Hydrogel beads

Abstract

The present invention relates to hydrogel beads having a liquid crystalline structured phase. A method for preparing crystalline hydrogel beads is also an object of the present invention. Perfumed compositions and consumer products, especially in the form of personal care products or flavor products, comprising or consisting of said crystalline hydrogel beads are also part of the present invention.

Description

[Technical Field]

[0001] The present invention relates to hydrogel beads. A method for preparing the hydrogel beads is also an object of the present invention. Perfumed compositions and consumer products, especially in the form of personal care products or flavor products, comprising or consisting of said hydrogel beads are also part of the present invention. [Background technology]

[0002] Fragrance plays a key role in the perception of efficacy of consumer products and therefore often determines the consumer's choice for a given product. Furthermore, the increasing consumer demand for fragrance experience is driving the development of new delivery systems.

[0003] Biopolymer hydrogels are used in numerous fields, including cosmetics, pharmaceuticals, and food. Their non-toxicity, biodegradability, and hypoallergenicity make them preferred components in many applications. In many industries, hydrogel capsules have been employed as delivery systems for retaining and / or delivering various molecules of interest that can be placed within the hydrogel core space. Typically, the resulting capsules have a structure comprising a hydrophobic core encapsulated within a hydrophilic hydrogel matrix capable of retaining a significant amount of water (e.g., at least 70%).

[0004] A key requirement from industry for these delivery systems is that they survive suspension in difficult bases without physical separation or degradation. For example, fragranced personal and household cleansers containing high levels of harsh surfactant detergents present significant challenges to the stability of such systems.

[0005] US Patent Application Publication No. 2006 / 0292280 discloses alginate particles having a heterogeneous matrix composed of a continuous phase of polymer gel and an oily discontinuous phase that optionally contains an active agent.

[0006] WO 2012 / 089819 describes alcohol-free fragrance capsules comprising an internal oil-in-water emulsion-type phase containing a perfume and an external gelled phase.

[0007] However, the hydrogel beads described in these publications have shown poor stability in difficult media, and therefore their use in cosmetics, personal care, and home care products has been very limited.

[0008] There is therefore a need to provide new environmentally friendly delivery systems that have good performance in terms of delivery of active ingredients, e.g., olfactory performance in the case of perfumery ingredients, while being stable in difficult media such as consumer product bases and that can be prepared in a simple manner.

[0009] The present invention proposes a solution to the above problems based on hydrogel beads comprising at least one liquid crystalline structured phase.

[0010] Summary of the Invention Surprisingly, it has been found that the intercalation of at least one liquid crystalline phase (lamellar, hexagonal, cubic, or nematic) within the matrix of hydrogel beads strengthens the beads against their dissolution in surfactant-based formulations and allows them to be deposited on the skin or other surface without leaving a solid residue, creating a creamy texture. Furthermore, solubilization of fragrance in such crystalline beads creates an aromatic fragrance performance during deposition on the skin or other surface.

[0011] In a first aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: (i) preparing a continuous phase comprising water and a biopolymer; (ii) preparing an internal phase comprising a hydrophobic active ingredient, preferably a perfume or flavor oil; (iii) mixing the continuous phase and the internal phase to form a dispersion; (iv) forming beads by inducing complexation of the dispersion obtained in step (iii); wherein a mesogenic compound is added in step (i) and / or (ii) under conditions that allow the formation of at least one liquid crystalline structured phase in the hydrogel beads.

[0012] In a second aspect, the present invention relates to hydrogel beads having an internal phase dispersed in a continuous phase, wherein: the internal phase comprises a hydrophobic active ingredient, preferably a perfume or flavor oil, and - the continuous phase comprises biopolymers and water, forming a hydrogel matrix; The hydrogel beads are characterized in that the beads contain at least one liquid crystalline structured phase.

[0013] In a third aspect, the present invention relates to a method for preparing hydrogel beads comprising a hydrophobic active ingredient dispersed in a biopolymer matrix, said method comprising the steps of: (i) preparing a continuous phase comprising water and a biopolymer; (ii) preparing an internal phase comprising a hydrophobic active ingredient, preferably a perfume or flavor oil; (iii) mixing the continuous phase and the internal phase to form a dispersion; (iv) forming beads by inducing complexation of the dispersion obtained in step (iii); wherein a mesogenic compound is added in step (i) and / or (ii) under conditions that allow the formation of at least one liquid crystalline structured phase in the hydrogel beads.

