BR112020017579B1 - COMPOSITION, METHOD FOR EMBEDDING AND/OR ATTACHING HYPERBRANCHED POLYSACCHARIDE INTO AND/OR ON WRAP OF MICROCAPSULES, MICROCAPSULATE, USE OF A HYPERRANCHED POLYMER AND CONSUMER PRODUCT - Google Patents

Abstract

The present invention relates to a composition comprising at least one core-shell type microcapsule in a suspension medium. The microcapsule comprises a core and a shell around said core. The core comprises a hyperbranched polysaccharide selected from the group consisting of amylopectins, dextrins, hyperbranched starches, glycogen and phytoglycogen and mixtures thereof.

Description

[001] The present invention refers to core-shell type microcapsules that exhibit better deposition on keratinous substrates and greater resistance to rinsing after deposited on these substrates.

[002] The incorporation of encapsulated functional materials into consumer products, such as household hygiene products, personal care products and fabric care products, is already known. Functional materials include, for example, fragrances, cosmetic agents, drugs, and substrate enhancers.

[003] Microcapsules that are particularly suitable for delivering such functional materials are core-shell microcapsules, in which the core typically comprises the functional materials and the shell is impermeable or partially impermeable to the functional material. These microcapsules are usually used in aqueous media and the encapsulated ingredients are hydrophobic. A wide selection of wrap materials can be used, as long as the wrap material is impermeable or partially impermeable to the encapsulated ingredient.

[004] Among functional materials, fragrance compositions are encapsulated for several reasons. Microcapsules can isolate and protect perfume-type ingredients from external suspending media, such as consumer product bases, where they may be incompatible or unstable. They are also used to assist in the deposition of perfume-type ingredients onto substrates such as skin, hair, fabric or hard surfaces. They can also act as a means of controlling the spatio-temporal release of perfume.

[005] Thermosetting resins are common encapsulating materials for perfume compositions. Core-shell microcapsules formed from aminoplast resins, polyurea resins, polyurethane resins, polyacrylate resins, and combinations thereof generally have sufficient resistance to fragrance loss when dispersed in aqueous suspension media, even in containing surfactant. Furthermore, when incorporated into consumer products, such as detergents or laundry conditioners, they offer perfumery benefits that cannot be obtained if the perfume is incorporated directly into these products.

[006] In many cases, however, the deposition and adhesion of these microcapsules to smooth surfaces and especially to keratinous surfaces, such as skin and hair, are insufficient and the expected benefits associated with the use of microcapsules are not ideal. This is especially the case with rinse-off products involving large amounts of water. In this case, the lack of deposition may be due to the dilution of the microcapsules to such a low level that the microcapsule is unlikely to reach the surface on which it is to be deposited. Large volumes of rinse water can also remove microcapsules from the surface.

[007] Document US 2012/0282309 A1 discloses a hair conditioner composition containing anionic polyacrylate microcapsules and a deposition aid, such as a cationic deposition polymer or an aminosilicone. Document US 8,927,026 B2 refers to a shampoo composition of anionic polyacrylate microcapsules and a microcapsule and cationic deposition polymer.

[008] In both cases, the microcapsules are coated with an anionic surfactant and the cationic polymer is added forming a premix with the coated microcapsules before being added to the shampoo or conditioner base. Such an approach is complex and can result in electrostatically induced incompatibility problems, such as aggregation of microcapsules in the premix and phase separation during mixing of the premix and shampoo or conditioner base. This may affect the properties of the final product and may require modification of the composition of the final product in which the microcapsules are used.

[009] It is, therefore, a secondary objective of the present invention to overcome the aforementioned drawbacks of the prior art. In particular, a secondary objective of the present invention is to present microcapsules presenting better deposition on keratinous substrates and greater resistance to rinsing after deposited on these substrates. Microcapsules must be cheap and simple to produce and versatile in terms of their application. No modification or only minimal modification of the composition of the product should be necessary in relation to its use.

[0010] In a first aspect of the present invention, it presents a composition comprising at least one core-shell type microcapsule in a suspension medium. Said microcapsule comprises a core and a shell around said core. The wrapper comprises a hyperbranched polysaccharide selected from the group consisting of amylopectins, dextrins, hyperbranched starches, glycogen and phytoglycogen, and mixtures thereof.

[0011] In the context of the present invention, the term "hyperbranched polysaccharide"; or more generally "hyperbranched polymer", refers to a polymer comprising a primary chain or core, one or more secondary chains attached to the primary chain or core, and one or more tertiary chains attached to at least one of said chains secondary.

[0012] Typically, a secondary chain has one or more tertiary chains attached to it, but - to avoid any ambiguity - some secondary chains in the hyperbranched polymer may also not have tertiary chains attached to them. Preferably, at least 10%, preferably more than 20%, even more preferably more than 25%, of the secondary chains in the hyperbranched polymer have one or more tertiary chains attached thereto.

[0013] The invention is based on the discovery that embedding and/or fixing a hyperbranched polysaccharide in core-shell microcapsules improves both the deposition and rinsing resistance of core-shell microcapsules, in particular on keratinous surfaces such as like skin or hair.

[0014] In particular, better deposition and greater resistance to rinsing are observed when core-shell microcapsules are applied to the skin or hair through rinsable consumer products, such as shampoos, shower gels, soaps and detergents and conditioning compositions, for example fabric conditioners or hair conditioners.

[0015] This discovery was surprising as it is known that surfaces treated with hyperbranched polyglycerols are known to be resistant to adhesion to cells and proteins, providing good protection against the formation of biofilms, see, for example, Y. Zhou et al., Adv Mater. 2010, 22, 4567-4590.

[0016] A suitable way to characterize the degree of branching of the above hyperbranched polysaccharides is by indicating their ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds.

[0017] In a specific embodiment of the invention, the ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds in the hyperbranched polysaccharide is greater than 1/50, more particularly greater than 1/40 and even more particularly greater than 1/35. Hyperbranched polysaccharides having a ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds of less than 1/50 have properties that are similar to those of linear polysaccharides and are therefore less suitable for the purpose of the present invention . In particular, the viscosity of microcapsule pastes with linear polysaccharides increases greatly with a decreasing ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds at a constant molecular weight of the polysaccharide, leaving the paste less fluid and harder. to be incorporated into the final product.

[0018] In the context of the present invention, the hyperbranched polymer can be embedded and/or fixed to the envelope of the microcapsules. The amount of hyperbranched polymer, in particular embedded and/or attached to the microcapsule shell, may vary from 0.01 to 1% by weight, more particularly from 0.02 to 0.5% by weight, and even more particularly from 0.05 to 0.25% by weight, relative to the total weight of the suspension in the microcapsule. In lower amounts, the hyperbranched polymer is ineffective, while in higher amounts the surface of the microcapsules becomes saturated and it is no longer possible to incorporate any amount of hyperbranched polymer into it. This may result in undesirable effects such as an increase in the viscosity of the microcapsule paste or a phase separation in the paste.

[0019] The core may comprise a perfume-type ingredient, a cosmetic ingredient or a mixture thereof.

[0020] In advantageous embodiments of the invention, the core of the at least one core-shell microcapsule comprises a thermosetting resin, in particular a thermosetting resin selected from the group consisting of aminoplast resins, polyurea resins, acrylic resins, and mixtures of the same. These resins are well known in the art as being particularly suitable for the encapsulation of small and/or volatile functional materials.

[0021] In a second aspect of the invention, the invention presents a method for embedding and/or fixing hyperbranched polymers in microcapsule shells, comprising the steps of: dispersing droplets of a core material in a suspension medium, in particular comprising an emulsifier, in the presence of shell-forming monomers, pre-polymers or pre-condensates to obtain an emulsion, in particular an oil-in-water emulsion; causing the monomers, pre-polymers or pre-condensates to react at the interface of the droplets and the suspension medium to obtain a paste of core-shell type microcapsules; adding a hyperbranched polymer; obtaining a composition comprising a paste of core-shell type microcapsules, in which the hyperbranched polymer is embedded and/or fixed in the shells of the core-shell type microcapsules; optionally adding to the paste one or more suspending agent or preservative; optionally dehydrating the paste to form a core-shell microcapsule composition, particularly in powder form.

[0022] Extraordinarily, the addition of a hyperbranched polymer can be carried out before the shell-forming monomer, pre-polymers or pre-condensates react, during the reaction of these materials or after the end of the reaction. The total amount of hyperbranched polymer can be added in a single operation, or it can be added sequentially and/or little by little.

[0023] In specific embodiments of the invention, the hyperbranched polymer is selected from the group consisting of hyperbranched polyglycerols, hyperbranched polyerythritols and hyperbranched polysaccharides. These hyper-branched polymers have the advantage of being dispersible and/or non-toxic, as well as completely biodegradable.

