 2000 rpm until homogenized. Then, phase A was gradually added to phase B while stirring at 2000 rpm. The components were stirred for 2 minutes and then sonicated (SFX 550, Branson) in an ice bath at 40% amplitude for 1.5 minutes (pulse 10 s / 5 s).

[0337] After treatment, 1.4 g of Aculyn 44N gelling agent (Dow) was added to the mixture while stirring at 200 rpm until gelation occurred to obtain Composition C1.

[0338] Preparation of the first emulsion (E1)

[0339] [Table 2]

[0340]

[0341] Composition C1 was gradually added to Composition C2 while stirring at 300 rpm.

[0342] Preparation of the second emulsion (E2)

[0343] [Table 3]

[0344]

[0345] Composition C3 was stirred at 1000 rpm until completely homogenized and then left to stand at room temperature (RT) for 1 hour.

[0346] Then, the first emulsion (E1) was gradually added to composition C3 under stirring at 2000 rpm. Thus, the second emulsion (E2) was obtained.

[0347] Adjusting the size of the second emulsion

[0348] The second polydisperse emulsion (E2) obtained in the above step was stirred at a speed of 2000 rpm for 3 minutes. This produced a monodisperse emulsion (E2).

[0349] Crosslinking of the capsule coating

[0350] The second monodisperse emulsion (E3) obtained in the previous step was irradiated with a UV light source (Dymax LightBox ECE 2000) having a maximum light intensity of 0.1 W / cm 2 and a wavelength of 365 nm for 10 minutes.

[0351] The average size of the resulting microcapsules was 9.5 μm, and the standard deviation of its size distribution was 3.1 μm, i.e., 33%.

[0352] The resulting microcapsules were subjected to 3 consecutive dilution cycles with distilled water and centrifuged in order to produce a microcapsule suspension in distilled water containing 50 mass% microcapsules.

[0353] Example 2: Biodegradability test

[0354] The biodegradability of the microcapsules prepared according to Example 1 was measured according to OECD guideline 301A, and the following website can be obtained from the OECD website: https: / / www.oecd-ilibrary.org / fr / environment / essai-n-301-biodegradabilite-facile_9789264070356-fr.

[0355] Briefly, the microcapsule suspension was diluted with distilled water so that its concentration (DOC) in dissolved organic carbon was between 10 and 40 mg DOC / L, and was incubated in a light-proof chamber stirred at 22 °C together with a seed solution from a municipal organic water treatment plant. DOC analysis was performed regularly, and the biodegradation rate was found to be 70% within 28 days.

[0356] Therefore, the microcapsules prepared according to Example 1 are biodegradable.

[0357] Example 3: Preparation of the main laundry product formulation

[0358] The formulation of the main washing product is as follows:

[0359] [Table 4]

[0360]

[0361] Two samples were prepared from a formulation containing the same concentration of Roman 0330 perfume: sample LP1 containing 5% by mass of the microcapsules prepared according to Example 1 and sample LP2 containing 0.97% by mass of Roman 0330 perfume.

[0362] Example 4: Fabric softening rinse formulation

[0363] The following fabric softener formulations were provided:

[0364] [Table 5]

[0365]

[0366] Two samples were prepared from a formulation containing the same concentration of Roman 0330 perfume: sample AD1 containing 5% by mass of the microcapsules prepared according to Example 1 and sample AD2 containing 0.97% by mass of Roman 0330 perfume.

[0367] Example 5: Preparation of the washed cotton fabric sample

[0368] 10 g of one of the products prepared according to Example 3 or 4 was mixed with 1 L of deionized water. Five 6×10 cm cotton fabric samples were stirred in the resulting solution for 5 minutes, drained, then stirred in 1 L of deionized water for 2 minutes, drained, and then air-dried for 12 hours.

