Detergent Compositions with Improved Olfactory Properties - Patent application

Abstract

The present invention relates to a composition comprising: at least one composition for cleaning and / or caring for fabrics; and at least one solid microcapsule having an average diameter between 1 μm and 30 μm and comprising a core made of a composition C1 comprising at least one fragrance, and a solid envelope of a crosslinked polymer around it completely encapsulating the core, the solid envelope comprising a crosslinked polymer obtained by polymerization of at least one monomer or polymer having at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties, the thickness of the solid envelope being between 0.1 μm and 20 μm.

Description

[Technical field]

[0001] The invention relates in particular to compositions for use in detergents or for cleaning and / or caring for laundry, comprising microcapsules and having improved olfactory properties. [Background technology]

[0002] Today, fragrance is an essential component of laundry care products, such as detergents and fabric softeners. A sensory attribute that is welcomed by consumers is for their laundry to have a long-lasting, pleasant, fresh fragrance.

[0003] This level of olfactory performance is a real technical challenge for those who exist in this field. Indeed, on the one hand, perfume is a volatile substance that tends to evaporate easily in the bottle of detergent or softener before it can give laundry a pleasant aroma. On the other hand, it should be noted that perfume, which is mostly hydrophobic, has very low adhesion to laundry due to the surfactants that are also contained in laundry care products. Therefore, the perfume contained in detergent or softener is mostly lost due to evaporation or due to the washing process, without fixing itself to laundry and giving it a fragrance.

[0004] One major innovation in the 2000s to address this problem is perfume microcapsules. In microcapsules, the polymer envelope that surrounds the perfume has several advantages. First, the polymer envelope allows to limit the evaporation rate of the perfume. In addition, the affinity of the polymer envelope to the materials that make up the textile fibers allows the microcapsules to fix themselves to these fibers, thus fixing the perfume to the laundry. Finally, the microcapsules provide a long-lasting fragrance to the textile, since due to the mechanical effects when the textile is used, they break down gradually, releasing the perfume bit by bit.

[0005] Microcapsules have therefore made it possible to improve the olfactory performance of detergents and fabric softeners while reducing the amount of perfume contained in these products and therefore their cost. However, faced with ever stricter environmental constraints, manufacturers are now seeking to make their products biodegradable. The microcapsules of the prior art, made of non-biodegradable microplastics, represent a major obstacle in this context.

[0006] The main microcapsules used in detergents and fabric softeners are produced by interfacial emulsion polymerization of compounds from the formaldehyde family and compounds from the melamine family. Such compositions for fabric cleaning and / or care products are detailed in the following applications, among others: US 2013 / 0203642, US 7119057, WO 2015 / 031418, US 2015 / 0252312, and US 2016 / 177241. These capsules performed well in terms of protecting perfume from evaporation and prolonging the scent, but are not biodegradable.

[0007] Biodegradable alternatives, such as microcapsules of non-polymerized cellulose-, polycaprolactone- or polyvinylpyrrolidone-based matrices, have been developed and are described, inter alia, in applications CN 106614564 or US 2015 / 265541. However, these microcapsules are highly porous and their ability to protect perfume from evaporation and to perfume fabrics is insufficient.

[0008] Thus, there is a need in the art for microcapsules that are biodegradable while at the same time further improving their ability to provide long-lasting fragrance to fabrics. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] US Patent Application Publication No. 2013 / 0203642 [Patent Document 2] U.S. Patent No. 7,119,057 [Patent Document 3] International Publication No. 2015 / 031418 [Patent Document 4] US Patent Application Publication No. 2015 / 0252312 [Patent Document 5] US Patent Application Publication No. 2016 / 177241 [Patent Document 6] Chinese Patent No. 106614564 [Patent Document 7] US Patent Application Publication No. 2015 / 265541 [Patent Document 8] European Patent No. 1954793 [Patent Document 9] International Publication No. 2016 / 003699 [Patent Document 10] U.S. Patent No. 9,284,261 [Patent Document 11] International Publication No. 2015 / 150124 [Patent Document 12] U.S. Patent No. 4,137,180 [Patent Document 13] British Patent No. 2039556 [Patent Document 14] European Patent No. 0415698 [Patent Document 15] European Patent No. 0458599 [Patent Document 16] European Patent No. 15306428.2 [Patent Document 17] U.S. Patent No. 5,938,581 [Patent Document 18] French Patent No. 1661787 [Non-patent literature]

[0010] [Non-Patent Document 1] "Surfaces active [sic] Agents and Detergents," Volumes I and II, Schwartz, Perry, and Berch [Non-Patent Document 2] S. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969) [Non-Patent Document 3] S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ, 1960) [Non-Patent Document 4] List of International Fragrance and Fragrance Association (IFRA http: / / www.ifraorg.org / en / ingredients) [Non-Patent Document 5] "Flavor and Fragrance Materials" 1991 (Allured Publishing Co. Wheaton, Ill. USA) [Non-Patent Document 6] Advanced Drug Delivery Reviews 54(2002)889~910 [Non-Patent Document 7] "Les photoinitiateurs dans la reticulation des revetements" G. Li Bassi, Double Liaison-Chimie des Peintures, No. 361, November 1985, pp. 34-41 [Non-Patent Document 8] "Applications industrielles de la polymerisation photoinduite" Henri Strub, L'Actualite Chimique, February 2000, pp. 5-13 [Non-Patent Document 9] "Photopolymers: considerations theoriques et reaction de prise" Marc, JM Abadie, Double Liaison-Chimie des Peintures, No. 435-436, 1992, pp. 28-34 [Non-Patent Document 10] Liu et al., Polymer Chemistry 2013, 4, 3431~3443 [Non-Patent Document 11] https: / / www.oecd-ilibrary.org / fr / environment / essai-n-301-biodegradabilite-facile_9789264070356-fr Summary of the Invention [Problem to be solved by the invention]

[0011] It is therefore an object of the present invention to provide a composition, in particular a composition for cleaning and / or caring for fabrics, which contains biodegradable microcapsules and makes it possible to provide fabrics with a long-lasting pleasant fragrance.

[0012] Another object of the present invention is to provide a detergent product which provides long-lasting pleasant fragrance to fabrics and reduces perfume evaporation as compared to conventional products containing microcapsules.

[0013] It is a further object of the present invention to provide a detergent product that is biodegradable and provides long-lasting, pleasant fragrance to fabrics. [Means for solving the problem]

[0014] Thus, the present invention provides - at least one composition for cleaning and / or caring for fabrics, at least one solid microcapsule having an average diameter between 1 μm and 30 μm, a core composed of a composition C1 comprising at least one flavoring agent, - a solid cross-linked polymer envelope around the core, completely encapsulating the core, said solid cross-linked polymer envelope comprising a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties, said solid cross-linked polymer envelope having a thickness between 0.1 μm and 20 μm, preferably between 0.2 μm and 8 μm, more preferably between 0.2 μm and 5 μm. and a solid microcapsule comprising The present invention relates to a composition comprising:

[0015] The present invention relates to - at least one composition for cleaning and / or caring for fabrics, at least one solid microcapsule having an average diameter between 1 μm and 30 μm, - a core composed of a composition C1 comprising at least one flavoring agent, the composition C1 being in the form of an emulsion, - a solid cross-linked polymer envelope completely encapsulating the core around itself, said solid cross-linked polymer envelope comprising a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties, said solid cross-linked polymer envelope having a thickness between 0.1 μm and 20 μm, preferably between 0.2 μm and 8 μm, more preferably between 0.2 μm and 5 μm. and a solid microcapsule comprising The present invention relates to a composition comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Surprisingly, the inventors have found that by associating detergent or softener formulations known from the prior art with microcapsules made of crosslinked polymers, such as crosslinked polyesters, crosslinked polyepoxys, or crosslinked polyurethanes, the resulting detergent products have the following properties: - Gives fabrics a long-lasting, pleasant fragrance - less perfume evaporation than products containing prior art microcapsules; and - It is biodegradable.

[0017] The compositions according to the present invention combine compositions that are commonly used in fabric cleaning and / or care, but that do not contain microcapsules, with biodegradable microcapsules having a perfume-containing core, as discussed below.

[0018] According to the present invention, the microcapsules do not contain compositions for cleaning and / or caring for fabrics. In particular, the core of the microcapsules used according to the present invention does not contain any softener, detergent or other such product.

[0019] In particular, the present invention comprises the use of biodegradable microcapsules having a perfume-containing core to improve the olfactory characteristics of fabric cleaning and / or care compositions, such as detergents and fabric softeners.

[0020] Within the meaning of this application, the terms "microcapsule" and "capsule" are synonymous.

[0021] Fabric cleaning and / or care compositions As noted above, the compositions of the present invention include compositions for cleaning and / or caring for fabrics.

[0022] These fabric washing and / or care compositions are selected from compositions known in the art for cleaning and maintenance of fabrics, as well as for bleaching, removing wrinkles, softening, making them easier to iron, or preventing wear or pilling.

[0023] Preferably, these compositions do not comprise (micro)capsules.

[0024] In particular, the composition for cleaning and / or caring for fabrics is a detergent composition, in particular a detergent composition in the form of a liquid, powder or tablet. Preferably, the fabric cleaning and / or care composition according to the invention is a detergent composition, in particular a first detergent (fabric cleaning) composition or a softener composition added to the rinse, in particular one described in the following applications: EP 1954793, WO 2016 / 003699, US 9284261 or WO 2015 / 150124.

[0025] The first cleaning composition may include a softening agent, and the softening agent added to the rinse may include a surfactant, particularly a non-ionic surfactant compound.

[0026] The choice of surfactant compound and the amount included will depend on the intended use of the detergent composition. In compositions for cleaning fabrics, various surfactant systems can be selected to adapt the detergent composition to different types of fabrics or washing machines, as is well known to those skilled in the art.