[0024] In other specific embodiments of the invention, the hyperbranched polysaccharide is selected from the group consisting of amylopectins, dextrins, hyperbranched starches, glycogen and phytoglycogen and mixtures thereof. These hyperbranched polymers have the advantage of being easily commercially available.

[0025] Furthermore, the present invention relates to a microcapsule, in particular a core-shell type microcapsule, obtainable by the method mentioned above. The present invention also relates to a composition comprising at least one such microcapsule in a suspension medium.

[0026] In a third aspect of the invention, a method is presented for improving the deposition of at least one core-shell type microcapsule on a surface, in particular a keratinous surface, the method comprising the step of embedding and/or fixing a hyper-branched polymer to the envelope of said core-shell type microcapsule. Advantageously, this is achieved by the method for embedding and/or attaching hyperbranched polymers to microcapsule shells mentioned above. The invention also relates to the use of a hyperbranched polymer to improve the deposition of at least one core-shell type microcapsule onto a surface, in particular a keratinous surface, by embedding and/or attaching the hyperbranched polymer to the skin envelope. said core-shell type microcapsule, in particular by the above method.

[0027] In a fourth aspect of the invention, a method is presented for increasing the rinsing resistance of at least one core-shell type microcapsule deposited on a surface, in particular on a keratinous surface, the method comprising the step of embedding and /or attach a hyperbranched polymer to the shell of the core-shell microcapsule. Advantageously, this is achieved by the method for embedding and/or attaching hyperbranched polymers to microcapsule shells mentioned above. The invention also relates to the use of a hyperbranched polymer to increase the rinsing resistance of at least one core-shell type microcapsule deposited on a surface, in particular on a keratinous surface, by embedding and/or fixing a hyperbranched polymer. -branched to the shell of the core-shell type microcapsule, in particular by the above method.

[0028] Furthermore, the invention relates to a consumer product comprising a composition such as that described above. The consumer product can be a shampoo, hair conditioner, shower gel or liquid soap.

[0029] If the hyperbranched polymer is generated from a core, the core may have two or more chemical functions to which the secondary chain may be attached. From now on, this will be called the polyfunctional nucleus. The secondary chain may develop from a core chemical function by polymerization or may be attached to a core chemical function by grafting. The polyfunctional core may include glycerol, erythritol, glycidol, 2,2-bismethylol-proionic acid, 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid, ethylene glycol di(meth)acrylate, triethylene glycol tri(meth)acrylate , pentaerythritol triacrylate, a furanose (such as fructose), 1,2-di(oxiran-2-yl)ethane-1,2-diol, or a pyranose (such as glucose).

[0030] In a preferred embodiment of the present invention, the polyfunctional core is selected from the group consisting of glycerol, erythritol, glycidol, furanose, pyranose and glycogenin.

[0031] In a particular embodiment, the hyperbranched polymer comprises tertiary secondary chains, and higher order chains, in which the secondary chains are attached to a primary chain or a core.

[0032] The primary, secondary, tertiary and higher order chains can be any polyfunctional polymer, with one or more functional groups, preferably a plurality of functional groups, such as hydroxy, amine, glycidyl, isocyanate, vinyl and (met )acryloyl.

[0033] In a preferred embodiment of the present invention, the primary, secondary, tertiary and higher order chains have a plurality of hydroxy groups and are selected from the group consisting of polyglycerol, polyerythritol and polysaccharides.

[0034] Polysaccharide chains may comprise several sugar-like portions and portions derived from sugars. The sugar-like moieties may include pyranoses and furanoses, such as glucose, rhamnose, xylose, arabinose, galactose, fucose, apiose and fructose. Sugar-derived moieties may include dehydrated pyranoses, dehydrated furanoses, glucuronic acid, mannuronic acid, glucosamine and sulfate-galactose. A chain may comprise different sugar-like portions and sugar-derived portions.

[0035] In one embodiment, the polysaccharide chains comprise pyranose monomers, such as glucose.

[0036] In a particular embodiment, the pyranose monomer is glucose. Typically, the covalent bonds between two glucose rings in a polysaccharide chain are formed between the hydroxyl groups on the C1 carbon of one of the rings and the hydroxyl group on the C4' carbon of the other ring (called a 1,4' glycosidic bond), resulting in starch-based polymers when α-D-glucose is involved or in cellulose-based polymers when β-D-glucose is involved.

[0037] On the other hand, the branching of a polysaccharide chain generally involves the hydroxyl group located at the C1 carbon of any of the rings located in the first chain and a hydroxyl group located at the C6' carbon, C3' carbon or C2' carbon of any one of the rings located in the second chain, resulting in the so-called 1,6'-glycosidic bond, 1,3'-glycosidic bond or 1,2'-glycosidic bond.

[0038] Particularly preferred hyperbranched polysaccharides include natural polysaccharides that can be selected from the group consisting of amylopectins, glycogen, phytoglycogen and enzymatically branched starches. These polysaccharide polymers are characterized by the existence of 1,4'-linked pyranose chains connected to each other by 1,6'-, 1,3'- and 1,2'- bonds.

[0039] Amylopectin is characterized by a dendritic structure similar to a tree of chains of a-D-glucose units linked to each other by 1,4'-glycosidic bonds, with a primary chain (or first order chain), secondary chains (or second order chains), tertiary chains (or third order chains), and higher order chains connected in such a way that each order X chain is attached to an order X-1 chain by its first glucose, where most of the bonds involved in branching are 1,6'-glycosidic bonds. The ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds in amylopectin typically varies between about 1/30 and about 1/24.

[0040] The number of pyranose units involved in the amylopectin portion depends on the origin of the starch source. For example, the number of bound pyranose units involved in the amylopectin moieties of corn starch ranges between 280 and 35,000, whereas the number of bound pyranose units involved in the amylopectin moieties of potato starch ranges between 1,100 and 220,000.

[0041] Acidic or enzymatic degradation of amylopectins results in the formation of hyperbranched dextrins. These dextrins may additionally comprise 1,2'-glycosidic linkages and 1,3'-glycosidic linkages. These dextrins are also useful for the purpose of the present invention.

[0042] Glycogen and phytoglycogen are similar to amylopectin in the sense that the branches are linked to each other, but are characterized by an almost spherical dendritic structure of the branches and a higher branch density compared to amylopectin. The ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds in amylopectin typically varies between 1/12 and 1/8.

[0043] Starches subjected to enzymatic treatment with a glycogen branching enzyme (identification number: EC 2.4.1.18, also called glucuronosyltransferase) typically have ratios of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds between 1/25 and 1/8 and are therefore also suitable for the purpose of the present invention. For example, hyperbranched starch is obtained by treating starch or a starch derivative in a partially or completely gelatinized form with a glycogen branching enzyme (identification number: EC 2.4.1.18). Hyperbranched starch has a degree of molecular branching equal to 6%, preferably 6.5%. The degree of molecular branching is defined as the percentage of α-1,6-glycosidic bonds of the total α-1,6- and α-1,4-glycosidic bonds (α-1,6/(α-1,6 +α -1.4) x 100%).

[0044] The level of 1,6'-glycosidic bonds in a polysaccharide can be determined by measuring the difference in the amount of reducing ends before and after enzymatic debranching of the product using isoamylase (see, for example, Y. Takeda et al ., Carbohydr. Res. 1993, 240, 253-263).

[0045] Starches rich in hydrophobically modified amylopectin, such as starch functionalized with octenyl succinic anhydride (OSA) or dodecenyl succinic anhydride (DDSA) are also useful for the purpose of the present invention. Typically, these modified starches have a degree of substitutions between 1 and 10% by weight of the dry starch.

[0046] Other specific hyperbranched polymers that may be useful in accordance with the present invention may be selected from the group consisting of synthetic poly(polyols), such as polyglycerols, polyerythritol, poly(3-ethyl-3-hydroxymethyloxane) and poly(2-hydroxymethyloxane), hyperbranched polymers such as poly(1,6-anhydro-β-D-gluco(manno, galacto)pyranose), poly(5,6-anhydro-1,2-O) glycopolymer -isopropylidene-α-D-glucofuranose) and hyperbranched polyether ketal, poly(3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid), poly(2,2-di(oxiran-2-yl) chloride propanoyl or hyperbranched poly(ether-co-ester) polymers.

[0047] In a particular embodiment of the present invention, core-shell microcapsules can be formed by preparing a paste containing core-shell microcapsules, and adding a hyperbranched polymer to the paste so that it is adsorbed on the surface of the microcapsules. .