[0369] Example 6: Sensory test after 12 hours

[0370] The cotton fabric samples prepared according to Example 5 were evaluated by a panel of 5 people on an odor intensity scale of 0 - 5, where 0 represents no odor and 5 represents a very strong odor. Each person had two fabric samples / fabric care product samples: one for evaluation without contact and the other for evaluation after rubbing the fabric against itself. The perceived intensity (mean ± standard deviation) of each sample is shown in the following table:

[0371] [Table 6]

[0372]

[0373] These results indicate the targeting vector of the microcapsules to the fabric fibers in the two types of fabric care products tested. In the samples containing microcapsules, the intensity perceived before rubbing was lower because the perfume was confined within the microcapsules. Under the action of rubbing, the microcapsules ruptured and released the perfume inside. Therefore, in the samples containing microcapsules, the intensity perceived after rubbing was greater, indicating that the amount of perfume deposited on the fabric fibers was greater than the amount deposited in the absence of perfume.

[0374] Example 7: Sensory test after 7 days

[0375] The cotton fabric samples prepared according to Example 5 were stored in an unsealed box for 7 days and then evaluated by a panel of 5 people according to the protocol described in Example 6. The perceived intensity (mean ± standard deviation) of each sample is shown in the table below:

[0376] [Table 7]

[0377]

[0378] These results show that the microcapsules provide protection against the evaporation of the perfume. In fact, after rubbing, when the fragrance is encapsulated, the perceived intensity is significantly greater than when it is not encapsulated, thus indicating a greater amount of perfume remaining on the fabric after 7 days.

Claims

1. A composition, comprising: - at least one composition for washing and / or caring for fabrics, and - at least one solid microcapsule having an average diameter of 1 to 30 μm, the solid microcapsule comprising: - a core, composed of a composition C1 containing at least one perfume, wherein the composition C1 is in the form of an emulsion, and - a solid crosslinked polymer coating, the solid crosslinked polymer coating completely enclosing the core around the core, wherein the solid coating comprises a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester, and carboxylate moieties, wherein the thickness of the solid coating is 0.1 to 20 μm.

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

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

4. The composition according to any one of claims 1 to 3, wherein, the composition C1 further comprises at least one aqueous gelling agent, preferably selected from cellulose derivatives, polyacrylates, polyvinylpyrrolidone, polyacrylamides and their derivatives, polyvinyl alcohols and their derivatives, polyethylene glycols, polypropylene glycols and their 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, and the emulsion comprises 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 polymer selected from: aliphatic or aromatic esters or polyesters, urethanes or polyurethanes, acid anhydrides or polyanhydrides, sugars or polysaccharides, ethers or polyethers, amides or polyamides, and carbonates or polycarbonates, wherein the monomer or polymer further comprises at least one reactive moiety selected from acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thioene, maleate, epoxy group, siloxane, amine, lactone, phosphate ester, and carboxylate moieties.

7. The composition according to any one of claims 1 to 6, wherein, the crosslinked polymer is selected from crosslinked polymers, crosslinked polyepoxides, and crosslinked polyurethanes.

8. The composition according to any one of claims 1 to 7, wherein, the crosslinked polymer of the coating of the solid microcapsule is obtained by polymerizing a composition C2, the composition C2 comprising at least one monomer or polymer having at least one reactive moiety 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 the composition C1 according to any one of claims 1 to 5 to the polymer composition C2 with stirring, wherein the compositions C1 and C2 are immiscible, wherein the viscosity of the composition C2 at 25 °C is 500 to 100,000 mPa·s and preferably greater than the viscosity of the composition C1, wherein the composition C2 comprises: - at least one monomer or polymer having at least one reactive moiety as described in claim 1, - at least one crosslinking agent, and - optionally at least one crosslinking photoinitiator or catalyst, to obtain an emulsion (E1) comprising droplets of the composition C1 dispersed in the composition C2; b) adding the emulsion (E1) to the composition C3 with stirring, wherein the compositions C2 and C3 are immiscible, wherein the viscosity of the composition C3 at 25 °C is 500 to 100,000 mPa·s and preferably greater than the viscosity of the emulsion (E1), to obtain a double emulsion (E2) comprising droplets dispersed in the composition C3; c) applying a shear stress to the emulsion (E2), to obtain a double emulsion (E3) comprising droplets of a controllable size dispersed in the composition C3; and d) polymerizing the composition C2, to obtain solid microcapsules dispersed in the composition C3.

10. Use of the composition according to any one of claims 1 to 9 for washing and / or caring for fabrics.

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