[0027] The total amount of surfactant present will also depend on the intended end use and may, for example, be up to 60% by weight in compositions for hand washing fabrics. In compositions for machine washing fabrics, an amount of 5-40% by weight is generally appropriate. Typically, fabric cleaning and / or care compositions for use according to the invention comprise at least 2% by weight, preferably 2-60% by weight, in particular 15-40% by weight, preferably 25-35% by weight, of surfactant based on the total weight of the composition.

[0028] Detergent compositions suitable for use in most automated washing machines generally contain a soap-free anionic surfactant, or a nonionic surfactant, or a combination of the two in any suitable ratio, optionally with soap.

[0029] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one surfactant, in particular one selected from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants, and mixtures thereof, in particular those detailed in the literature, for example "Surfaces active [sic] Agents and Detergents", volumes I and II, Schwartz, Perry and Berch.

[0030] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one anionic surfactant, in particular one selected from linear alkylbenzenesulfonates, in particular linear alkylbenzenesulfonates with an alkyl chain length of C8 to C16. Preferably, the surfactant content is between 0 and 40% by weight, in particular between 1 and 25% by weight, more preferably between 2 and 15% by weight, based on the total weight of the composition.

[0031] Additional examples of anionic surfactants include saturated or unsaturated alkaline fatty acid salts having 12 to 18 carbon atoms, sulfuric acid-fatty alcohol half ester salts having 12 to 18 carbon atoms, and sulfated products of the nonionic surfactants with low degree of ethoxylation mentioned above; primary alkyl sulfates and secondary alkyl sulfates, especially branched statistical primary C8 to C15 alkyl sulfates; secondary C10 to C18 (2,3) alkyl sulfates; alkyl ether sulfates; sulfated fatty alcohol ethoxylates (FAE), preferably alkyl alkyl alkoxy sulfates; C10 to C18 alkyl alkyl alkoxy carboxylates; mid-chain branched alkyl sulfates; mid-chain branched alkyl alkoxy sulfates; modified alkyl benzene sulfonates; methyl ester sulfonates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and fatty acid (acid) sulfonates. Generally, sodium salts are preferred.

[0032] In one embodiment, the fabric cleaning and / or care compositions used in accordance with the present invention comprise at least one non-ionic surfactant.

[0033] Examples of non-ionic surfactants include alkyl glycoside ethoxylates or propoxylates and / or primary and secondary alcohols, in particular C8-C20 ethoxylated fatty alcohols having an average of 1-20 moles of ethylene oxide per mole of alcohol, and primary C10-C15 ethoxylated fatty alcohols; C6-C12 alkyl alkyl phenol alkoxylates in which the alkoxylate motif is a mixture of ethyleneoxy and propyleneoxy units; C12-C18 alcohol condensates and C6-C12 alkyl phenol condensates with alkyl polyamine ethoxylates having the sequence ethylene oxide / propylene oxide; alkyl polysaccharides; polyhydric fatty acid amides; and alkoxylated ester surfactants, such as fatty methyl ester ethoxylates (MEE).

[0034] Examples of nonionic surfactants also include non-ethoxylated nonionic surfactants such as alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamides), ethoxylated and / or propoxylated products of N-alkylamines, vicinal diols, fatty acid esters, and fatty acid amides.

[0035] Such surfactants may be contained in these compositions in an amount ranging from 0% to 40% by weight, preferably from 1% to 25% by weight, more preferably from 2% to 15% by weight, relative to the total weight of the composition.

[0036] In one embodiment, the fabric cleaning and / or care compositions used in accordance with the present invention comprise at least one amphoteric surfactant.

[0037] Examples of amphoteric surfactants include secondary and tertiary amine derivatives, secondary and tertiary heterocyclic amine derivatives, or derivatives of quaternary ammonium compounds, quaternary phosphonium compounds, or tertiary sulfonium compounds, such as betaines such as alkyl dimethyl betaine and cocodimethylamidopropyl betaine, C8-C18 amine oxides, and sulfobetaines and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propanesulfonates, where one alkyl group may be a C8-C18 or C10-C14 alkyl group, water-soluble amine oxides, such as C10-C18 alkyl dimethyl amine oxides or C8-C12 alkoxyethyl dihydroxyethyl oxides.

[0038] In one embodiment, when the fabric cleaning and / or care composition is a softener, the composition contains at least one cationic softening compound for softening fabrics.

[0039] Examples of cationic softening compounds include cationic surfactants, e.g., those with a water solubility of 1×10 in demineralized water at 20° C. -3% by weight or less; compounds preferably containing two alkyl or alkenyl chains with a polar head group and an average molecular chain length of C14 or more. Preferably, these compounds have two long alkyl or alkenyl chains, each of which has an average length of C16 or more. Preferably, at least 50% of the alkyl or alkenyl groups have a molecular chain length of C18 or more. The long alkyl or alkenyl groups are preferably mainly linear. For example, distearyl dimethyl ammonium chloride and di(hardened tallow alkyl) dimethyl ammonium, di(sulphoxyloxyethyl) dimethyl ammonium and / or its tallow analogues, triethanolamine (TEA quat) derivatives such as tallow N-methyl-N,N,N-triethanolamine diester or quaternary tallow ammonium chloride diester, or tallow methosulfate diester. Other examples include quaternary dimethylhydroxyethylammonium, dimethylhydroxyethyllaurylammonium chloride, benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalconium B (C2-2m,p-dichlorobenzyldimethyl-alkyl chloride), benzoxonium chloride, (2-hydroxyethyl)ammonium chloride, cetrimonium bromide (N-hexadecyl-N,N-trimethylammonium bromide), benzethonium chloride, dialkyldimethylammonium chlorides, such as di-n-decyl. Examples of suitable ammonium salts include dimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride, benzalkonium chloride having a C8 to C22 alkyl residue, methyl-N-(2-hydroxyethyl)-N,N-di(acyloxyethyl)ammonium methosulfate, bis(palmitoyl)ethyl hydroxyethylmethylammonium methosulfate, or (2-hydroxyethyl)ammonium methyl-N,N-bis(acyloxyethyl)-N-methosulfate, and cationic polyamines.

[0040] Such cationic softening compounds may be contained in these compositions in an amount of 0.5 to 35% by mass, preferably 1 to 30% by mass, more preferably 3 to 25% by mass, based on the total mass of the composition.

[0041] In one embodiment, if the fabric cleaning and / or care composition is a fabric softening composition, the composition contains at least one biodegradable cationic fabric softening compound, such as a biodegradable quaternary ammonium-based material, such as 1,2-bis(hardened sulfonyloxy)-3-trimethylammonium propane chloride, as described in US Patent Publication No. 4,137,180. Preferably, these materials contain a small amount of the corresponding monoester, such as hardened sulfonyloxy-2-hydroxy-3-trimethylammonium propane chloride.

[0042] 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 alkylpolyamines.

[0043] Such cationic compounds may be contained in these compositions in an amount of 0.5 to 35 mass %, preferably 1 to 30 mass %, and more preferably 3 to 25 mass %, based on the total mass of the composition.

[0044] In one embodiment, if the fabric cleaning and / or care composition is a fabric softening composition, the composition contains at least one water soluble cationic fabric softening compound as described in GB 2039556.

[0045] In one embodiment, if the fabric cleaning and / or care composition is a fabric softening composition, the composition contains at least one non-ionic fabric softening compound, such as lanolin and its derivatives, lecithin, and other phospholipids.

[0046] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one stabiliser, in particular for stabilising the microcapsules.

[0047] Examples of stabilizers include any known component capable of suspending particles and / or adjusting the rheology of liquid compositions, in particular crystalline materials containing hydroxyl groups, polyacrylates, polycarboxylates, alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolammonium salts, C12-C20 fatty alcohols, di-benzylidene 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 moles of alkylene oxide, C10-C20 alcohols, and mixtures thereof can also be used. Other stabilizers include deflocculating polymers, as described in EP 0415698 and EP 0458599. Advantageously, the non-ionic stabilizer is a C8-C22 linear alcohol alkoxylated with 10-20 moles of alkylene oxide. Advantageously, gums and other polysaccharides can also be used, such as gellan gum, carrageenan gum, xanthan gum, polyvinyl alcohol and its derivatives, cellulose and its derivatives, including cellulose ethers and cellulose esters, as well as tamarind gum (including, for example, xyloglucan polymers), guar gum, locust bean gum. Finally, examples further include fatty acids and fatty waxes, such as alkyl or alkenyl acids of C8 to C24 monocarboxylic acids and their polymers, castrol oil, and its derivatives. Preferably, saturated fatty acids are used, in particular hydrogenated C16 to C18 tallow fatty acids. Preferably, the fatty acids are not saponified, more preferably fatty acids such as oleic acid, lauric acid, or tallow fatty acids are not included.

[0048] Such stabilizers may be contained in these compositions in an amount of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, and more preferably 1 to 4% by mass, based on the total mass of the composition.

[0049] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one inorganic additive which improves the detergent properties of the product, for example sodium carbonate, optionally in combination with crystallization germs for calcium carbonate, amorphous crystalline aluminosilicates such as zeoliths, inorganic phosphates and polyphosphates such as sodium orthophosphate de sodium, pyrophosphates and tripolyphosphates.

[0050] Preferably, such inorganic additives are present in an amount ranging from 5 to 40% by weight relative to the total weight of the composition.

[0051] In one embodiment, the fabric cleaning and / or care composition used according to the present invention comprises at least one organic detergent additive, such as polycarboxylic acids, in particular citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, as well as polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic) acid, ethylenediaminetetrakis(methylenephosphonic) compounds, and polymeric acids, such as (poly)dextrins, polymeric acrylic acid, methacrylic acid, maleic acid, and polymeric mixtures thereof. All of the aforementioned acids are generally used in the form of their water-soluble salts, in particular their alkali salts.

[0052] Preferably, such organic detergent additives are present in an amount of from 0.5 to 25% by weight, preferably from 1 to 10% by weight, based on the total weight of the composition.