[0048] In another particular embodiment, the hyper-branched polymer can be incorporated into core-shell microcapsules by adding the hyper-branched polymer to the nascent microcapsule paste and embedding and/or fixing the hyper-branched polymer in the microcapsule shells. core-envelope type springs as they form.

[0049] In the context of the present invention, the term "nascent" when referring to microcapsules, describes microcapsules that are in the process of being formed and where an envelope-forming reaction occurs, such as interfacial polymerization, polyaddition, polycondensation, radical polymerization , ring opening polymerization, among others.

[0050] In these envelope formation processes, the reaction site is typically the interface that separates the droplets of hydrophobic core material from an external aqueous phase in which the droplets are dispersed. In a typical microencapsulation process, this interface is stabilized by surfactants or polymeric emulsifiers.

[0051] In a particular embodiment of the present invention, the hyperbranched polymer is added during the microcapsule shell formation process, so that the polymer is physically embedded in the shells as microencapsulation continues.

[0052] In a more particular embodiment, the composition of the present invention can be formed according to a method comprising the following steps: dispersing the droplets of functional material in an aqueous phase comprising an emulsifier in the presence of envelope-forming monomers, pre- polymers or precondensed to form an oil-in-water emulsion; causing the monomers, prepolymers or precondensates to react at the interface of the droplets and the aqueous phase to form a paste of nascent core-shell microcapsules; adding a hyperbranched polymer to the nascent core-shell microcapsule paste to form a composition comprising a core-shell microcapsule paste, wherein the hyperbranched polymer is embedded in the shells of the core-shell microcapsules; optionally adding to the paste one or more of a suspending agent, a preservative or any other conventional excipients; optionally dehydrating the paste to form a core-shell microcapsule composition in powder form.

[0053] When carrying out step a), the mixing apparatus and mixing speed can be controlled in a manner known per se, in order to provide any desired droplet size. Mixing can be carried out with a propeller, a turbine, a cross-beam agitator with an inclined beam, such as a Mig agitator. Typically, the emulsion is formed at an agitation speed in the range of 100 to 2000 rpm, more particularly 250 to 1500 rpm, and even more particularly 500 rpm to 1000 rpm for a container with a volume of 1 liter, equipped with a cross-beam agitator with inclined beam, and having a ratio of the agitator diameter to the reactor diameter equal to 0.7. The agitator may comprise a turbine, a Mig agitator. The person skilled in the art, however, will understand that such stirring conditions can be altered depending on the size of the reactor and the volume of the slurry, the exact geometry of the stirrer and the ratio of the stirrer diameter to the reactor diameter. For example, for a Mig stirrer with a ratio of stirrer diameter to reactor diameter of 0.5 to 0.9 and slurry volumes ranging from 0.5 to 8 tons, the preferable stirring speed in the context of the present invention varies from 150 rpm to 50 rpm.

[0054] When carrying out step c), the addition of the hyperbranched polymer can be carried out before the shell-forming monomer, pre-polymers or pre-condensates react, or during the reaction of these materials. The total amount of hyperbranched polymer can be added in a single operation, or it can be added sequentially and/or little by little.

[0055] A wide selection of functional materials can be used in the core-shell microcapsules of the present invention. The core may in particular comprise a hydrophobic material selected from the group consisting of oils, essential oils, fragrance oils, biocides, pheromones, lipophilic cosmetic ingredients and topical drugs.

[0056] In one embodiment, the hydrophobic core material is a fragrance composition comprising at least one fragrance ingredient.