[0014] Another subject of the present invention is (i) hydrogel beads as defined above, wherein the hydrophobic active ingredient comprises a fragrance; (ii) at least one ingredient selected from the group consisting of perfume carriers and perfume co-ingredients; (iii) optionally, at least one flavor adjuvant and a fragrance composition comprising:

[0015] Another subject of the invention is a consumer product comprising: a) 2 to 65% by weight of at least one surfactant, based on the total weight of the consumer product; b) water or a water-miscible hydrophilic organic solvent; c) Hydrogel beads or perfumed compositions as defined above and consumer products including.

[0016] Detailed Description of the Invention Unless otherwise specified, percentages (%) are meant to indicate weight percentages of the composition.

[0017] The beads of the present invention are crystalline beads. By "crystalline beads" it is meant that the beads contain at least one liquid crystalline structured phase.

[0018] "Liquid crystal structured phase" means a phase that is highly organized, has a dense structure with physical properties such as viscosity and permeability, and is intermediate between a liquid and a real liquid crystal (lamellar, hexagonal, cubic or nematic phase). The main advantage that makes them interesting delivery systems for industrial applications is their ability to solubilize large amounts of both hydrophilic and hydrophobic molecules.

[0019] The presence of an anisotropic liquid crystal phase can be confirmed by cross-polarized light microscopy.

[0020] According to a particular embodiment, the liquid crystal structured phase is selected from the group consisting of a nematic phase, a lamellar phase, a hexagonal phase and mixtures thereof.

[0021] "Liquid crystal (LC)" or "liquid crystal structured phase" are used interchangeably in the present invention.

[0022] "Mesogenic compounds" refers to compounds capable of forming liquid crystalline structured phases. Many compounds are known to exhibit one or several liquid crystalline phases. These compounds share common chemical and physical characteristics. For example, they are slightly soluble in water.

[0023] The crystalline beads of the present invention comprise a hydrogel matrix.

[0024] By hydrogel beads, we mean that the beads are made of a three-dimensional network of biopolymer chains with an aqueous phase filling the spaces between the polymers. The biopolymer is preferably selected from the group consisting of alginate, xanthan, carrageenan, chitosan, pectin, gellan, agar, hydroxycellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, and mixtures thereof.

[0025] The crystalline beads of the present invention are spherical and preferably have a size of 0.1 mm to 10 mm, preferably 1 mm to 7 mm.

[0026] According to a particular embodiment, the beads are macroscopic beads.

[0027] "Active ingredient" means a single compound or a combination of ingredients.

[0028] By "perfume or flavor oil" is meant a single perfuming or flavoring compound or a mixture of several perfuming or flavoring compounds.

[0029] "Consumer product" or "finished product" means a manufactured product that is ready for distribution, sale, and consumer use. [Brief explanation of the drawings]

[0030] [Figure 1a] FIG. 1 shows a schematic diagram of crystalline beads according to one embodiment of the present invention, in which a liquid crystalline structured phase is dispersed in a continuous phase. [Figure 1b]FIG. 1 shows a microscopic image of the hydrogel matrix obtained in Example 1, observed under a polarizing microscope. [Figure 2] FIG. 1 is a diagram illustrating a crystalline bead of the present invention. [Figure 3a] FIG. 2 shows a schematic diagram of crystalline beads according to another embodiment of the present invention, in which a liquid crystalline structured phase is located at the interface between the internal and continuous phases. [Figure 3b] FIG. 1 shows a microscopic image of the hydrogel matrix obtained in Example 4, observed under a transmission microscope. [Figure 3c] FIG. 1 shows a microscopic image of the hydrogel matrix obtained in Example 4, observed under a polarizing microscope. [Figure 4a] FIG. 1 shows fragrance release performance (for benzyl acetate). [Figure 4b] FIG. 1 shows fragrance release performance (for dihydromyrcenol). [Figure 5] FIG. 1 represents normal force as a function of concentration of mesogenic compound in crystalline beads according to the present invention.