[0053] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one polycarboxylate monomeric organic detergent additive, such as citrate, gluconate, oxydisuccinate, glycerol monosuccinate, glycerol disuccinate, and glycerol trisuccinate, carboxymethyloxysuccinate, carboxymethyloxymalonate, dipicolinate, hydroxyethyliminodiacetate, alkyl and alkenyl malonates and succinates, and sulfonated fatty acid salts.

[0054] Preferably, such organic detergent additives are present in an amount of from 5 to 30% by weight, preferably from 10 to 25% by weight, based on the total weight of the composition.

[0055] In one embodiment, the fabric cleaning and / or care composition used according to the present invention comprises at least one peroxide bleaching compound, such as an inorganic persalt or an organic peracid capable of generating hydrogen peroxide in aqueous solution.Suitable peroxide bleaching compounds include organic peroxides, such as urea peroxide, and inorganic persalts, such as alkali metal perborates, percarbonates, perphosphates, persilicates, and persulfates.Examples include monohydrate and tetrahydrate sodium perborate and sodium percarbonate, phthalimide peroxycaproic acid, peroxybenzoic acid, hypohalites, peroxyacetic acid, diperoxoazelaic acid, diperoxododecane diacid, and oxidase system, or diperoxydodecanedioic acid salts.

[0056] Preferably, such peroxide bleaching compounds are contained in an amount ranging from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight, relative to the total weight of the composition.

[0057] In one embodiment, the fabric cleaning and / or care composition used according to the present invention comprises at least one bleach activator or bleach precursor, such as catalytic metal complexes, peroxycarboxylic acid precursors, more particularly peracetic acid precursors and peronanoic acid precursors, such as N,N,N',N'-tetracetylethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (SNOBS), octanoylcaprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, benzoylvalerolactam, and methyldodecanobenzyl acrylate, which can be used together with the bleaching compound to improve the bleaching effect at low washing temperatures. Similarly, peracids, such as imidoperoxypercarboxylic acid and phthalimidoperoxycaproic acid (PAP), can be used.

[0058] Preferably, such bleach activators or bleach precursors are contained in an amount of from 0.1 to 8% by weight, preferably from 0.5 to 5% by weight, relative to the total weight of the composition.

[0059] In one embodiment, the fabric cleaning and / or care composition used in accordance with the present invention comprises at least one bleach stabilizer (transition metal sequestrant), such as ethylenediaminetetraacetate (EDTA), a polyphosphonate, such as Dequest™, and a non-phosphate stabilizer, such as EDDS (ethylenediaminedisuccinic acid).

[0060] In one embodiment, the fabric cleaning and / or care composition used in accordance with the present invention comprises at least one enzyme, such as proteases (especially subtilisin), cutinase, amylase, pullulanase, hemicellulase, cellulase, hemicellulase mannanase, pectin-separating enzymes, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase, lipase, and peroxidase, and mixtures thereof. Particularly suitable are enzymatically active substances obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, or Pseudomonas cepacian. Any enzymes used may be adsorbed onto a carrier material and / or incorporated into an encapsulating material to protect them against premature inactivation.

[0061] Preferably, such enzymes are present in an amount of approximately 0.1% by weight and an amount of approximately 3.0% by weight, relative to the total weight of the composition.

[0062] In one embodiment, the fabric cleaning and / or care composition used in accordance with the present invention comprises at least one powder structurant, such as a fatty acid (or fatty acid soap), sugar, acrylate or acrylate / maleate copolymer, or sodium silicate.

[0063] Preferably, such powder structurants are present in an amount of from 1 to 5% by weight, relative to the total weight of the composition.

[0064] The fabric cleaning and / or care compositions 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.

[0065] In one embodiment, the fabric cleaning and / or care composition used according to the present invention comprises at least one free, i.e., unencapsulated, fragrance. Such fragrances are well known to those skilled in the art, and include, inter alia, those mentioned in S. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969), S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ, 1960), the International Fragrance Association list (IFRA http: / / www.ifraorg.org / en / ingredients), and "Flavor and Fragrance Materials", 1991 (Allured Publishing Co. Wheaton, Ill. USA).

[0066] Preferably, such free flavouring agents are contained in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on the total weight of the composition.

[0067] In one embodiment, the fabric cleaning and / or care composition used in accordance with the present invention comprises at least one antifoaming agent, such as silicone oil or paraffin oil.

[0068] Preferably, such an antifoaming agent is contained in an amount of 0.05% to 4% by mass, preferably 0.1% to 3% by mass, more preferably 0.2% to 1% by mass, based on the total mass of the composition.

[0069] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one degreasing agent or antiredposition agent, such as non-ionic cellulose ethers, such as methylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, polymers of phthalic acid and / or terephthalic acid, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate, or anionically and / or nonionically modified derivatives thereof, preferably in an amount of from 0 to 5% by weight, relative to the total weight of the composition.

[0070] In one embodiment, the fabric cleaning and / or care composition used according to the invention comprises at least one anti-transfer or anti-fading agent, such as polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridinium chloride, polyethylene glycol copolymers of vinylpyrrolidone and vinylimidazole, and mixtures thereof, preferably in an amount of from 0% to 2% by weight, based on the total weight of the composition.

[0071] In one embodiment, the fabric cleaning and / or care composition used according to the present invention comprises at least one optical brightener, which may include any compound with fluorescence, such as compounds that absorb UV light and re-emit it in the form of "blue" visible light. Such brighteners include derivatives of stilbene, 4,4'-diaminostilbene, biphenyl, and distyrylbiphenyl, five-membered heterocycles such as triazoles, pyrazolines, oxazoles, imidazoles, or six-membered heterocycles (e.g., coumarins, naphthalamides, s-triazines).

[0072] Preferably, such optical brighteners are present in an amount of 0 to 0.4% by weight, preferably 0.1 to 0.3% by weight, based on the total weight of the composition.

[0073] In one embodiment, the fabric cleaning and / or care compositions used in accordance with the present invention comprise at least one non-aqueous solvent, such as a mono- or polyhydric alcohol, an alkanolamine, or a glycol ether, provided that, in the specified concentration ranges, they are miscible in water. Preferably, the solvent is selected from ethanol, n-propanol, isopropanol, butanol, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, and ethylene glycol, ethylene glycol propylene ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol ether, t-butyl ether, di-n-octyl ether, and mixtures of these solvents.

[0074] Preferably, such a non-aqueous solvent is contained in an amount of 0 to 25% by mass, preferably 1% to 20% by mass, more preferably 2 to 15% by mass, based on the total mass of the composition.

[0075] In one embodiment, the fabric cleaning and / or care compositions used in accordance with the present invention comprise water.

[0076] Solid Microcapsules As mentioned above, the composition according to the invention comprises at least one solid microcapsule, as defined above.

[0077] Preferably, the composition according to the present invention comprises a plurality of solid microcapsules, ie a series or population of solid microcapsules, all of which may be the same or different.

[0078] Microcapsules according to the invention are referred to as "solid microcapsules" due to the solid nature of the crosslinked polymer envelope.

[0079] In one embodiment, a solid microcapsule according to the invention comprises a liquid (non-solid) core.

[0080] If specific monomers and polymers are selected, the microcapsules used in accordance with the present invention can be biodegradable.

[0081] Here, biodegradability is defined as the ability to degrade in the natural environment as defined in the OECD guidelines: OECD 301 (ready biodegradability), i.e. OECD 301A (Dissolved Organic Carbon (DOC) Loss), OECD 301B (CO2 Emission Test), OECD 301C (Modified MITI Test (I)), OECD 301D (Closed Bottle Test), OECD 301E (Modified OECD Screening Test), OECD 301F (Manometric Respiration Test), or OECD 304A (Soil Biodegradation), OECD 306 (Biodegradability in Seawater), and OECD 310 (Ready Biodegradability in Closed Containers - CO2 (Headspace Test)).

[0082] The microcapsules according to the invention are characterized by comprising a core which comprises at least one perfume, with the proviso that the perfume is different from the fabric cleaning and / or care composition.

[0083] In accordance with the present invention, the fabric cleaning and / or care composition described above and the solid microcapsules (series or groups of solid microcapsules) are distinct components.

[0084] In one embodiment, a composition according to the invention comprises solid microcapsules, each of which is as defined above, and the standard deviation of the diameter distribution of the microcapsules is less than 50% or less than 1 μm.

[0085] The size distribution of the solid microcapsules can be measured, for example, by image analysis of selected microcapsules, or by optical microscopy, or by light scattering using a Mastersizer 3000 equipped with a Hydro SV measuring cell (Malvern Instruments).

[0086] Composition C1 As mentioned above, composition C1 is preferably in the form of an emulsion and therefore comprises a continuous phase and a dispersed phase.

[0087] In one embodiment, composition C1 of the solid microcapsule core defined above comprises at least 20% by weight of flavoring agent relative to the total weight of composition C1, preferably from 25 to 60% by weight, more preferably from 30 to 50% by weight, relative to the total weight of composition C1.

[0088] In one embodiment, composition C1 further comprises at least one gelling agent.

[0089] The gelling agent is particularly preferably from the following group: cellulose derivatives, for example cellulose ethers: methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose; - polyacrylates (also known as carbomers), such as polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(hydroxyethyl methacrylate) (pHEMA), poly(N-2-hydroxypropyl methacrylate) (pHPMA); - polyacrylamides, such as poly(N-isopropylacrylamide) (PNIPAM); - Polyvinylpyrrolidone (PVP) and its derivatives; - Polyvinyl alcohol (PVA) and its derivatives; - poly(ethylene glycol), poly(propylene glycol) and its derivatives, such as poly(ethylene glycol) acrylate / methacrylate, poly(ethylene glycol) diacrylate / dimethacrylate, polypropylene carbonate; - polysaccharides, such as carrageenan, locust bean gum or tara gum, dextran, xanthan gum, chitosan, agarose, hyaluronic acid, gellan gum, guar gum, gum arabic, tragacanth gum, diutan gum, oat gum, karaya gum, ghatti gum, curdlan gum, pectin, konjac gum, starch; - protein derivatives, for example gelatin, collagen, fibrin, polylysine, albumin, casein; - Polyurethane and its derivatives The polymer may be selected from the group of water-soluble or water-dispersible polymers, including water-based polymers selected from the group consisting of:

[0090] The gelling agent may also be selected from the group of solid particles that can be used as gelling agents when dispersed in water, such as clays, silicas, and silicates.