[0057] An exhaustive list of perfume-type ingredients that can be encapsulated according to the present invention can be found in the perfumery literature, for example, "Perfume & Flavor Chemicals", S. Arctander (Allured Publishing, 1994). The encapsulated perfume according to the present invention preferably comprises perfume-like ingredients selected from ADOXALTM (2,6,10-trimethylundec-9-enal); AGRUMEXTM (2-(tert-butyl)cyclohexyl acetate); ALDEHYDE C 10 DECYLIC (decanal); ALDEHYDE C 11 MOA (2-methyldecanal); UNDECYLENIC C 11 ALDEHYDE (undec-10-enal); UNDECYLIC ALDEHYDE C 110 (undecanal); ALDEHYDE C 12 LAURIC (dodecanal); ALDEHYDE C 12 MNA PURE (2-methylundecanal); ALDEHYDE ISO C 11 ((E)-undec-9-enal); MANDARINE ALDEHYDE 10%/TEC ((E)-dodec-2-enal); ALLYL AMYL GLYCOLATE (allyl 2-(isopentyloxy)acetate); ALLYL CYCLOHEXYL PROPIONATE (allyl 3-cyclohexylpropanoate); ALLYL OENANTATE (allyl heptanoate); AMBER CORETM (1-((2-(tert-butyl)cyclohexyl)oxy)butan-2-ol); AMBERMAXTM (1,3,4,5,6,7-hexahydro-beta-1,1,5,5-pentamethyl-2H-2,4a-methanonaphthalene-8-ethanol); AMYL SALICYLATE (pentyl 2-hydroxybenzoate); APHERMATE (1-(3,3-dimethylcyclohexyl)ethyl formate); BELAMBRETM ((1R,2S,4R)-2'-isopropyl-1,7,7-trimethylspiro[bicyclo[2,2,1]heptane-2,4'-[1,3]dioxane]); BIGARYL (8-(sec-butyl)-5,6,7,8-tetrahydroquinoline); BOISAMBRENETM FORTETM ((ethoxymatoxy)cyclododecane); BOISIRISTM ((1S,2R,5R)-2-ethoxy-2,6,6-trimethyl-9-methylenebicyclo[3,3,1]nonane); BORNYL ACETATE ((2S,4S)-1,7,7-trimethylbicyclo[2,2,1]heptan-2-yl acetate); BUTYL BUTYRO LACTATE (1-butoxy-1-oxopropan-2-yl butyrate); BUTYL CYCLOHEXYL ACETATE FOR (4-(tert-butyl)cyclohexyl acetate); CARYOPHYLLENE ((Z)-4,11,11-trimethyl-8-methylenebicyclo[7,2,0]undec-4-ene); CASHMERANTM (1,1,2,3,3-pentamethyl-2,3,6,7-tetrahydro-1H-inden-4(5H)-one); CASSYRANETM (5-tert-butyl-2-methyl-5-propyl-2H-furan); CITRAL ((E)-3,7-dimethylocta-2,6-dienal); CITRAL LEMAROMETM N ((E)-3,7-dimethylocta-2,6-dienal); CITRATHALTM R ((Z)-1,1-diethoxy-3,7-dimethylocta-2,6-diene); CITRONELLAL (3,7-dimethyloct-6-enal); CITRONELLOL (3,7-dimethyloct-6-en-1-ol); CITRONELLYL ACETATE (3,7-dimethyloct-6-en-1-yl acetate); CITRONELLYL FORMIATE (3,7-dimethyloct-6-en-1-yl formate); CITRONELLYL NITRILE (3,7-dimethyloct-6-enonitrile); CITRONELLYL PROPIONATE (3,7-dimethyloct-6-en-1-yl propionate); CLONAL (dodecanonitrile); CORANOL (4-cyclohexyl-2-methylbutan-2-ol); COSMONETM ((Z)-3-methylcyclotetradec-5-enone); CYCLAMEN ALDEHYDE (3-(4-isopropylphenyl)-2-methylpropanal); CYCLOGALBANATE (allyl 2-(cyclohexyloxy)acetate); CYCLOHEXYL SALICYLATE (cyclohexyl 2-hydroxybenzoate); CYCLOMYRAL (8,8-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalene-2-carbaldehyde); DAMASCENONE ((E)-1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one); DAMASCONE ALPHA ((E)-1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one); DAMASCONE DELTA ((E)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-1-one); DECENAL-4-TRANS ((E)-dec-4-enal); DELPHONE (2-pentylcyclopentanone); DIHYDRO ANETHOLE (1-(1-(3,3-dimethylcyclohexyl)ethyl) propanedioic acid 3-ethyl ester); DIHYDRO JASMONE (3-methyl-2-pentylcyclopent-2-enone); DIMTHYL BENZYL CARBINOL (2-methyl-1-phenylpropan-2-ol); DIMTHYL BENZYL CARBYNYL ACETATE (2-methyl-1-phenylpropan-2-yl acetate); DIMTHYL BENZYL CARBYNYL BUTYRATE (2-methyl-1-phenylpropan-2-yl butyrate); DIMETHYL OCTENONE (4,7-dimethyloct-6-en-3-one); DIMETOL (2,6-dimethylheptan-2-ol); DIPENTENE (1-methyl-4-(prop-1-en-2-yl)cyclohex-1-ene); DUPICALTM ((E)-4-((3aS,7aS)-hexahydro-1H-4,7-methanoinden-5(6H)-ylidene)butanal); EBANOLTM ((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); ETHYL CAPROATE (ethyl hexanoate); ETHYL CAPRYLATE (ethyl octanoate); ETHYL LINALOOL ((E)-3,7-dimethylnone-1,6-dien-3-ol); ETHYL LINALYL ACETATE ((Z)-3,7-dimethylnone-1,6-dien-3-yl acetate); ETHYL OENANTATE (ethyl heptanoate); ETHYL SAFRANATO (ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate); EUCALYPTOL ((1s,4s)-1,3,3-trimethyl-2-oxabicyclo[2,2,2]octane); FENCHYL ACETATE ((2S)-1,3,3-trimethylbicyclo[2,2,1]heptan-2-yl acetate); FENCHIL ALCOHOL ((1S,2R,4R)-1,3,3-trimethylbicyclo[2,2,1]heptan-2-ol); FIXOLIDETM (1-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethanone); FLORALOZONETM (3-(4-ethylphenyl)-2,2-dimethylpropanal); FLORHYDRAL (3-(3-isopropylphenyl)butanal); FLOROCYCLENETM ((3aR,6S,7aS)- 3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl propionate); FLOROPALTM (2,4,6-trimethyl-4-phenyl-1,3-dioxane); FRESKOMENTHETM (2-(sec-butyl)cyclohexanone); FRUITATE ((3aS,4S,7R,7aS)-ethyl octahydro-1H-4,7-methanoindene-3a-carboxylate); FRUTONILE (2-methyldecanonitrile); GALBANONETM PURE (1-(3,3-dimethylcyclohex-1-en-1-yl)pent-4-en-1-one); GARDOCYCLENETM ((3aR,6S,7aS)- 3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl isobutyrate); GERANIOL ((E)-3,7-dimethylocta-2,6-dien-1-ol); SYNTHETIC GERANYL ACETATE ((E)-3,7-dimethylocta-2,6-dien-1-yl acetate); GERANYL ISOBUTYRATE ((E)-3,7-dimethylocta-2,6-dien-1-yl isobutyrate); GIVESCONETM (ethyl 2-ethyl-6,6-dimethylcyclohex-2-enecarboxylate); HABANOLIDETM ((E)-oxacyclohexadec-12-en-2-one); HEDIONETM (methyl 3-oxo-2-pentylcyclopentaneacetate); HERBANATETM ((2S)-ethyl 3-isopropylbicyclo[2,2,1]hept-5-ene-2-carboxylate); HEXENYL-3-CIS BUTYRATE ((Z)-hex-3-en-1-yl butyrate); CYNAMIC HEXYL ALDEHYDE ((E)-2-benzylideneoctanal); HEXYL ISOBUTYRATE (hexyl isobutyrate); HEXYL SALICYLATE (hexyl 2-hydroxybenzoate); INDOFLORTM (4,4a,5,9b- tetrahydroindene[1,2-d][1,3]dioxin); IONONE BETA ((E)-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one); IRISONE ALFA ((E)-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); IRONE ALFA ((E)-4-(2,5,6,6-tetramethylcyclohex-2-en-1-yl)but-3-en-2-one); ISO E SUPERTM (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); ISOCYCLOCITRAL (2,4,6-trimethylcyclohex-3-enecarbaldehyde); ISONONYL ACETATE (3,5,5-trimethylhexyl acetate); ISOPROPYL METHYL-2-BUTYRATE (isopropyl 2-methyl butanoate); ISORALDEINETM 70 ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); JASMACYCLENETM ((3aR,6S,7aS)-3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl acetate); JASMONE CIS ((Z)-3-methyl-2-(pent-2-en-1-yl)cyclopent-2-enone); KARANALTM (5-(sec-butyl)-2-(2,4-dimethylcyclohex-3-en-1-yl)-5-methyl-1,3-dioxane); KOAVONE ((Z)-3,4,5,6,6-pentamethyl-hept-3-en-2-one); LEAF ACETAL ((Z)-1-(1-ethoxyethoxy)hex-3-ene); LEMONILETM ((2E,6Z)-3,7-dimethylnone-2,6-dienonitrile); LIFFAROMETM GIV ((Z)-hex-3-en-1-yl methyl carbonate); LILIALTM (3-(4-(tert-butyl)phenyl)-2-methylpropanal); LINALOOL (3,7-dimethylocta-1,6-dien-3-ol); LINALYL ACETATE (3,7-dimethylocta-1,6-dien-3-yl acetate); MAHONIALTM ((4E)-9-hydroxy-5,9-dimethyl-4-decenal); MALTYL ISOBUTYRATE (2-methyl-4-oxo-4H-pyran-3-yl isobutyrate); MANZANATO (ethyl 2-methylpentanoate); MELONALTM (2,6-dimethylhept-5-enal); MENTHOL (2-isopropyl-5-methylcyclohexanol); MENTHONE (2-isopropyl-5-methylcyclohexanone); METHYL CEDRYL KETONE (1-((1S,8aS)-1,4,4,6-tetramethyl-2,3,3a,4,5,8-hexahydro-1H-5,8a-methanoazulen-7-yl )ethanone); EXTRA METHYL NONYL KETONE (undecan-2-one); METHYL OCTINO CARBONATE (methyl non-2-Inoate); METHYL PAMPLEMOUSSE (6,6-dimethoxy-2,5,5-trimethyl-hex-2-ene); MYRALDENE (4-(4-methylpent-3-en-1-yl)cyclohex-3-enocarbaldehyde); NECTARYL (2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentanone); NEOBERGAMATETM FORTE (2-methyl-6-methylene-oct-7-en-2-yl acetate); NEOFOLIONETM ((E)-methyl non-2-enoate); NEROLIDYLETM ((Z)-3,7,11-trimethyldodeca-1,6,10-trien-3-yl acetate); NERYL ACETATE HC ((Z)-3,7-dimethylocta-2,6-dien-1-yl acetate); NONADYL (6,8-dimethylnonan-2-ol); NONENAL-6-CIS ((Z)-non- 6-enal); NYMPHEALTM (3-(4-isobutyl-2-methylphenyl)propanal); ORIVONETM (4-(ter-pentyl)cyclohexanone); PARADISAMIDETM (2-ethyl-N-methyl-N-(m-tolyl)butanamide); PELARGENE (2-methyl-4-methylene-6-phenyltetrahydro-2H-pyran); PEONILETM (2-cyclohexylidene-2-phenylacetonitrile); PETALIATM (2-cyclohexylidene-2-(o-tolyl)acetonitrile); PIVAROSETM (2,2-dimethyl-2-phenylethyl propanoate); PRECYCLEMONETM B (1-methyl-4-(4-methylpent-3-en-1-yl)cyclohex-3-enecarbaldehyde); PYRALONETM (6-(sec-butyl)quinoline); RADJANOLTM SUPER ((E)-2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-en-1-ol); RASPBERRY KETONE (N112) (4-(4-hydroxyphenyl)butan-2-one); RHUBAFURANETM (2,2,5-trimethyl-5-pentylcyclopentanone); ROSACETOL (2,2,2-trichloro-1-phenylethyl acetate); ROSALVA (dec-9-en-1-ol); ROSYFOLIA ((1-methyl-2-(5-methyl-hex-4-en-2-yl)cyclopropyl)-methanol); ROSYRANETM SUPER (4-methylene-2-phenyltetrahydro-2H-pyran); SERENOLIDE (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl cyclopropanecarboxylate); SILVIALTM (3-(4-isobutylphenyl)-2-methylpropanal); SPIROGALBANONETM (1- (spiro[4,5]dec-6-en-7-yl)pent-4-en-1-one); STEMONETM ((E)-5-methylheptan-3-one oxime); SUPER MUGUETTM ((E)-6-ethyl-3-methyloct-6-en-1-ol); SYLKOLIDETM ((E)-2-((3,5-dimethyl-hex-3-en-2-yl)oxy)-2-methylpropyl cyclopropanecarboxylate); GAMMA TERPINENE (1-methyl-4-propan-2-ylcyclohexa-1,4-diene); TERPINOLENE (1-methyl-4-(propan-2-ylidene)cyclohex-1-ene); TERPYNYL ACETATE (2-(4-methylcyclohex-3-en-1-yl)propan-2-yl acetate); TETRAHYDRO LINALOOL (3,7-dimethyloctan-3-ol); TETRAHYDRO MYRCENOL (2,6-dimethyloctan-2-ol); THIBETOLIDE (oxacyclohexadecan-2-one); TRIDECENE-2-NITRILE ((E)-tridec-2-enonitrile); UNDECAVERTOL ((E)-4-methyldec-3-en-5-ol); VELOUTONETM (2,2,5-trimethyl-5-pentylcyclopentanone); VIRIDINETM ((2,2-dimethoxyethyl)benzene); ZINARINETM (2-(2,4-dimethylcyclohexyl)pyridine); and mixtures thereof.