[0031] The present invention relates to a method for producing a method for manufacturing a computer-readable recording medium, comprising the steps of: (i) preparing a continuous phase comprising water and a biopolymer; (ii) preparing an internal phase comprising a hydrophobic active ingredient, preferably a perfume or flavor oil; (iii) mixing the continuous phase and the internal phase to form a dispersion; (iv) forming beads by inducing complexation of the dispersion obtained in step (iii); wherein a mesogenic compound is added in step (i) and / or (ii) under conditions that allow the formation of at least one liquid crystalline structured phase in the hydrogel beads.

[0032] Crystalline beads as defined in the present invention comprise an internal phase dispersed in a continuous phase that forms a hydrogel matrix.

[0033] An inner phase containing a hydrophobic active ingredient "Hydrophobic active ingredient" means any hydrophobic active ingredient (single ingredient or mixture of ingredients) that forms a two-phase dispersion when mixed with water. A hydrophobic active ingredient is a liquid at about 20°C.

[0034] The hydrophobic active ingredient is preferably selected from the group consisting of flavors, flavor ingredients, fragrances, fragrance ingredients, nutraceuticals, cosmetics, pesticides, biocide actives and mixtures thereof.

[0035] According to certain embodiments, the hydrophobic active ingredient comprises a mixture of a fragrance and another ingredient selected from the group consisting of a nutraceutical, a cosmetic, a pesticide, and a biocide active.

[0036] According to certain embodiments, the hydrophobic active ingredient comprises a mixture of a biocidal active and another ingredient selected from the group consisting of fragrances, nutraceuticals, cosmetics, and pesticides.

[0037] According to certain embodiments, the hydrophobic active ingredient comprises a mixture of a pesticide and another ingredient selected from the group consisting of fragrances, nutraceuticals, cosmetics, and biocide actives.

[0038] According to certain embodiments, the hydrophobic active ingredient comprises a fragrance.

[0039] According to a particular embodiment, the hydrophobic active ingredient consists of a fragrance.

[0040] According to certain embodiments, the hydrophobic active ingredient comprises a flavor.

[0041] According to a particular embodiment, the hydrophobic active ingredient consists of a flavor.

[0042] By "perfume" (also referred to as "perfume oil") herein is meant an ingredient or composition that is liquid at about 20°C. According to any one of the above embodiments, the perfume oil may be a perfuming ingredient alone or a mixture of ingredients in the form of a perfume composition. By "perfuming ingredient" herein is meant a compound used primarily for the purpose of imparting or modifying an odor. In other words, such an ingredient is considered to be perfuming and must be recognized by those skilled in the art as being at least capable of imparting or modifying the odor of the composition in a positive or pleasant sense, and not merely possessing an odor. For the purposes of the present invention, perfume oils include combinations of perfuming ingredients with substances that together improve, enhance, or modify the delivery of the perfuming ingredient, such as perfume precursors, emulsions, or dispersions, as well as combinations that provide additional benefits beyond modifying or imparting an odor, such as substantivity, fragrance, malodor control, antibacterial effect, microbial stability, insect repellency, etc.

[0043] The nature and type of perfuming ingredients present in the oil phase do not warrant a more detailed description here, which is in any case not exhaustive, and those skilled in the art can select them based on their general knowledge and depending on the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming ingredients belong to various chemical classes, such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as S. Arctander, *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its latest edition, or other similar works, as well as in the abundant patent literature in the field of perfumery. It is understood that said ingredients can also be compounds known to control the release of various types of perfuming compounds.

[0044] The perfuming ingredients can be dissolved in solvents currently used in the perfume industry. The solvent is preferably not alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, Abalyn® (a rosin resin available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is very hydrophobic and highly sterically hindered, such as Abalyn® or benzyl benzoate. Preferably, the perfume contains less than 30% solvent. More preferably, the perfume contains less than 20%, and even more preferably less than 10%, of solvent, all of these percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially solvent-free.

[0045] According to another embodiment, the hydrophobic active ingredient comprises a flavor oil.

[0046] The term "biocide" refers to a chemical substance that can kill living organisms (e.g., microorganisms) or reduce or prevent their growth and / or deposition. Biocides are commonly used in medicine, agriculture, forestry, and industries to prevent fouling of, for example, water, agricultural products including seeds, and oil pipelines. Biocides can be pest control agents, including fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides, and rodenticides; and / or antimicrobial agents, such as bactericides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals, and / or antiparasitics.