[0091] Examples of solid particles that can be used in composition C1 as gelling agents include clays and silicates, especially in the category of phyllosilicates (also known as "flaky silica"). Examples of silicates that can be used in the present invention include bentonite, hectorite, attapulgite, sepiolite, montmorillonite, saponite, sauconite, nontronite, kaolinite, talc, sepiolite, and chalk. Fumed synthetic silicates can also be used. The aforementioned clays, silicates, and silicas can be advantageously modified with organic molecules, such as polyethers, ethoxylated amides, quaternary ammonium salts, long-chain diamines, long-chain esters, polyethylene glycols, and polypropylene glycols.

[0092] Preferably, the gelling agent is selected from the group consisting of cellulose derivatives, polyacrylates, poly(ethylene glycol) derivatives, and synthetic silicas.

[0093] In one embodiment, composition C1 comprises between 0.1 and 30% by weight of gelling agent, preferably between 0.5 and 20% by weight, more preferably between 0.5 and 10% by weight.

[0094] In one embodiment, composition C1 comprises between 30 and 70% by weight of water, preferably between 35 and 65% by weight, more preferably between 35 and 60% by weight.

[0095] In one embodiment, composition C1 further comprises at least one surfactant, in particular one selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.Examples of surfactants include oxyethylenated / oxypropylenated block polymers, such as poloxamers; fatty acid esters of sorbitan and its oxyethylenated derivatives, such as sorbitan monostearate, sorbitan monopalmitate, oxyethylenated sorbitan stearate, palmitate and oleate; derivatives of polyethylene glycol, and mixtures of caprylic and capric glycerides (monoglycerides, diglycerides and triglycerides); alkyl polyglycosides, in particular alkyl polyglucosides, such as caprylyl / capryl glucoside or lauryl glucoside.

[0096] In one embodiment, composition C1 further comprises at least one agent for adjusting the hydrophobicity of the perfume. These agents are hydrophobic materials with ClogP 4 or more, preferably ClogP 6 or more, and good miscibility with the perfume used. Examples of these agents include monoglyceride oils, diglyceride oils, and triglyceride oils, such as capric triglyceride / caprylic triglyceride; fatty acid esters of oligomers of polyglycerol, polyethylene glycol, polypropylene glycol, and polybutylene glycol; nonionic fatty alcohol alkoxylates, such as isopropyl myristate, diethyl phthalate, dibutyl phthalate, diisodecyl adipate; mineral oils; silicone oils, such as polydimethylsiloxane and polydimethylcyclosiloxane; diethyl phthalate; polyalphaolefins; castor oil.

[0097] Preferably, composition C1 is in the form of a nanoemulsion in which the continuous phase is an aqueous gel. Preferably, the nanoemulsion droplets have an average diameter between 50 nm and 5 μm, preferably between 100 nm and 3 μm, more preferably between 100 nm and 1 μm.

[0098] Preferably, composition C1 is in the form of an emulsion, the continuous phase of which is an aqueous gel.

[0099] Preferably, the average diameter of the emulsion droplets is between 50 nm and 5 μm, preferably between 100 nm and 3 μm, more preferably between 100 nm and 1 μm.

[0100] The inventors have found that one determining parameter for limiting the evaporation of the fragrance of the microcapsules is the stability of the emulsion of composition C1 over time, i.e. that the size distribution remains substantially unchanged over time.

[0101] To reach this level of stability, the addition of a gelling agent is particularly advantageous since it makes it possible to slow down the coalescence of the emulsion droplets.

[0102] Flavoring agent As mentioned above, composition C1 contains at least one flavoring agent.

[0103] Thus, composition C1 according to the invention may contain a single flavoring agent (or fragrance) or a mixture of several flavoring agents (or fragrances).

[0104] The example of flavoring agent includes all kinds of flavors or fragrances; these terms are used interchangeably herein.These flavors or fragrances are well known to those skilled in the art, and include, for example, those mentioned in S. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969), S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ, 1960), the list of the International Fragrance Association (IFRA http: / / www.ifraorg.org / en / ingredients), and "Flavor and Fragrance Materials" 1991 (Allured Publishing Co. Wheaton, Ill. USA).

[0105] Perfumes for use in the present invention may include natural products such as extracts, essential oils, absolutes, resinoids, resins, concretes, etc., as well as synthetic base materials such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, alicyclic, and heterocyclic compounds.

[0106] In one embodiment, the flavoring agent comprises less than 10% by weight, or less than 7.5% by weight, based on the total weight of the flavoring agent, of any compound having a ClogP of less than 2.1. In one embodiment, the flavoring agent does not comprise any compound having a ClogP of less than 2.1.

[0107] Solid Envelope In one embodiment, the solid microcapsules described above comprise a solid envelope composed entirely of a crosslinked polymer, as defined above.

[0108] The aforementioned solid envelope is composed of a crosslinked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties.

[0109] Within the meaning of the present invention, the term "monomer" or "polymer" includes any basic unit suitable for the formation of a solid material by polymerization, whether alone or in combination with other monomers or polymers. The term "polymer" also encompasses oligomers.

[0110] In one embodiment, the crosslinked polymer is obtained by polymerization from monomers or polymers selected from aliphatic or aromatic, esters or polyesters, urethanes or polyurethanes, anhydrides or polyanhydrides, saccharides or polysaccharides, ethers or polyethers, amides or polyamides, and carbonates and polycarbonates, which monomers or polymers further comprise at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate, and carboxylate moieties.

[0111] Examples of such monomers or polymers include, but are not limited to, the following compounds and mixtures thereof: In particular, polyglycolide (PGA), polylactide (PLA), poly(lactide-co-glycolide) (PLGA), poly(orthoesters), such as polycaprolactone (PCL), polydioxanone, poly(ethylene succinate), poly(butylene succinate) (PBS), poly(ethylene adipate), poly(butylene adipate), poly(ethylene sebacate), poly(butylene sebacate), poly(valerolactone) (PVL), poly(decalactone), polyhydroxyvalerate, poly(beta- 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-hydroxycaproate), 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), ate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(4-hydroxybutyrate), poly(4-hydroxybutyrate-co-2-hydroxybutyrate), poly(4-hydroxypropionate), poly(4-hydroxyvalerate), poly(5-hydroxybutyrate), poly(5-hydroxyvalerate), poly(6-hydroxyhexanoate),Poly(alkylene alkanoates), poly(alkylene dicarboxylates), poly(butylene adipate), poly(butylene adipate-co-terephthalate), poly(butylene carbonate), poly(butylene pimelate), poly(butylene succinate), 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), polydiaxanone, poly(ethylene azelate), poly(ethylene carbonate), poly(ethylene decamthylate), poly(ethylene furanoate), poly(ethylene oxalate), poly(ethylene succinate), poly(ethylene succinate-co-adipate), poly(ethylene sebacate), poly(ethylene succinate-co-terephthalate), poly(ethylene suberate), poly(hexamethylene sebacate), poly(glycolide) -co-caprolactone), poly(lactide-co-epsilon-caprolactone), polymandelate, poly(B-malic acid), poly(b-propiolactone), poly(propylene succinate), poly(tetramethylene adipate-co-terephthalate), poly(tetramethylene carbonate), poly(trimethylene carbonate), poly(tetramethylene succinate)-co-(tetramethylene carbonate), poly(trimethylene adipate), poly(methylene adipate-co-terephthalate), poly(tetrameth a family of aliphatic or aromatic esters and polyesters including poly(ethylene adipate), poly(tetramethyl glycolide), poly(butylene succinate), poly(valerolactone), further comprising at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, ctone, phosphate, and carboxylate moieties; the family of anhydrides or polyanhydrides, which further comprise at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties, such as those derived from polysebacic acid, polyadipic acid, polyterephthalic acid, poly(bis(p-carboxyphenoxy)alkanoic acid) or more broadly, the polyanhydrides described, for example, in Advanced Drug Delivery Reviews 54 (2002) 889-910; the family of saccharides and polysaccharides, including in particular carrageenans, dextrans, cyclodextrins, such as hyaluronic acid, agarose, chitosan, chitin, alginates, starch, cellulose and its derivatives, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose, which further comprises at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties; - the family of ethers and polyethers, including in particular the polyethylene glycols, further comprising at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties; and - the family of amides and polyamides, including in particular the poly(ester amides) or polyphthalamides, further comprising at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties; In particular, a family of polyurethanes comprising the reaction products of polyols and polyisocyanates, the reaction products further comprising at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties. Examples of the aforementioned polyols include 1,4-butanediol, 1,2-propanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, methylpropanediol, bisphenol A, polyoxypropylenediol, polybutadienediol, oxytetramethylene glycol, ethylene glycol adipate diol, polyethylene adipate glycol propylene glycol diol, polyadipate diethylene glycol diol, polyethylene adipate-diethylene glycol ester diol, pentaerythritol, glycerol, trimethylolpropane, trishydroxyethylpropane or oxypropylenetriol. Examples of the aforementioned polyisocyanates include hexamethylene diisocyanate derivatives, methylene dicyclohexyl diisocyanate derivatives, or isophorone diisocyanate derivatives.

[0112] In one preferred embodiment, the crosslinked polymer is selected from the group consisting of crosslinked polyesters, crosslinked polyepoxies, and crosslinked polyurethanes.

[0113] Preferably, the crosslinked polymer of the envelope of the solid microcapsules is obtained by polymerizing a composition C2 comprising at least one monomer or polymer having at least one reactive moiety as defined above, at least one crosslinking agent, and optionally at least one crosslinking photoinitiator or catalyst.