[0058] Perfume-type ingredients and cosmetic actives for use in encapsulated compositions are preferably hydrophobic. Preferably, the cosmetic actives have a calculated octanol/water partition coefficient (ClogP) of 1.5 or more, more preferably 3 or more. Preferably, the ClogP of the cosmetic active ingredient ranges from 2 to 7.

[0059] Particularly useful cosmetic actives can be selected from the group consisting of emollients, softening actives, moisturizing actives, calming and relaxing actives, decorative actives, deodorants, anti-aging actives, draining actives, remodeling actives, skin leveling actives , preservatives, antioxidant actives, antibacterial or bacteriostatic actives, cleaning actives, lubricating actives, structuring actives, hair conditioning actives, whitening actives, texturizing actives, softening actives, anti-dandruff actives, and exfoliating actives.

[0060] Particularly useful cosmetic actives include, but are not limited to, hydrophobic polymers, such as alkyldimethylsiloxanes, polymethylsilsesquioxanes, polyethylene, polyisobutylene, styrene-ethylene-styrene and styrene-butylene-styrene block copolymers, among others; mineral oils, such as hydrogenated isoparaffins, silicone oils, among others; vegetable oils such as argan oil, jojoba oil, aloe vera oil, among others; fatty acids and fatty alcohols and their esters; glycolipids; phospholipids; sphingolipids, such as ceramides; sterols and steroids; terpenes, sesquiterpenes, triterpenes and their derivatives; essential oils such as arnica oil, mugwort oil, tannin oil, birch leaf oil, calendula oil, cinnamon oil, echinacea oil, eucalyptus oil, ginseng oil, jujube oil, sunflower oil , jasmine oil, lavender oil, lotus seed oil, perilla oil, rosemary oil, sandalwood oil, tea tree oil, thyme oil, valerian oil, wormwood oil, ylang ylang oil, yucca, among others.

[0061] In one embodiment, the cosmetic active can be selected from the group consisting of sandalwood oil, such as fusanus spicatus seed oil; panthenyl triacetate (CAS-No.: 94089-18-6); tocopheryl acetate; tocopherol, naringinin (CAS-No.: 480-41-1); ethyl linoleate; farnesyl acetate; farnesol; citronellyl methyl crotonate (CAS-No.: 20770-405); ceramide-2 (1-stearoyl-C18-sphingosine, CAS-No: 100403-19-8); and mixtures thereof.

[0062] The functional core material can optionally be mixed with various hydrophobic excipients, such as non-polar solvents, oils, waxes and non-polar polymers.

[0063] A wide selection of shell-forming monomers, pre-polymers or pre-condensates can be used to form the core-shell microcapsules of the present invention. These shell-forming materials may be selected from the group consisting of inorganic materials, such as silicate, metals and metal oxides, or organic materials, such as surfactants, natural, semi-synthetic and synthetic organic polymers, and mixtures thereof. Particularly suitable are wraps comprising silicates, gelatin, gelatin/gum arabic complexes, gelatin/carboxymethyl cellulose complexes, alginate/calcium complexes, lamellar surfactant phases, and thermosetting resins, such as aminoplast resins, polyurea resins, polyurethane and polyacrylate resins.

[0064] In a particular embodiment, the shell of the core-shell microcapsules comprises an aminoplast resin. Such microcapsules can be obtained by the steps of: dispersing droplets of functional material in an aqueous phase comprising an emulsifier in the presence of an amino-aldehyde precondensate; cause the monomers, prepolymers or precondensates to react at the interface of the droplets and the aqueous phase to form a slurry of nascent core-shell microcapsules. Polycondensation is carried out at a temperature of 85 ± 10 ° C for about 1 to about 4 hours at a pH of 3.9 ± 1.0; adding a hyperbranched polymer to the paste of nascent core-shell microcapsules to form a composition comprising a paste of core-shell microcapsules, wherein the hyperbranched polymer is embedded and/or attached to the shells of the core-shell microcapsules; optionally adding to the paste one or more of a suspending agent, a preservative or any other conventional excipients; optionally dehydrating the paste to form a core-shell microcapsule composition in powder form.

[0065] The emulsifier is preferably a polymeric stabilizer selected from the group consisting of acrylic copolymers containing sulfonate groups, such as those commercially available under the registered trademark LUPASOLTM (e.g. BASF), such as LUPASOLTM PA 140 or LUPASOLTM VFR; copolymers of acrylamide and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as those available under the trademark LUVISKOLTM (e.g. LUVISKOLTM K 15, K 30 or K 90 ex. BASF); sodium polycarboxylates (e.g. Polyscience Inc.) or sodium poly(styrene sulfonate) (e.g. Polyscience Inc.); vinyl and methyl vinyl ether-maleic anhydride copolymers (e.g. AGRIMERTM VEMA AN, e.g. ISP), and ethylene, isobutylene or styrene-maleic anhydride copolymers (e.g. ZEMACTM); ampholytic copolymers formed from a cationic monomer containing quaternary ammonium groups; and a monomer that can form anions, more particularly a monomer based on acrylic acid, methacrylic acid or a derivative thereof, such as a copolymer of acrylic acid or methacrylic acid, and acrylamidopropyl-trimethylammonium chloride (APTAC) or methacrylamidopropyl chloride -trimethylammonium (MAPTAC), a terpolymer formed from an acrylic acid monomer, a MAPTAC monomer and an acrylamide monomer).

[0066] The amino-aldehyde precondensate may be a reaction product, such as a polymer or copolymer of at least one amine, such as urea, thiourea, alkyl urea, 6-substituted-2,4-diamino-1, 3,5-triazines such as benzoguanamine or glycoluril, and melamine; and at least one aldehyde, such as formaldehyde, acetaldehyde, glyoxal or glutaraldehyde. Suitable amino aldehyde precondensates include, but are not limited to, partially methylated mono- and polymethylol-1,3,5-triamino-2,4,6-triazine precondensates, such as those commercially available under the registered trademark CYMELTM (e.g. Cytec Technology Corp.) or LURACOLLTM (e.g. BASF), and/or mono- and polyalkyl-benzoguanamine pre-condensates, and/or mono- and polyalkyl-glucouryl pre-condensates. re-condensates. These alkylated polyamines can be presented in partially alkylated forms, obtained by the addition of lower alcohols typically having 1 to 6 methylene units.

[0067] In another particular embodiment, the shell of the core-shell type microcapsules comprises a polyurea resin. Such microcapsules are obtained by the steps of: dispersing droplets of functional material in an aqueous phase comprising an emulsifier in the presence of a polyisocyanate; cause the monomers, prepolymers or precondensates to react at the interface of the droplets and the aqueous phase to form a slurry of nascent core-shell microcapsules. The reaction is carried out in the presence of a polyamine at a temperature of 80 ± 5 ° C for about 2 to about 6 hours and at a pH of 8.5 ± 1.0; adding a hyperbranched polymer to the nascent core-shell microcapsule paste to form a composition comprising a core-shell microcapsule paste, wherein the hyperbranched polymer is embedded in the shells of the core-shell microcapsules; optionally adding to the paste one or more of a suspending agent, a preservative or any other conventional excipients; optionally dehydrating the paste to form a core-shell microcapsule composition in powder form.