[0047] As used herein, "pesticide" refers to a substance that serves to repel or attract pests, or reduces, inhibits, or promotes their growth, development, or activity. A pest refers to any living organism, whether animal, plant, or fungus, that invades or causes problems for plants or animals, and includes insects, especially arthropods, mites, spiders, fungi, weeds, bacteria, and other microorganisms.

[0048] According to any one of the embodiments of the present invention, the hydrophobic active ingredient represents about 0.0001% to 50% by weight (w / w), or even 0.01% to 30% by weight (w / w), relative to the total weight of the beads.

[0049] According to one embodiment, the internal phase comprises an oil.

[0050] According to one embodiment, the internal phase consists of oil.

[0051] According to another embodiment, the internal phase comprises a water-in-oil emulsion.

[0052] According to one embodiment, the water-in-oil emulsion comprises an aqueous phase, an oil phase, an emulsifier and a complexing agent.

[0053] According to this embodiment, the emulsifier may be selected from the group consisting of unsaturated long chain surfactants such as oleic acid, polyoxyethylene (n) oleyl ether, sorbitan monooleate, dioleate, trioleate, polyoxyethylene (n) sorbitan monooleate, dioleate, trioleate, glycerol monooleate, dioleate, sucrose monooleate, dioleate, trioleate and mixtures thereof.

[0054] Preferably, the emulsifier is used in an amount of 0.01 to 50% by weight based on the water-in-oil emulsion.

[0055] According to one embodiment, the complexing agent is selected from the group consisting of divalent electrolytes such as calcium chloride, magnesium chloride and mixtures thereof.

[0056] Preferably, the complexing agent is used in an amount of 0.01 to 5% by weight, based on the water-in-oil emulsion.

[0057] The use of water-in-oil emulsions (inverse emulsions) containing a complexing agent as the internal phase allows the complexing agent to be delivered at the oil-continuous phase interface, creating an internal membrane that protects the oil from diffusion outside the bead.

[0058] According to another embodiment, the internal phase comprises an oil phase dispersed in encapsulated and / or free form.

[0059] According to a particular embodiment, the internal phase consists of a microcapsule slurry.

[0060] The encapsulated form may be a microcapsule, which has been widely described in the prior art, preferably of the core-shell type having a polymeric shell.

[0061] The nature of the polymer shell from the microcapsules of the present invention can vary. By way of non-limiting example, the shell can be aminoplast-based, polyurea-based, or polyurethane-based. The shell can also be hybrid, i.e., organic-inorganic, for example, a hybrid shell composed of at least two types of crosslinked inorganic particles, or even a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0062] According to one embodiment, the shell comprises an aminoplast copolymer such as melamine-formaldehyde or urea-formaldehyde or crosslinked melamine formaldehyde or melamine glioxal.

[0063] According to another embodiment, the shell is polyurea-based, for example, but not limited to, made from isocyanate-based monomers and amine-containing crosslinkers, such as guanidine carbonate and / or guanazole. Preferred polyurea microcapsules comprise a polyurea wall that is the reaction product of the polymerization between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (e.g., a water-soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of the amine can be omitted.

[0064] According to a particular embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol, 0.6% to 1% cationic copolymer of vinylpyrrolidone and quaternized vinylimidazole (all percentages defined by weight relative to the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is preferably an anionic or amphiphilic biopolymer selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate and mixtures thereof.

[0065] According to another embodiment, the shell is polyurethane-based, made from, for example, but not limited to, polyisocyanates and polyols, polyamides, polyesters, and the like.

[0066] The preparation of aqueous dispersions / slurries of core-shell microcapsules is well known to those skilled in the art. In one embodiment, the microcapsule wall material may comprise any suitable resin, including, among others, melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, and the like. Suitable resins include reaction products of aldehydes and amines, and suitable aldehydes include formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include methylolmelamine, methylated methylolmelamine, iminomelamine, and mixtures thereof. Suitable ureas include dimethylolurea, methylated dimethylolurea, urea-resorcinol, and mixtures thereof. Suitable materials for manufacturing can be obtained from one or more of the following companies: Solutia Inc. (St. Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), Sigma-Aldrich (St. Louis, Missouri USA).