[0114] "Crosslinking agent" refers to a compound containing at least two reactive moieties capable of crosslinking a monomer or polymer, or a mixture of monomers or polymers, during polymerization.

[0115] The crosslinker can be selected from molecules having at least two, the same or different, moieties selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate, and carboxylate moieties.

[0116] Examples of crosslinkers include, among others: 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-methacryloxyethyl) N,N'-1,9-nonylenebiscarbamate, 1,4-butanediol diacrylate acrylate, 1,5-pentanediol dimethacrylate, allyl methacrylate, N,N'-methylenebisacrylamide, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, tetraethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, N,N-diallylacrylamide, or glycidyl methacrylate; polyfunctional acrylates, such as dipentaerythritol pentaacrylate, 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane trimethacrylate, ethylenediamine tetramethacrylate, pentaerythritol triacrylate or pentaerythritol tetraacrylate; and - acrylates which also contain another reactive moiety, such as propargyl methacrylate, N-acryloxysuccinimide, N-(2-hydroxypropyl)methacrylamide, N-(t-BOC-aminopropyl)methacrylamide, monoacryloxyethyl phosphate, acrylic anhydride, 2-(tert-butylamino)ethyl methacrylate, N,N-diallylacrylamide, or glycidyl methacrylate.

[0117] "Photoinitiator" refers to a compound that can fragment under the effect of light radiation.

[0118] Photoinitiators which can be used according to the invention are known from the prior art and are described, for example, in "Les photoinitiateurs dans la reticulation des revetements" G. Li Bassi, Double Liaison-Chimie des Peintures, No. 361, November 1985, pages 34-41; "Applications industrielles de la polymerisation photoinduite" Henri Strub, L'Actualite Chimique, February 2000, pages 5-13; and "Photopolymeres: considerations theoriques et reactions of the price" Marc, JM Abadie, Double Liaison-Chimie des Peintures, No. 435-436, 1992, pages 28-34.

[0119] These photoinitiators include: - α-hydroxyketones, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone, such as those sold under the names DAROCUR® 1173 and DAROCUR® 4265, IRGACURE® 184, IRGACURE® 2959 and IRGACURE® 500 by the company BASF, and ADDITOL® CPK by the company CYTEC; - α-aminoketones, in particular 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, such as those sold under the names IRGACURE® 907 and IRGACURE® 369 by the company BASF; - aromatic ketones, such as those sold under the name ESACURE® TZT by the company LAMBERTI; or thioxanthones, such as those sold under the name ESACURE® ITX by the company LAMBERTI, and quinones. Most often, these aromatic ketones require the presence of a hydrogen donor compound, such as a tertiary amine, and in particular an alkanolamine. An example is the tertiary amine ESACURE® EDB, sold by the company LAMBERTI. - α-dicarbonyl derivatives, the most common example of which is benzil dimethyl ketal, sold under the name IRGACURE® 651 by the company BASF. Another commercial product is sold under the name ESACURE® KB1 by the company LAMBERTI. - acylphosphine oxides, such as bis-acylphosphine oxides (BAPO), such as those sold under the names IRGACURE® 819, IRGACURE® 1700 and IRGACURE® 1800, DAROCUR® 4265, LUCIRIN® TPO and LUCIRIN® TPO-L by BASF.

[0120] Other examples of photoinitiators include aromatic ketones such as benzophenones, phenylglyoxylates such as phenylglyoxylic acid methyl ester, oxime esters such as [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, sulfonium salts, iodonium salts, and oxime sulfonates.

[0121] Microcapsule production In one embodiment, solid microcapsules are prepared by the following process: a) adding, with stirring, composition C1 as defined above to a polymer composition C2, wherein compositions C1 and C2 are not miscible, the viscosity of composition C2 is between 500 and 100,000 mPa.s at 25° C., preferably higher than the viscosity of composition C1; Composition C2 is - at least one monomer or polymer having at least one reactive moiety as defined above at least one crosslinking agent, and - optionally containing at least one crosslinking photoinitiator or catalyst, This results in an emulsion (E1) comprising droplets of composition C1 dispersed in composition C2, b) adding emulsion (E1) to composition C3 with stirring, wherein compositions C2 and C3 are not miscible; the viscosity of composition C3 is between 500 and 100,000 mPa.s at 25° C., preferably higher than the viscosity of emulsion (E1); This results in a double emulsion (E2) comprising droplets dispersed in composition C3; c) subjecting the emulsion (E2) to shear stress, resulting in a double emulsion (E3) containing droplets of controlled size dispersed in composition C3; d) polymerizing composition C2, resulting in solid microcapsules dispersed in composition C3. The method is obtained by a method comprising the steps of:

[0122] The method described above consists of forming a double emulsion composed of droplets containing at least one flavoring agent surrounded by a crosslinkable liquid phase. These double droplets are then made monodisperse in size before being converted into hard capsules by crosslinking or polymerization. The preparation involves four steps, which are described in detail below.

[0123] In one embodiment, the process according to the invention comprises a preliminary step, prior to the aforementioned step a), of preparing a composition C1 in the form of an emulsion.

[0124] In this step, composition C1 containing the fragrance is added to hydrophilic composition C2, except that this step is carried out with stirring, which means that composition C1 is typically mechanically stirred at the same time as composition C1 containing the fragrance is added in order to emulsify the mixture of composition C1.

[0125] During this step, the composition C1 containing the flavoring agent is at a temperature between 0° C. and 100° C., preferably between 10° C. and 80° C., more preferably between 15° C. and 60° C. During this step, the hydrophilic composition C2 is at a temperature between 0° C. and 100° C., preferably between 10° C. and 80° C., more preferably between 15° C. and 60° C.

[0126] Any type of agitator commonly used to form emulsions can be used to carry out this step, such as a mechanical blade agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high pressure homogenizer, a colloid mill, a high shear disperser, or a high speed homogenizer.

[0127] In one embodiment, the hydrophilic composition hydrophilic substance C2 contains a gelling agent.

[0128] In another embodiment, the gelling agent is added to composition C1 immediately after composition C1 containing the fragrance is emulsified in hydrophilic composition C2. In this embodiment, any type of stirrer used to homogenize solutions can be used to add the gelling agent to composition C1, for example a mechanical blade stirrer with a low rotation speed.

[0129] Step a) of the process according to the invention consists in preparing a first emulsion (E1).

[0130] The first emulsion is composed of a dispersion of droplets of composition C1 (containing at least one fragrance agent) in a polymer composition C2 that is not miscible with C1, produced by adding C1 dropwise to C2 with stirring.

[0131] In step a), composition C1 is added to the crosslinkable polymer composition C2, with the proviso that this step is carried out with stirring, which means that composition C2 is typically mechanically stirred at the same time that composition C1 is added in order to emulsify the mixture of composition C1 and composition C2.

[0132] The addition of composition C1 to composition C2 is typically dropwise.

[0133] During step a), composition C1 is at a temperature between 0° C. and 100° C., preferably between 10° C. and 80° C., more preferably between 15° C. and 60° C. During step a), composition C2 is at a temperature between 0° C. and 100° C., preferably between 10° C. and 80° C., more preferably between 15° C. and 60° C.

[0134] Under the addition conditions of step a), compositions C1 and C2 are not miscible, which means that the amount (by mass) of composition C1 that may be soluble in composition C2 is not more than 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total mass of composition C2, and the amount (by mass) of composition C2 that may be soluble in composition C1 is not more than 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total mass of composition C1.

[0135] Thus, when composition C1 is brought into contact with composition C2 with stirring, the latter is dispersed in the form of small droplets ("single droplets").

[0136] The miscibility of compositions C1 and C2 also makes it possible to prevent the migration of the active ingredients of composition C1 into composition C2.

[0137] Composition C2 is stirred to form an emulsion containing droplets of composition C1 dispersed in composition C2, also referred to as a "simple emulsion" or a "C1-in-C2 emulsion."

[0138] To carry out step a), any type of agitator commonly used to form emulsions can be used, such as a mechanical blade agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser, or a high-speed homogenizer.

[0139] Composition C2 will ultimately form the solid envelope of the microcapsules.

[0140] To control the thickness of the capsule envelope resulting from the process, the volume fraction of C1 in C2 can be varied from 0.1 to 0.6.

[0141] In one embodiment, the ratio of the volume of composition C1 to the volume of composition C2 varies between 1:10 and 10:1. Preferably, the ratio is between 1:3 and 5:1, more preferably between 1:3 and 3:1.

[0142] Preferably, the viscosity of composition C2 at 25° C. is between 1000 and 50000 mPa.s, more preferably between 2000 and 25000 mPa.s, for example between 3000 and 15000 mPa.s.

[0143] Preferably, the viscosity of composition C2 is higher than the viscosity of composition C1.

[0144] Viscosity is measured using a Haake RheostressTM600 rheometer equipped with a cone diameter of 60 mm at an angle of 2° and a temperature controlled cell set at 25° C. Viscosity readings are taken at a shear rate of 10 s -1 It is held.

[0145] In this embodiment, the destabilization kinetics of the droplets of emulsion (E1) is rather slow, allowing the microcapsule envelope to polymerize in step d) before the emulsion is destabilized. Thus, once complete, polymerization provides thermodynamic stability. Thus, the relatively high viscosity of composition C2 ensures the stability of emulsion (E1) obtained from step a).

[0146] Preferably, the interfacial tension between compositions C1 and C2 is low. Typically, these interfacial tensions vary between 0 and 50 mN / m, preferably between 0 and 20 mN / m.

[0147] Advantageously, the low interfacial tension between compositions C1 and C2 also ensures the stability of the emulsion (E1) obtained from step a).

[0148] Composition C2 contains 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 composition C2 is crosslinkable.

[0149] In one embodiment, composition C2 comprises 50 to 99% by weight of a monomer or polymer as defined above, or a mixture of monomers or polymers as defined above, relative to the total weight of composition C2.