[0068] Polyisocyanates can be selected from the group consisting of 1,6-diisocyanate-hexane (CAS No.: 822-06-0), 1,5-diisocyanate-2-methylpentane (CAS No.: 34813- 62-2), 1,4-diisocyanate-2,3-dimethylbutane, 2-ethyl-1,4-diisocyanatobutane, 1,5-diisocyanatopentane (CAS No.: 4538-42-5), 1,4-diisocyanatobutane ( CAS No.: 4538-37-8), 1,3-diisocyanatopropane (CAS No.: 3753-93-3), 1,10-diisocyanatodecane (CAS No.: 538-39-0), 1,2-diisocyanatocyclobutane , bis(4-isocyanatocyclohexyl)methane (CAS No.: 5124-30-1), 3,3,5-trimethyl-5-isocyanatomethyl-1-isocyanatocyclohexane (CAS No.: 4098-71-9) , 2-imidodicarbanic diamide (CAS No.: 4035-89-6), biuret (CAS No.: 108-19-0), toluene diisocyanate polyisocyanurate (CAS No.: 141-78-6, commercially available from Bayer under the trade name DESMODURTM RC), precondensate of 1,6-diisocyanate-hexane polyisocyanurate in trimethylol propane (CAS No.: 53200-31-0, commercially available from Bayer under the trade name DESMODURTM N100), precondensate of toluene diisocyanate in trimethylol propane (CAS No.: 9081-90-7, commercially available from Bayer under the trade name DESMODUR L75), precondensed xylylene diisocyanate in trimethylol propane (CAS No.: 865621-91-6; commercially available from Mitsui Chemicals under the trade name TAKENATO D-110N). Also included are modified isocyanates, such as aliphatic polyisocyanate based on hexamethylene diisocyanate and alkylene oxide, especially ethylene oxide, (marketed under the name BAIHIDURTM), for example, BaihidurTM XP 2547 (commercially available from Bayer); and mixtures thereof. Polyamines can be selected from the group consisting of 1,2-ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, hydrazine; 1,4-diaminocyclohexane, 1,3-diamino-1-methylpropane, diethylenetriamine, triethylenetetramine, bis(2-methylaminoethyl)ether (CAS No.: 3033-62-3), guanidine (CAS No.: 113-00 -8), guanidine carbonate salt (CAS No. 593-85-1), 3,5-diamino-1,2,4-triazole (CAS No.: 1455-77-2), melamine, urea, polymeric polyamines such as poly(vinylamine), such as those commercially available under the trade name LUPAMINATM (e.g. BASF), poly(ethyleneimine) (CAS No.: 9002-98-6)), such as those commercially available under the trade name LUPASOLTM (e.g. BASF); poly(etheramine), such as those commercially available under the trade name JEFFAMINATM (e.g. Huntsman); and mixtures thereof.

[0069] The emulsifier is preferably a polymeric stabilizer selected from the group consisting of maleic/vinyl copolymers, sodium lignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, and propylene oxide, ethylenediamine and oxide copolymers. of ethylene, polyvinylpyrrolidone, polyvinyl alcohols, fatty acid esters of polyoxyethylenated sorbitol and sodium dodecyl sulfate. Polyvinylpyrrolidone and polyvinyl alcohols are polymer type G, with a degree of hydrolysis in the range of 85 to 99.9%, available under the trade name GOSHENOLTM from Nippon Gohsei Nichigo.

[0070] When carrying out step c), the addition of the hyperbranched polymer can be carried out before the shell-forming monomer, pre-polymers or pre-condensates react, or during the reaction of these materials. The total amount of hyperbranched polymer can be added in a single operation, or it can be added sequentially and/or little by little.

[0071] The amount of hyperbranched polymer added can vary within wide limits, and more particularly it can be added in an amount of about 0.01 to about 1% by weight, more particularly about 0.02 to about 0.5% by weight and even more particularly from 0.05 to 0.25% by weight, based on the total weight of the system (i.e., the emulsion in case the hyperbranched polymer is added before encapsulation or paste if the hyperbranched polymer is added during or after encapsulation).

[0072] The degree of incorporation of the hyper-branched polymer into or on the microcapsule shell can be obtained by subtracting the amount of free hyper-branched polymer present in the paste from the nominal amount of hyper-branched polymer initially added to the system, then the coating process has finished.

[0073] A considerable advantage of hyperbranched polymers compared to linear polymers that are conventionally used as deposition aids is their low thickening potential, which allows them to be used at much lower levels in microcapsule pastes without inducing serious problems. of viscosity. This results in greater incorporation of hyperbranched polymer into or onto the microcapsule shell.

[0074] The level of free hyper-branched polysaccharides present in the paste can be determined by the Alabamesh method (A. Albalasmeh et al., Carbohyd, Poly,2013, 97, 253-261), based on the colorimetric determination of carbohydrates according with Dubois (M. Dubois et al., Anal.Chem. 1956, 28, 350-356). The method involves separating the microcapsules from the aqueous phase of the paste by centrifugation, adding concentrated sulfuric acid to the diluted supernatant and measuring the UV/VIS absorbance at a wavelength of 350 nm. A detailed procedure is presented in Example 2.

[0075] Typically, from 40 to 99%, more particularly from 50 to 80% and even more particularly from 55 to 70% of the added hyperbranched polymer are effectively embedded in the envelope of the microcapsules and/or fixed thereto.

[0076] Although the addition of one or more suspending agent, a preservative or any other conventional excipients to the paste is optional, it is conventional to stabilize a paste by adding certain well-known excipients.

[0077] For example, after the paste is formed, it is possible to add a suspending agent to it to prevent the paste from undergoing phase separation, such as creaming or sedimentation. Any of the conventional suspending agents may be employed in the present invention. Conventional suspending agents include, but are not limited to, a hydrocolloid selected from the group consisting of starch and starch derivatives, such as modified starch, dextrin, maltodextrin; gums, such as gum arabic or acacia gum, xanthan gum, gum tragacanth, caray gum, guar gum; cellulose and cellulose derivatives, such as carboxy methyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose/lauryl-dimethylammonioepoxy condensate, hydroxypopyl cellulose, cationic cellulose (e.g. polyquaternium-4), gum cellulose; carrageenan; agar-agar; pectins and pectic acid; gelatin; protein hydrolysates; polymers and copolymers of vinyl to allylic monomers, such as polyvinylpyrrolidone; poly(vinyl pyrrolidone-co-vinylacetate); poly(vinyl alcohol-co-vinyl acetate) (more particularly hydrolyzed polyvinyl acetates with a degree of hydrolysis between 85 and 92%), vinyl ester homopolymers and copolymers, such as vinyl acetate, vinyl pivalate, vinyl versatate; poly(methyl vinyl ether), poly(vinyl alkyl amines), such as polyvinylmethylamine, quaternized polyvinyl alkyl amines, vinyl pyridine and quaternized vinyl pyridine, vinyl imidazoline, vinyl imidazole, vinyl imidazolinium, dimethyldiallyl ammonium chloride, homopolymers and/or copolymers of vinyl sulfonate, polyamines and polyimines, ethoxylated polyamines, polymers, copolymers and cross-linked polymers derived from (meth)acryloyl monomers, such as methyl methyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, C10-C30 alkyl acrylate, hydroxyalkyl (meth)acrylate, such as 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, acrylamidodimethyl taurate; aryl (meth)acrylates, such as phenyl acrylate and benzyl acrylate, (meth)acrylic acids and their salts, such as sodium and potassium (meth)acrylates, sodium acryloyldimethyltaurate; (meth)acrylamides; N-alkyl (meth)acrylamides, such as N,N-dimethylaminoalkyl methacrylate; quaternized N-alkyl (meth)acrylamides, such as methacrylamidopropyltrimethylammonium chloride; acrylamidoethyltrimonium chloride; acrylamidolauryltrimethylammonium chloride; and (meth)acrylamido alkyl sulfonates poly(maleic anhydride) and poly(maleic anhydride-co-vinyl ether), and their hydrolysates; copolymer of poly(acrylic acid-co-maleic acid), poly(alkylene oxide), polyurethanes and polyureas, such as anionic, cationic, nonionic and amphoteric polyurethanes and polyureas; mixed copolymers thereof; and mixtures thereof.

[0078] It is also conventional to add biological preservatives to aqueous pastes to prevent the unwanted growth of molds and other microorganisms.

[0079] Suitable preservatives include, but are not limited to, quaternary compounds, biguanide compounds (CAS No.: 32289-580, 27083-27-8, 28757-47-3, 133029-32-0), polyaminopropyl biguanidine, hexetidine, for -chloro-meta-cresol, methenamine, 3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione, quaternium-15, benzoic acid, salicylic acid, undec-10-enoic acid, formic acid, biphenyl- 2-ol and its salts, 4-hydroxybenzoic acid and its esters and salts; sorbic acid and its salts, isothiazolinones, 2-bromo-2-nitro-1,3-propanediol, 5-bromo-5-nitro-1,3-dioxane, 2-(thiazol-4-yl) benzimidazole, benzimidazole carbamate, 3-(4-chlorophenyl)-1-(3,4-dichlorophenyl)urea, 3-iodo-2-propynylbutylcarbamate, ethyl(2-mercaptobenzoate-(2-)-O,S) mercurate(1-) sodium, 5 -chloro-2-(2,4-dichlorophenoxy)phenol, dichlorobenzyl alcohol, chloroxylenol, imidazolidinyl urea, phenoxyethanol, benzyl alcohol and mixtures thereof.

[0080] Compositions in the form of a core-shell microcapsule paste can be incorporated into all types of consumer products. However, for some applications, it may be desirable to add the core-shell microcapsules in the form of a dry powder. Therefore, in accordance with the present invention, in a further step to dehydrate the paste to form a core-shell microcapsule composition in powder form, the paste can be dehydrated to provide the composition of the present invention in the form of a powder. dry.