[0067] According to certain embodiments, the core-shell microcapsules are formaldehyde-free capsules. A typical method for preparing a slurry of aminoplast formaldehyde-free microcapsules comprises: 1) mixing a slurry of the aminoplast formaldehyde-free microcapsules with the following: a) a polyamine component in the form of melamine or a mixture of melamine with at least one C1-C4 compound containing two NH2 functional groups; b) Glyoxal and C 4~6 an aldehyde component in the form of a mixture of 2,2-dialkoxy-ethanal and, optionally, glyoxalate, wherein the glyoxal / C 4~6 an aldehyde component having a molar ratio of 2,2-dialkoxy-ethanal of 1 / 1 to 10 / 1; c) Protonic Acid Catalyst preparing an oligomeric composition comprising the reaction product of, or an oligomeric composition obtained by reacting them together; 2) preparing an oil-in-water dispersion, wherein the droplet size is between 1 and 600 μm, the dispersion comprising: I. Oil; ii.Aqueous medium; iii. at least one oligomeric composition obtained in step 1; iv. Below: A) C4~C 12 Aromatic or aliphatic diisocyanates or triisocyanates, and their biurets, triuret, trimers, trimethylolpropane adducts and mixtures thereof; and / or B) Formula A-(oxiran-2-ylmethyl)n Dioxirane or trioxirane compounds of the formula: wherein n is 2 or 3, and A is a C2-C6 group optionally containing 2 to 6 nitrogen and / or oxygen atoms. at least one crosslinker selected from the group consisting of v. C1-C4 compounds optionally containing two NH2 functional groups a step including: 3) heating the dispersion; 4) Cooling the dispersion Includes.

[0068] This method is described in more detail in WO 2013 / 068255, the contents of which are incorporated by reference.

[0069] According to another embodiment, the shell of the microcapsules is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea- and polyurethane-based microcapsule slurries are described, for example, in WO 2007 / 004166, EP 2300146, and EP 2579976, the contents of which are also incorporated by reference. Typically, the method for preparing polyurea- or polyurethane-based microcapsule slurries comprises the following steps: a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase; b) preparing an aqueous solution of an emulsifier or colloidal stabilizer to form an aqueous phase; c) adding an oil phase to an aqueous phase to form an oil-in-water dispersion, wherein the average droplet size is between 1 and 500 μm, preferably between 5 and 50 μm; d) applying conditions sufficient to induce interfacial polymerization to form microcapsules in the form of a slurry. Includes.

[0070] A continuous phase containing biopolymers As previously mentioned, the crystalline beads defined in the present invention comprise an internal phase dispersed in a continuous phase made of at least one biopolymer that forms a hydrogel matrix.

[0071] According to one embodiment, the biopolymer in the continuous phase is selected from the group consisting of alginate, xanthan, carrageenan, chitosan, pectin, gellan, agar, hydroxycellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose and mixtures thereof. These biopolymers are preferred because they are natural, non-toxic products that are completely biodegradable and safe for the environment.

[0072] According to a particular embodiment, the continuous phase is made of an alginate, preferably sodium alginate, or xanthan.

[0073] According to a particular embodiment, the continuous phase represents at least 50% by weight, preferably at least 70% by weight, based on the total weight of the beads.

[0074] According to a particular embodiment, the amount of biopolymer represents 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total weight of the beads.

[0075] liquid crystal structured phase The crystalline beads according to the invention are characterized by the fact that they comprise at least one liquid crystalline structured phase.

[0076] According to one embodiment, the liquid crystalline structured phase is dispersed in a continuous phase.

[0077] According to another embodiment, the liquid crystalline structured phase is at the interface between the internal phase and the continuous phase.

[0078] According to one embodiment, the liquid crystal phase is formed by mesogenic compounds selected from the group consisting of long chains of alcohols (long chain: CH2 groups > 12), long chains of fatty acids, long chains of fatty acid salts, long chains of glycerol fatty acids; long chains of lipophilic linear or branched, single or double chain surfactants with an HLB of less than 10, long chains of cholesterol esters, polymers and copolymers with an HLB of less than 10, such as diblock and triblock polymers, e.g. Pluronics.

[0079] By "long chain" is meant a compound having a hydrocarbon chain of at least 12 carbons.

[0080] According to one embodiment, the mesogenic compound is a surfactant with a long hydrocarbon chain of at least 12 carbons and an HLB of less than 10.