[0150] In one embodiment, composition C2 comprises from 1 to 20% by weight of a crosslinker or a mixture of crosslinkers as defined above relative to the total weight of composition C2.

[0151] In one embodiment, composition C2 comprises from 0.1 to 5% by weight of a photoinitiator or a mixture of photoinitiators as defined above, relative to the total weight of composition C2.

[0152] In one embodiment, the composition C2 contains 0.001 to 20% by mass of a crosslinking agent based on the total mass of the composition.

[0153] In one embodiment, 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.

[0154] Examples of these additional monomers or polymers include monomers or polymers that have pH-responsive groups, temperature-responsive groups, or UV- or IR-responsive groups.

[0155] These additional monomers or polymers can cause the rupture of the solid microcapsules and thus the release of their contents after stimulation, for example by pH, temperature, UV or IR.

[0156] These additional monomers or polymers may be selected from monomers or polymers having at least one of the following groups: - pH-responsive groups, such as primary, secondary, or tertiary amines, carboxylic acids, phosphates, sulfates, nitrates, or carbonates; - UV-responsive or UV-cleavable groups (or photochromic grops), such as azobenzene, spiropyran, 2-diazo-1,2-naphthoquinone, o-nitrobenzylated, thiol or 6-nitro-veratroyloxycarbonyl groups, such as poly(ethylene oxide)-bloc-poly(2-nitrobenzyl methacrylate) and other block copolymers, as described, for example, in Liu et al., Polymer Chemistry 2013, 4, 3431-3443; - IR-responsive or IR-cleavable groups, such as o-nitrobenzil or 2-diazo-1,2-naphthoquinone, for example the polymers described in Liu et al., Polymer Chemistry 2013, 4, 3431-3443; - hydrolysis responsive groups, such as poly(lactic acid), poly(glycolic acid), poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxybutyrate, chitosan, dextran, agarose, cellulose, and derivatives thereof; and - Temperature responsive groups, for example poly(N-isopropylacrylamide).

[0157] Step b) of the process according to the invention consists in preparing a second emulsion (E2).

[0158] The second emulsion consists of a dispersion of droplets of the first emulsion in a composition C3, which is not miscible with C2, produced by adding emulsion (E1) dropwise to C3 with stirring.

[0159] During step b), emulsion (E1) is at a temperature between 15° C. and 60° C. During step b), composition C3 is at a temperature between 15° C. and 60° C.

[0160] Under the addition conditions of step b), compositions C2 and C3 are not miscible, which means that the amount (by mass) of composition C2 that may be soluble in composition C3 is not more than 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total mass of composition C3, and the amount (by mass) of composition C3 that may be soluble in composition C2 is not more than 5%, preferably less than 1%, more preferably less than 0.5%, relative to the total mass of composition C2.

[0161] Thus, when emulsion (E1) is brought into contact with composition C3 under stirring, the latter is dispersed in the form of droplets ("double droplets") and the dispersion of these droplets of emulsion (E1) in the continuous phase C3 is called emulsion (E2).

[0162] Typically, the double droplet formed in step b) corresponds to a single droplet of composition C1 described above, surrounded by an envelope of composition C2, which completely encapsulates the single droplet.

[0163] The double droplets formed in step b) may also comprise at least two single droplets of composition C1, which are surrounded by an envelope of composition C2, completely encapsulating the single droplets.

[0164] Thus, a double droplet comprises one or more single droplets of composition C1 and a core composed of a layer of composition C2 surrounding the core.

[0165] The resulting emulsion (E2) is generally a double polydisperse emulsion (C1 in C2 in C3 emulsion or C1 / C2 / C3 emulsion), which means that the double droplets do not have a distinct size distribution in the emulsion (E2).

[0166] The immiscibility of Composition C2 and Composition C3 can prevent the layers of Composition C2 and Composition C3 from mixing, and can also ensure the stability of the emulsion (E2).

[0167] The immiscibility of Compositions C2 and C3 also prevents water-soluble materials of Composition C1 from migrating from the core of the droplets to Composition C3.

[0168] To carry out step b), any type of agitator commonly used to form emulsions can be used, such as a mechanical blade agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser, or a high-speed homogenizer.

[0169] In one embodiment, the viscosity of composition C3 at 25°C is higher than the viscosity of emulsion (E1) at 25°C.

[0170] According to the invention, the viscosity of composition C3 at 25° C. is between 500 and 100 000 mPa.s.

[0171] Preferably, the viscosity of composition C3 at 25° C. is between 3000 and 100000 mPa.s, more preferably between 5000 and 80000 mPa.s, for example between 7000 and 70000 mPa.s.

[0172] In this embodiment, taking into account the extremely high viscosity of the continuous phase formed by composition C3, the destabilization rate of the double droplets of emulsion (E2) is considerably slower relative to the duration of the process according to the invention, thus allowing the kinetic stabilization of emulsion (E2) and emulsion (E3) until the entire capsule envelope has been polymerized. Once polymerized, the capsules are thermodynamically stable.

[0173] The very high viscosity of composition C3 therefore ensures the stability of the emulsion (E2) obtained from step b).

[0174] The low surface tension between C3 and the first emulsion and the high viscosity of the system advantageously ensures the kinetic stability of the double emulsion (E2) and thus prevents it from dephasing over the length of the manufacturing process.

[0175] Preferably, the interfacial tension between composition C2 and composition C3 is low. A low interfacial tension between composition C2 and composition C3 can advantageously ensure the stability of the emulsion (E2) obtained from step b).

[0176] The volume fraction of the first emulsion in C3 can be varied from 0.05 to 0.5, on the one hand to improve the manufacturing performance and, on the other hand, to change the average capsule diameter. At the end of this process, the size distribution of the second emulsion is relatively wide.

[0177] 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, the ratio is between 1:9 and 3:1, more preferably between 1:9 and 1:1.

[0178] In one embodiment, composition C3 is preferably 5000 g.mol -1 and / or at least one branched polymer having a molecular weight greater than 5000 g.mol -1 and / or solid particles, such as silicates, having a molecular weight greater than

[0179] In one embodiment, composition C3 is preferably 5000 g.mol -1 Molecular weight greater than 10,000 g.mol -1 to 500000 g.mol -1 Molecular weights between 50,000 g.mol and 50,000 g.mol -1 to 300,000 g.mol -1 The polymer comprises at least one branched polymer having a molecular weight between 100 and 200.

[0180] A "branched polymer" refers to a polymer having at least one branch point between its two end groups, a "branch point" being a point on the molecular chain to which a side chain (also called a "pendant chain") is attached.

[0181] Examples of branched polymers include graft polymers, comb polymers, star polymers and dendrimers.

[0182] In one embodiment, composition C3 is 5000 g.mol -1 Molecular weight greater than 10,000 g.mol -1 to 500000 g.mol -1 For example, between 50,000 g.mol -1 to 300,000 g.mol -1 The polymer comprises at least one branched polymer having a molecular weight between 100 and 200.

[0183] Examples of polymers that can be used in composition C3 include the following compounds, used alone or mixed with one another: cellulose derivatives, for example cellulose ethers: methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or methylhydroxypropylcellulose; - polyacrylates (also known as carbomers), such as polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(hydroxyethyl methacrylate) (pHEMA), poly(N-2-hydroxypropyl methacrylate) (pHPMA); - polyacrylamides, such as poly(N-isopropylacrylamide) (PNIPAM); - Polyvinylpyrrolidone (PVP) and its derivatives; - Polyvinyl alcohol (PVA) and its derivatives; - poly(ethylene glycol), poly(propylene glycol) and its derivatives, such as poly(ethylene glycol) acrylate / methacrylate, poly(ethylene glycol) diacrylate / dimethacrylate, polypropylene carbonate; - polysaccharides, such as carrageenan, locust bean gum or tara gum, dextran, xanthan gum, chitosan, agarose, hyaluronic acid, gellan gum, guar gum, gum arabic, tragacanth gum, diutan gum, oat gum, karaya gum, ghatti gum, curdlan gum, pectin, konjac gum, starch; - protein derivatives, for example gelatin, collagen, fibrin, polylysine, albumin, casein; Silicone derivatives, such as polydimethylsiloxane (also known as dimethicone), alkyl silicones, aryl silicones, alkylaryl silicones, polyethylene glycol dimethicone, polypropylene glycol dimethicone; waxes, such as diester waxes (alkanediol diesters, hydroxy acid diesters), trimester waxes (triacylglycerol, alkane-1,2-diol triesters, ω-hydroxy acid and fatty acid triesters, hydroxymalonic acid, fatty acid and alcohol esters, hydroxy acid, fatty acid and fatty alcohol triesters, fatty acid, hydroxy 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, myristyl stearate, cetyl myristate, isocetyl stearate, glyceryl trimyristate, glyceryl tripalmitate, glyceryl monostearate or glyceryl palmitate and cetyl palmitate; fatty acids which can be used as waxes, such as cerotic acid, palmitic acid, stearic acid, dihydroxystearic acid, behenic acid, lignoceric acid, arachidic acid, myristic acid, lauric acid, tridecyclic acid, pentadecyclic acid, margaric acid, nonadecyclic acid, heneicosylic acid, tricosylic acid, pentacosylic acid, heptacosylic acid, montanic acid or nonacosylic acid; - fatty acid salts, in particular fatty acid aluminum salts, such as aluminum stearate, hydroxyaluminum bis(2-ethylhexanoate); - Isomerized Jojoba Oil; - Hydrogenated sunflower oil; - Hydrogenated coconut oil; - Hydrogenated Lanolin Oil; - castor oil and its derivatives, in particular modified hydrogenated castor oil or compounds obtained by esterification of castor oil with fatty alcohols; - polyurethanes and their derivatives; styrene polymers, for example styrene butadiene; and Polyolefins, for example polyisobutene.

[0184] In one embodiment, composition C3 includes solid particles such as clays, silicas, and silicates.