[0081] If desired, the microcapsules can be isolated in the form of a dry powder. For example, solid capsules can be isolated by filtration and dried. Drying of the insulated capsules can be carried out by heating, for example in an oven or by contact with a stream of hot gas. Preferably, drying of the dispersion is carried out by spray drying or fluid bed drying. Spray drying techniques and apparatus are well known in the literature. A spray drying process forces the suspended capsules through a nozzle and into a drying chamber. The capsules may be carried in a fluid (such as air) that moves into a drying chamber. The fluid (which can be heated, for example, to a temperature of 150 and 120°C, more preferably between 170°C and 200°C, and even more preferably between 175°C and 185°C) causes the liquid evaporate, leaving dry capsules that can be removed from the process equipment and further processed.

[0082] Before or after the spray drying step, it may be desirable to add a flow aid such as silica or similar to the paste to ensure the formation of fine, free-flowing powder microcapsules with low surface perfume oil content. . Flow aids include silicas or silicates, such as precipitated, fumed or colloidal silicas, starches, calcium carbonate, sodium sulfate, modified cellulose, zeolites or other inorganic particulates known in the art.

[0083] The microcapsule paste can be spray-dried in a conventional spray-drying tower using a two-fluid nozzle, or it can be spin-dried in a conventional centrifugal dryer. If desired, at least one hydrocolloid may be added to the microcapsule paste, either as is or in the form of an aqueous solution. Typical hydrocolloids include starch, modified starch such as dextrin modified with octenyl succinate anhydride, and gum arabic. Optionally, maltodextrins and sugar alcohols, such as sorbitol, mannitol or maltitol, can also be added. The hydrocolloid itself may contain a functional material. This functional material may be the same as the core material in the capsule, or different from the core material in the capsule. This can be achieved by carrying out the step of (1) emulsifying a second functional material in an aqueous hydrocolloid solution, optionally comprising maltodextrins and sugars or sugar alcohols to form a second paste, (2) mixing the second paste with a paste of microcapsules comprising a first functional material, and (3) drying this mixture. Such a process is described in document WO 2007/137441 A1, Example 5.

[0084] By means of the present invention it is possible to obtain compositions in the form of a paste of core-shell type microcapsules that have a high core content, typically in the range of 30 to 50% by weight, and more particularly from 35 to 45%. in weight.

[0085] Furthermore, the core-shell type microcapsules may have a volumetric average diameter of 0.5 to 25 microns, more particularly 1 to 20 microns, even more particularly 5 to 15 microns, for example, 10 ± 2 microns .

[0086] The size of the microcapsules can be determined in a manner known in the literature. One particular method for measuring particle size is light scattering. Light scattering measurements can be made with a Malvern Mastersizer 2000S instrument and using Mie scattering theory. The principle of Mie theory and how light scattering can be used to measure droplet size can be found in, for example, H. C. van de Hulst, Light scattering by small particles. Dover, New York, 1981. The primary information provided by static light scattering is the angular dependence of the light scattering intensity, which in turn is associated with the size and shape of the droplets. However, in a traditional operating method, the size of a sphere with a size equivalent to the size of the diffracting object, whatever the shape of this object, is calculated by the patented Malvern software supplied with the apparatus. In the case of polydisperse samples, the angular dependence of the total scattering intensity contains information about the size distribution in the sample. The result is a histogram representing the total volume of droplets belonging to a given size class as a function of the capsule size, considering that it is possible to choose an arbitrary number of 50 size classes. Thus, the size obtained is called volumetric mean particle size.

[0087] Experimentally, a few drops of paste are added to a circulating stream of degassed water flowing through a spreading cell. The angular distribution of scattering intensity is measured and analyzed by the patented Malvern software to provide the average size and size distribution of droplets present in the sample. In the case of a unimodal (monodisperse) droplet distribution, the percentiles Dv(10), Dv(50) and Dv(90) are used as characteristics of the droplet size distribution, while Dv(50) corresponds to the median of the droplet size distribution. distribution and is considered as a measure of the average volumetric size of the microcapsules. The compositions according to the present invention can be incorporated into all types of consumer products.

[0088] Typical consumer products targeted by the present invention include personal care and hygiene compositions, such as shampoos, shower gels, liquid soaps, bar soaps and the like, laundry products, such as detergents, and household hygiene products, such as hard surface cleaners.

[0089] In many cases, the consumer products targeted by the present invention contain surfactants, such as anionic, cationic, amphoteric or non-ionic surfactants.

[0090] In a preferred embodiment of the present invention, the consumer product comprising a composition described above is a shampoo comprising anionic surfactants, nonionic surfactants, water-soluble solvents, one or more preservatives, and optionally beneficial agents that may be selected from the group consisting of humectants, emollients, thickeners, anti-dandruff agents, hair growth stimulating agents, vitamins, nutrients, dyes, hair coloring, and the like.

[0091] Typical formulation ingredients for use in shampoo with or without microcapsules can be found, for example, in document EP 0 191 564 A2 or WO 1997/023194 A1.

[0092] The microcapsules are preferably present at a level of about 0.01 to 5% by weight, more particularly from about 0.1 to 2.5% by weight and even more particularly from about 0.2 to 1% by weight of the personal care product, in relation to the total weight of the shampoo composition.

[0093] In another embodiment of the present invention, the consumer product comprising core-shell type microcapsules is a liquid soap comprising one or more anionic surfactants, and other surfactants that may be selected from the group consisting of mixtures of fatty acids and fatty acids. neutralized fatty acids, aminoxide-type surfactants, non-ionic surfactants, zwitterionic surfactants, and mixtures thereof; electrolytes; one or more preservatives; and optionally beneficial agents that may be selected from the group consisting of pH controlling agents, skin care agents, humectants, emollients, thickeners, vitamins, nutrients and dyes.

[0094] Typical formulation ingredients for use in liquid soaps can be found, for example, in document CA 2812137 A1 or US 2003/0050200 A1.

[0095] The core-shell microcapsules are preferably present at a level of about 0.01 to 5% by weight, more particularly about 0.1 to 2.5% by weight, and even more particularly about 0.2 to 1% by weight of the personal care product, in relation to the total weight of the liquid soap composition.

[0096] In another embodiment of the present invention, the consumer product comprising core-shell microcapsules is a shower gel comprising one or more anionic surfactants, and other surfactants that may be selected from the group consisting of mixtures of fatty acids and neutralized fatty acids, aminoxide-type surfactants, non-ionic surfactants, zwitterionic surfactants, aminoxide-type surfactants, aminoxide-type surfactants, and mixtures thereof; electrolytes, such as one or more preservatives; and optionally beneficial agents that may be selected from the group consisting of thickeners, pH controlling agents, skin care agents, humectants, emollients, thickeners, vitamins, nutrients and dyes, and the like.

[0097] Typical formulation ingredients for use in shower gels can be found, for example, in US 5,607,678 or US 2012/0263668 A1.

[0098] Core-shell microcapsules are preferably present at a level of about 0.01 to 5% by weight, more particularly about 0.1 to 2.5% by weight, and even more particularly about 0.2 to 1% by weight of the personal care product, in relation to the total weight of the shower gel composition.

[0099] After being deposited on the keratinous surfaces, the core-shell type microcapsules are capable of releasing their functional material by diffusion through the microcapsule envelope or after mechanical rupture of the microcapsule envelope. Mechanical breakage can occur after a mechanical action, such as rubbing, squeezing, combing, washing, among others, or heating, for example, with a hairdryer.

[00100] Diffusion-mediated release is particularly desired when the functional material is a fragrance composition, because in this case a pleasant smell can be perceived for a long time, for example, several hours, after application of the microcapsules to the substrate . On the other hand, a mechanical rupture can cause a surprising and pleasant explosion of odor.

[00101] Other advantages and particular features of the present invention will become apparent from Figure 1 and from the following discussion of several examples.

[00102] Figure 1 illustrates the deposition and rinse resistance for the shampoo and hair conditioner compositions obtained in Example 3.

Example 1:

[00103] Preparation of aminoplast core-shell microcapsules comprising a hyperbranched polymer embedded in the shell of the core-shell microcapsules and a fragrance as core material.