[0185] Examples of solid particles that can be used in composition C3 include clays and silicates, especially in the category of phyllosilicates (also known as "flaky silica"). Examples of silicates that can be used in the present invention include bentonite, hectorite, attapulgite, sepiolite, montmorillonite, saponite, sauconite, nontronite, kaolinite, talc, sepiolite, and chalk. Fumed synthetic silicates can also be used. The aforementioned clays, silicates, and silicas can be advantageously modified with organic molecules, such as polyethers, ethoxylated amides, quaternary ammonium salts, long-chain diamines, long-chain esters, polyethylene glycols, and polypropylene glycols.

[0186] These particles may be used alone or mixed with each other.

[0187] In one embodiment, composition C3 is 5000 g.mol -1 Mixtures of any of the foregoing compounds may be used.

[0188] Step c) of the method according to the invention consists of adjusting the size of the droplets of the second emulsion (E2).

[0189] This process is carried out with an applied shear rate of 10 s -1 From 100000 seconds -1 The emulsion (E2) may comprise a step of subjecting the emulsion (E2) to a controlled and uniform shear stress ranging from

[0190] In one embodiment, the polydisperse double droplets resulting from step b) are subjected to a sizing step consisting of subjecting them to a shear stress capable of fragmenting them into new double droplets of uniform and controlled diameter. Preferably, this shearing step is carried out using a Couette high shear cell according to the method described in patent application EP 15306428.2.

[0191] In one embodiment, in step c), the second emulsion (E2) resulting from step b), composed of polydisperse double droplets dispersed in a continuous phase, is subjected to shear deformation in a mixer applying a controlled uniform shear stress.

[0192] Thus, in this embodiment, step c) is performed when the applied shear rate is 1000 s -1 From 100000 seconds -1 The emulsion (E2) is subjected to a controlled and uniform shear stress for a period of time ranging from 0.1 to 1.5 seconds.

[0193] In this embodiment, in the mixer, the shear rate is considered to be controlled and uniform if it occurs at the same maximum value for all parts of the emulsion at a given time, which may vary from one point of the emulsion to another, regardless of the length of time. The exact configuration of the mixer is not important for the present invention, provided that the entire emulsion undergoes the same maximum shear deformation in existing equipment. Mixers suitable for carrying out step c) are described, inter alia, in the document US Pat. No. 5,938,581.

[0194] The second emulsion is - Two concentric rotating cylinders (also known as the "Couette mixer"); - Two parallel rotating discs; or - Two parallel diaphragms The cells are composed of a material that can undergo uniform and controlled shear deformation while cycling.

[0195] In this embodiment, the shear rate applied to the second emulsion is 1000 s -1 From 100000 seconds -1 Preferably for up to 1000 seconds -1 From 50000 seconds -1 Between 2000 and 3000 seconds, preferably 2000 seconds -1 From 20000 seconds -1 Until then.

[0196] In this embodiment, in step c), the second emulsion is inserted into a mixer and then subjected to shear stress, resulting in the formation of a third emulsion. The third emulsion (E3) is chemically the same as the second emulsion (E2), but is composed of monodisperse double droplets, whereas emulsion (E2) is composed of polydisperse double droplets. Typically, the third emulsion (E3) is composed of a dispersion of double droplets comprising a core composed of one or more droplets of composition C1 and a layer of composition C2 encapsulating the core, the double droplets being dispersed in composition C3.

[0197] The difference between the second and third emulsions is the diversity of the size of the double droplets: the droplets of the second emulsion are polydisperse in size, whereas the droplets of the third emulsion are monodisperse due to the fragmentation mechanism described above.

[0198] Preferably, in this embodiment, the second emulsion is continuously inserted into the mixer, meaning that the amount of double emulsion (E2) inserted at the inlet of the mixer is the same as the amount of third emulsion (E3) at the outlet of the mixer.

[0199] If the size of the droplets of the emulsion (E3) essentially corresponds to that of the solid microcapsules after polymerization, it is possible to adjust the size of the microcapsules and the thickness of the envelope by adjusting the shear rate in step c), with a high correlation between a decrease in droplet size and an increase in shear rate, which allows the adjustment of the resulting size of the microcapsules by varying the shear rate applied in step c).

[0200] In a preferred embodiment, the mixer used in step c) comprises two concentric cylinders, with an inner radius R o an outer cylinder with outer radius R i where the outer cylinder is fixed and the inner cylinder rotates with an angular velocity ω.

[0201] A Couette mixer suitable for the process according to the invention can be obtained from TSRFrance.

[0202] In one embodiment, the angular velocity ω of the rotating inner cylinder of the Couette mixer is 30 rad.s -1 That's all.

[0203] For example, the angular velocity ω of the rotating inner cylinder of a Couette mixer is approximately 70 rad.s -1 It is.

[0204] The size of the stationary outer cylinder of the Couette mixer is determined by the space between the rotating inner cylinder and the stationary outer cylinder (d=R o -R i ) can be selected to modulate

[0205] In one embodiment, the space between two concentric cylinders of the Couette mixer (d=R o -R i ) is between 50 μm and 1000 μm, preferably between 100 μm and 500 μm, for example between 200 μm and 400 μm.

[0206] For example, the distance d between two concentric cylinders is equal to 100 μm.

[0207] In this embodiment, during step c), the second emulsion is inserted at the inlet of the mixer, typically by means of a pump, and directed into the space between two concentric cylinders, the outer cylinder being fixed and the inner cylinder rotating with angular velocity ω.

[0208] The shear rate applied to the double emulsion while it is in the space between the two cylinders is given by the following equation:

[0209]

number

[0210] (In the formula, - ω is the angular velocity of the inner rotating cylinder, - R o is the inner radius of the fixed outer cylinder, - R i is the outer radius of the rotating inner cylinder)

[0211] In another embodiment, when the viscosity of composition C3 is higher than 2000 mPa.s at 25° C., step c) is performed at a shear rate of 1000 s -1 to the emulsion (E2).

[0212] In this embodiment, the fragmentation step c) is carried out by stirring the mixture in any type of agitator commonly used to form emulsions at a shear rate of 1000 s -1 It is possible to carry out the process using less than 2000 mPa.s, ie using the conditions described in patent application FR 1 661 787, in which case the viscosity of composition C3 is higher than 2000 mPa.s.

[0213] The geometry of the double droplets formed at the end of this process will determine the geometry of the subsequent capsules.

[0214] In this embodiment, in step c), the emulsion (E2) composed of polydisperse droplets dispersed in a continuous phase is mixed, for example, in a mixer at low shear rates, i.e., 1000 s -1 Less than this, it is subjected to shear stress.

[0215] In this embodiment, for example, the shear rate applied in step c) is 10 s -1 From 1000 seconds -1 Until then.

[0216] Preferably, the shear rate applied in step c) is exactly 1000 s -1 is less than.

[0217] In this embodiment, the droplets of emulsion (E2) cannot be efficiently fragmented into fine, monodisperse droplets of emulsion (E3) without subjecting them to high shear stress.

[0218] The shear stress σ exerted on the droplets of emulsion (E2), in step d), is defined as the tangential force per unit surface area of ​​the droplet resulting from the macroscopic shear exerted on the emulsion during stirring.

[0219] In step d), the shear stress σ (expressed in Pa), the viscosity η (expressed in Pa sec) of composition C3, and the shear rate γ (expressed in sec) applied to the emulsion (E2) during stirring are -1 is represented by the following formula: σ=ηγ are related by

[0220] Thus, in this embodiment, the increased viscosity of composition C3 allows extremely high shear stress to be applied to the droplets of emulsion (E2) in the mixer, even if the shear rate is low and the shear is non-uniform.

[0221] To carry out step c), in this embodiment, any type of agitator commonly used to form emulsions can be used, such as a mechanical blade agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloid mill, a high-shear disperser, or a high-speed homogenizer.

[0222] In a preferred embodiment, step c) is carried out using a simple emulsifier, such as a mechanical blade stirrer or a static stirrer. Indeed, this is because this embodiment also involves controlled shear deformation, e.g., 1000 s -1 This is possible because no shear exceeding this is required.

[0223] Step d) of the method according to the invention consists of a cross-linking step, thus forming the envelope of the solid microcapsules according to the invention.

[0224] Both steps allow obtaining the expected capsule retention performance and ensure its thermodynamic stability while crucially preventing any destabilization mechanisms, such as coalescence or hardening.

[0225] In one embodiment, when composition C2 comprises a photoinitiator, step d) is a photopolymerization step consisting of exposing emulsion (E3) to a light source suitable for initiating the photopolymerization of composition C2, in particular a UV light source preferably emitting in the wavelength range from 100 nm to 400 nm, in particular for a time length shorter than 15 minutes.

[0226] In this embodiment, step d) consists of subjecting the emulsion (E3) to photopolymerization, thereby making it possible to photopolymerize the composition C2, which makes it possible to obtain microcapsules encapsulating said water-soluble substances.

[0227] In one embodiment, step d) consists of exposing the emulsion (E3) to a light source suitable for initiating the photopolymerization of composition C2.

[0228] Preferably, the light source is a UV light source.

[0229] In one embodiment, the UV light source emits in the wavelength range between 100 nm and 400 nm.

[0230] In one embodiment, the emulsion (E3) is exposed to the light source for a period of time less than 15 minutes, preferably between 5 and 10 minutes.

[0231] In step d), the envelope of the aforementioned double droplets, composed of photocrosslinkable composition C2, is crosslinked and converted into a viscoelastic polymer envelope that encapsulates the water-soluble substance and protects it from release in the absence of a mechanical trigger.

[0232] In another embodiment, when composition C2 does not contain a photoinitiator, step d) is a polymerization step without exposure to a light source, the duration of the polymerization step d) is preferably between 8 hours and 100 hours, and / or this step d) is carried out at a temperature between 20°C and 80°C.

[0233] In this embodiment, polymerization is initiated, for example, by exposure to heat (thermal initiation), or simply by contacting the monomers, polymer, and crosslinker with each other or with a catalyst. Polymerization times in this case are generally longer than several hours.

[0234] Preferably, step d) of polymerizing composition C2 is carried out at a temperature between 20° C. and 80° C. for a period of between 8 and 100 hours.

[0235] The composition comprising solid microcapsules dispersed in composition C3 resulting from step d) is ready for use and does not require any additional post-treatment of the capsules and can be used.

[0236] The thickness of the envelope of the microcapsules thus obtained is between 0.1 μm and 20 μm, preferably between 0.2 μm and 8 μm, more preferably between 0.2 μm and 5 μm.

[0237] In one embodiment, the solid microcapsules obtained from step d) are surfactant-free.

[0238] The method according to the invention has the advantage that it does not require any surfactants in any of the steps described, thus making it possible to reduce the amount of additives obtained after release of the flavoring agent, which may modify the properties of the final product.

[0239] The present invention also relates to the use of a composition as defined above for cleaning and / or caring for fabrics.

[0240] The present invention also relates to the use of microcapsules as defined above for improving the olfactory and / or organoleptic properties of a fabric cleaning and / or care composition.

[0241] The present invention also relates to the use of microcapsules as defined above for reducing or preventing the evaporation of the flavoring agent provided by the microcapsules.

[0242] The expressions "between ... and ..." and "from ...- ..." are to be considered as inclusive, unless otherwise indicated.

[0243] The following examples illustrate the invention without limiting its scope. EXAMPLES

[0244] Example 1 Microcapsule production All stirring steps are carried out using a mechanical stirrer (Ika Eurostar 20) equipped with a sawtooth propeller.

[0245] Preparation of Composition C1

[0246] [Table 1]

[0247] The ingredients of Phase A are stirred together at 300 rpm until homogenous. To prepare Phase B, Tween 80 is gradually added to distilled water while stirring at 2000 rpm until homogenous. Phase A is then gradually added to Phase B while stirring at 2000 rpm. The ingredients are stirred for 2 minutes and sonicated (SFX 550, Branson) in an ice bath at 40% amplitude for 1.5 minutes (pulse 10 sec / 5 sec).

[0248] After cooling, 1.4 g of Aculyn 44N gelling agent (Dow) are added to the mixture, stirring at 200 rpm, until gelling, to obtain composition C1.

[0249] Preparation of the first emulsion (E1)

[0250] [Table 2]

[0251] Composition C1 is gradually added to composition C2 with stirring at 300 rpm.

[0252] Preparation of the second emulsion (E2)

[0253] [Table 3]

[0254] Composition C3 is stirred at 1000 rpm until completely homogenous and then left to rest for 1 hour at room temperature (RT).

[0255] The first emulsion (E1) is then gradually added to the composition C3, with stirring at 2000 rpm, thus obtaining the second emulsion (E2).

[0256] Adjusting the size of the second emulsion The second polydisperse emulsion (E2), obtained from the previous step, is stirred at 2000 rpm for 3 minutes, which results in a monodisperse emulsion (E2).

[0257] Cross-linking of capsule envelope The second monodisperse emulsion (E3) obtained from the previous step was then photochromatographed using a UV light source (Dymax LightBox ECE2000) with a maximum light intensity of 0.1 W / cm 2 Then, irradiate with light at a wavelength of 365 nm for 10 minutes.

[0258] The microcapsules obtained have a mean size of 9.5 μm and a size distribution with a standard deviation of 3.1 μm, ie 33%.

[0259] The microcapsules obtained are subjected to three successive dilution cycles with distilled water and centrifuged in order to produce a suspension of microcapsules in distilled water containing 50% by weight of microcapsules.

[0260] Example 2 Biodegradability Test The biodegradability of the microcapsules produced according to Example 1 is measured according to OECD guideline 301A available on the OECD website at the following URL: https: / / www.oecd-ilibrary.org / fr / environment / essai-n-301-biodegradabilite-facile_9789264070356-fr.

[0261] Briefly, the microcapsule suspension is diluted in distilled water such that its concentration in dissolved organic carbon (DOC) is between 10 mg DOC / L and 40 mg DOC / L and incubated with inoculum from a municipal organic water treatment plant in a light-tight chamber with stirring at 22° C. DOC analysis is performed at regular intervals and reveals a biodegradation rate of 70% in 28 days.

[0262] Thus, the microcapsules produced according to Example 1 are biodegradable.

[0263] Example 3 Preparation of main cleaning product formulations The following formulations for the main cleaning products are provided:

[0264] [Table 4]

[0265] Two samples are prepared from this formulation containing the same concentration of Romance 0330 perfume: sample LP1 containing 5% by weight of microcapsules prepared according to example 1 and sample LP2 containing 0.97% by weight of Romance 0330 perfume.

[0266] Example 4 Fabric softening rinse formulation The following formulations of fabric softeners are provided:

[0267] [Table 5]

[0268] Two samples are prepared from this formulation containing the same concentration of Romance 0330 perfume: sample AD1 containing 5% by weight of microcapsules prepared according to example 1 and sample AD2 containing 0.97% by weight of Romance 0330 perfume.

[0269] Example 5 Preparation of washed cotton fabric samples 10 g of one of the products produced according to Example 3 or Example 4 is mixed with 1 L of deionized water. A 56×10 cm cotton fabric sample is stirred in the resulting solution for 5 minutes, drained, then stirred in 1 L of deionized water for 2 minutes, drained, and then dried in the open air for 12 hours.

[0270] Example 6 Sensory test after 12 hours Cotton fabric samples prepared according to Example 5 are rated by a panel of five people according to a scent intensity scale of 0 to 5, where 0 represents no scent and 5 represents very strong scent. Each person has two fabric samples for each fabric care product sample: one is rated intact and the other is rated after rubbing the fabric against itself. The perceived intensity (mean ± SD) for each sample is shown in the table below (Table 6).

[0271] [Table 6]

[0272] These results show the desired quality of microcapsules on fabric fibers for the two fabric care products tested. The perceived intensity before rubbing is lower in the samples containing microcapsules because the perfume is trapped inside the microcapsules. Under the effect of rubbing, the microcapsules break and release the perfume inside. Thus, the perceived intensity after rubbing is greater in the samples containing microcapsules, indicating that the amount of perfume attached to the fabric fibers is greater than the amount that would be attached if the perfume were free.

[0273] Example 7 Sensory test after 7 days The cotton fabric samples prepared according to Example 5 are stored in non-airtight boxes for 7 days and evaluated by a panel of five people according to the procedure described in Example 6. The perceived intensity (mean ± SD) for each sample is shown in the table below (Table 7).

[0274] [Table 7]

[0275] These results show that the microcapsules provide protection to the perfume against evaporation: indeed, after rubbing, the perceived intensity is significantly greater when the perfume is encapsulated than when the perfume is free, thus indicating a greater amount of perfume remaining on the fabric after 7 days.

Claims

1. - at least one composition for cleaning and / or caring for fabrics, at least one solid microcapsule having an average diameter between 1 μm and 30 μm, - a core composed of a composition C1 comprising at least one flavoring agent and at least one agent for adjusting the hydrophobicity of the flavoring agent, the agent having a ClogP of 4 or more, the composition C1 being in the form of an emulsion comprising a continuous phase in the form of an aqueous gel; and - a solid cross-linked polymer envelope around and completely encapsulating the core, the solid cross-linked polymer envelope comprising a cross-linked polymer obtained by polymerizing at least one monomer or polymer having at least one reactive moiety selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, vinyl ester, thiolene, maleate, epoxy, siloxane, amine, lactone, phosphate and carboxylate moieties, the thickness of the solid cross-linked polymer envelope being between 0.1 μm and 20 μm. and a solid microcapsule comprising A composition comprising:

2. 2. The composition of claim 1, wherein each of the solid microcapsules is as defined in claim 1, and the standard deviation of the diameter distribution of the solid microcapsules is less than 50% or less than 1 μm.

3. 3. The composition according to claim 1, wherein the composition C1 of the core of the solid microcapsules comprises at least 20% by weight of flavoring agent relative to the total weight of the composition C1.

4. 4. The composition according to claim 1, wherein composition C1 further comprises at least one aqueous gelling agent.

5. 5. The composition of claim 4, wherein the aqueous gelling agent is selected from the group consisting of cellulose derivatives, polyacrylates, polyvinylpyrrolidones, polyacrylamides and their derivatives, polyvinyl alcohols and their derivatives, poly(ethylene glycols), poly(propylene glycols) and their derivatives, polysaccharides, protein derivatives, polyurethanes and their derivatives, and clays and silicates.

6. 6. The composition according to any one of claims 1 to 5, wherein the crosslinked polymer is obtained by polymerization from monomers or polymers selected from aliphatic or aromatic esters or polyesters, urethanes or polyurethanes, anhydrides or polyanhydrides, saccharides or polysaccharides, ethers or polyethers, amides or polyamides, and carbonates and polycarbonates, said monomers or polymers further comprising at least one reactive moiety selected from the group consisting of acrylate moieties, methacrylate moieties, vinyl ether moieties, N-vinyl ether moieties, vinyl ester moieties, thiolene moieties, maleate moieties, epoxy moieties, siloxane moieties, amine moieties, lactone moieties, phosphate moieties and carboxylate moieties.

7. 7. The composition of claim 1, wherein the crosslinked polymer is selected from the group consisting of crosslinked polyesters, crosslinked polyepoxies, and crosslinked polyurethanes.

8. 8. The composition according to claim 1, wherein the crosslinked polymer of the envelope of the solid microcapsules is obtained by polymerizing a composition C2 comprising at least one monomer or polymer having at least one reactive moiety as defined in claim 1, at least one crosslinking agent, and optionally at least one crosslinking photoinitiator or catalyst.

9. 9. Use of a composition according to any one of claims 1 to 8 for cleaning and / or caring for fabrics.

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