[00104] The microcapsules were prepared by the steps of: preparation of an aqueous solution containing 72 g of the LUPASOLTM PA 140 emulsifier (e.g. BASF, 20% active, effective amount of active: 14 g), 19 g of the LURACOLLTM resin precursor SD (e.g. BASF, 70% active, effective amount of active: 13.3 g) and 6.7 g of resorcinol and 324 g of water; emulsifying 355 g of fragrance in the aqueous solution obtained in step a) by mixing at a stirring speed of 1000 rpm, using a cross-beam agitator with an inclined beam; adjusting the pH of the emulsion obtained in a) to a value of 3.5 ± 0.3 by adding 11.1 g of 10% formic acid and heating the emulsion to 90°C; maintaining the temperature at 90°C for a period of one hour with stirring, to form a wall of thermosetting aminoplast resin around the droplets, thus forming a paste of microcapsules with a diameter of 10 microns (μm); adding a defined amount of a selected 2% by weight solution of hyperbranched polysaccharide in water (as specified below); addition of 11.1 g of 10% formic acid and 11.1 g of LURACOLLTM SD resin precursor (e.g. BASF, 70% active, effective amount of active: 7.8 g), with the temperature being maintained at 90 °C for another 2 hours; cooling the paste to room temperature and adding 3.2 g of a 10% ammonium solution in water to obtain a pH between 5.5 and 7.

[00105] The defined amounts of the 2% by weight hyperbranched polysaccharide solution in water were 50 g of solution (corresponding to 0.1% by weight of hyperbranched polysaccharide in the paste) and 150 g of solution (corresponding to 0.3% by weight of hyperbranched polysaccharide in the paste). The hyperbranched polysaccharide was amylopectin.

[00106] The solids content of the paste was measured with a thermal balance operating at 120°C. The solids content, expressed as a percentage by weight of the initial paste deposited on the scale, was measured at the point where the rate of drying-induced weight change fell to less than 0.1%/min. The solids content of the paste was 42 ± 1% by weight. A comparative example without hyperbranched polymer is obtained by substantially the same process as that described above, but with omission of step f) of adding hyperbranched polymer.

Example 2:

[00107] Determination of free polysaccharides in pastes prepared according to Example 1.

[00108] The level of free polysaccharides is determined by the steps of:

[00109] dilute the paste to obtain a solids content of about 10% by weight (dilution factor 4);

[00110] centrifuge the diluted paste for 30 minutes at 3000 rpm;

[00111] collect a sample of the supernatant with a syringe and ultracentrifuge this supernatant for 30 minutes at 13000 rpm;

[00112] collect a sample of the supernatant again and filter this supernatant through a microporous filter;

[00113] mix 3 ml of filtered supernatant diluted 10 times in deionized water with 7 ml of concentrated sulfuric acid at 98% by volume (supplied by Sigma Aldrich);

[00114] cool to mix and top up to 10 ml with deionized water;

[00115] measure the absorbance at a wavelength of 350 nm and compare the absorbance value with the values of a calibration curve obtained from standard hyperbranched polymer solutions.

[00116] The levels of free hyperbranched polymer in the different samples are presented in Table 1 below.

[00117] The level of hyper-branched polymer embedded in the shell of core-shell microcapsules is obtained by subtracting the level of free hyper-branched polymer from the total level of hyper-branched polymer added to the paste.

Example 3:

[00118] Preparation of shampoo and hair conditioner compositions and deposition data.

[00119] The microcapsule pastes of Example 1 were added to a shampoo composition with gentle stirring with a paddle mixer so that the paste level in the shampoo base was 0.5% by weight of the total weight of shampoo base. The mixture was left to macerate for one night before deposition measurements were taken. 4.8 g of base was applied to 48 g of hair samples by rubbing for 20 seconds. The samples were then allowed to rest for 1 minute and then rinsed for 30 seconds with running water at 37°C at a flow rate of 3.2 l/min, without hands touching the sample.

[00120] Deposition values were obtained by analyzing micrographs of images obtained with an optical fluorescence microscope at an amplification of 40 x, with the help of Stream Motion software and Hostasol Yellow 3G as a fluorescent agent at 0.02% by weight. in perfume, excitation wavelength 450 nm and emission wavelength 500 nm.

[00121] In the case of hair conditioner, the microcapsule pastes of Example 1 were added to a hair conditioner composition with gentle stirring with a paddle mixer, such that the paste level in the hair conditioner base was 1% by weight in relation to the total weight of the hair conditioner base. 1.5 g of hair conditioner was applied to 15 g samples moistened with 12 g of water. The samples were massaged, allowed to rest for 1 minute and then rinsed for 30 seconds with running water at 37°C at a flow rate of 3.2 l/min, without hands touching the sample.

[00122] The deposition values were determined in the manner described above for the case of shampoo.

[00123] The compositions of the exemplary shampoo and hair conditioner bases are shown in Tables 2 and 3. Table 1: Results for the shampoo Table 2: Results for hair conditioner

[00124] The results of Tables 1 and 2 are illustrated in Figure 1. They confirm that core-shell microcapsules with a core comprising a hyper-branched polymer, in shampoo and conditioner compositions, present better deposition and greater resistance to rinsing in hair compared to situations where no polymer or a linear polymer is used. Table 3: Base composition for exemplary shampoo Table 4: Base composition for exemplary hair conditioner

Claims (14)

1. Composition, characterized by the fact that it comprises at least one core-shell type microcapsule in a suspension medium, wherein said microcapsule comprises a core and a shell around said core, wherein the shell comprises a hyper- branched selected from the group consisting of amylopectins, dextrins, hyperbranched starches, glycogen and phytoglycogen and mixtures thereof, in which the amount of hyperbranched polysaccharide is 0.01 to 1% by weight, relative to the total weight of the microcapsule suspension. 2. Composition according to claim 1, characterized by the fact that the ratio of 1,6'-glycosidic bonds to 1,4'-glycosidic bonds in the hyperbranched polysaccharide is greater than 1/50, more particularly greater than 1 /40 and even more particularly greater than 1/35. 3. Composition according to claim 1 or 2, characterized by the fact that the hyperbranched polysaccharide is embedded in the microcapsule envelope and/or fixed thereto. 4. Composition according to any one of the preceding claims, characterized by the fact that the amount of hyperbranched polysaccharide is 0.02 to 0.5% by weight and more particularly 0.05 to 0.25% by weight , in relation to the total weight of the microcapsule suspension. 5. Composition according to any one of the preceding claims, characterized in that the core comprises a fragrance ingredient, a cosmetic ingredient or a mixture thereof. 6. Composition according to any one of the preceding claims, characterized in that the envelope of the at least one core-shell type microcapsule comprises a thermosetting resin, in particular a thermosetting resin selected from the group consisting of aminoplast resins, polyurea, polyacrylic resins and mixtures thereof. 7. Method for embedding and/or fixing hyperbranched polysaccharide within and/or on microcapsule shells, characterized in that it comprises the steps of: - dispersing droplets of a core material in a suspension medium, in particular comprising an emulsifier, in the presence of shell-forming monomers, pre-polymers or pre-condensed to obtain an emulsion; - cause the monomers, pre-polymers or pre-condensates to react at the interface of the droplets and the suspension medium to obtain a paste of core-shell type microcapsules; - add a hyperbranched polysaccharide; - obtaining a composition comprising a paste of core-shell microcapsules, in which the hyperbranched polysaccharide is embedded and/or fixed within and/or on the shells of the core-shell microcapsules; - optionally, add one or more suspending agent or preservative to the paste; - optionally dehydrating the paste to form a core-shell microcapsule composition, in particular in powder form, in which the hyperbranched polysaccharide is selected from the group consisting of amylopectins, dextrins, hyperbranched starches, glycogen and phytoglycogen and mixtures thereof, in which the amount of hyperbranched polysaccharide is 0.01 to 1% by weight, relative to the total weight of the microcapsule suspension. 8. Microcapsule, characterized by the fact that it is obtainable by a method as defined in claim 7. 9. Method for improving the deposition of at least one core-shell type microcapsule on a surface, in particular a keratinous surface, characterized by the fact that it comprises the step of embedding and/or fixing a hyperbranched polymer into and/or on the envelope of said core-shell type microcapsule by a method as defined in claim 7. 10. Method for increasing the rinsing resistance of at least one core-shell type microcapsule deposited on a surface, in particular on a keratinous surface, characterized by the fact that it comprises the step of embedding and/or fixing a hyper-branched polymer within of and/or on the shell of the core-shell microcapsule by a method as defined in claim 7. 11. Use of a hyperbranched polymer, characterized in that it is to improve the deposition of at least one core-shell type microcapsule on a surface, in particular a keratinous surface, by embedding and/or fixing the hyperbranched polymer within of and/or on the envelope of said core-shell type microcapsule by a method as defined in claim 7. 12. Use of a hyperbranched polymer, characterized in that it is to increase the rinsing resistance of at least one core-shell type microcapsule deposited on a surface, in particular on a keratinous surface, by embedding and/or fixing a hyperbranched polymer within and/or on the shell of the core-shell microcapsule by a method as defined in claim 7. 13. Consumer product, characterized by the fact that it comprises a composition as defined in any one of claims 1 to 6. 14. Consumer product according to claim 13, characterized by the fact that it is a shampoo, a hair conditioner, a shower gel or a liquid soap.