[0081] According to certain embodiments, the mesogenic compound is selected from the group consisting of glyceryl stearate citrate; sucrose stearate; sucrose distearate; myristyl alcohol; palmityl alcohol; stearyl alcohol; oleyl alcohol; behenyl alcohol; lauric acid; myristic acid; palmitic acid; stearic acid; oleic acid; linoleic acid; behenic acid; polyglyceryl-10 myristate; lecithin; a mixture of steareth-2 and PEG-8 distearate; glyceryl distearate; ethylene glycol distearate; a mixture of ceteth-20, glyceryl stearate, PEG-6 stearate, and steareth-20; a mixture of glyceryl stearate, polyglyceryl-6 palmitate, and cetearyl alcohol; and mixtures thereof.

[0082] For example, there may be mentioned commercially available products such as Dermofeel GCS, Symbio® muls GC, Symbio® muls WO products from Dr. Straetmans, Nikkomulese LC products from Nikkol Corp., Natragem EW-FL-(MV) products from Croda and mixtures thereof.

[0083] According to one embodiment, the mesogenic compound does not comprise cetearyl alcohol in combination with behentrimonium methosulfate.

[0084] According to another embodiment, the mesogenic compound does not comprise polyglyceryl diisostearate.

[0085] According to one embodiment, the beads comprise a liquid crystal phase in an amount of 0.0001% to 70%, preferably 1% to 50%, more preferably 3 to 10%, based on the total weight of the beads.

[0086] The complexation of the dispersion in step (iii) can be obtained in different ways depending on the nature of the biopolymer matrix.

[0087] According to a particular embodiment, step (iv) consists in adding the dispersion of step (iii), preferably dropwise, to a water bath containing water-soluble complexing agent ions. This embodiment is particularly suitable when the biopolymer is alginate.

[0088] According to one embodiment, the water-soluble complexing agent used in step (iv) is selected from the group consisting of calcium, barium, magnesium, and is preferably used at a concentration of 0.01 to 5%.

[0089] According to another embodiment, step (iv) consists of adding the dispersion of step (iii) to a cold oil bath. This embodiment is particularly suitable when the biopolymer is agar.

[0090] The amount of water added in step (i) is preferably from 90% to 99%, preferably from 95 to 99%, based on the weight of the dispersion.

[0091] The amount of biopolymer added in step (i) is preferably 0.1% to 10%, preferably 0.2% to 5%, based on the weight of the dispersion.

[0092] The hydrophobic active ingredient is preferably added in an amount of 0.001% to 50%, preferably 0.01% to 30%, based on the weight of the dispersion.

[0093] According to one embodiment, the weight ratio of complexing agent to biopolymer should be between 0.01:1 and 1:0.2.

[0094] According to a particular embodiment, step (ii) consists in preparing a water-in-oil emulsion.

[0095] According to one embodiment, the water-in-oil emulsion is prepared in the presence of an emulsifier and a complexing agent, and consists of mixing an aqueous phase, preferably in an amount of 0.001 to 10%, a hydrophobic active ingredient, preferably in an amount of 50 to 90%, an emulsifier, preferably in an amount of 0.01 to 40%, and a complexing agent, preferably in an amount of 0.1 to 10%, based on the weight of the water-in-oil emulsion, until a homogeneous emulsion is obtained.

[0096] According to the present invention, the mesogenic compounds are added in steps (i) and / or (ii) under conditions that allow the compounds to form liquid crystals.

[0097] The amount of mesogenic compound added in step (i) and / or (ii) is preferably from 0.0001% to 50%, preferably from 0.001% to 30%, based on the weight of the dispersion.

[0098] It is well known that liquid crystals can be generated by adjusting physical parameters such as concentration or temperature.

[0099] Those skilled in the art will be able to select appropriate conditions for forming liquid crystals depending on the properties of the mesogenic compounds.

[0100] As an example, a solution containing a liquid crystal phase can be heated, for example, at a temperature between 40° C. and 70° C., and subsequently cooled, for example, to room temperature, to promote the formation of the liquid crystal phase.

[0101] When the mesogenic compound is added in step (i) (i.e., to the aqueous phase), the crystalline beads prepared by the process contain liquid crystals dispersed in the continuous phase, whereas when the mesogenic compound is added in step (ii) (i.e., to the oil phase), the crystalline beads prepared by the process contain liquid crystals at the interface between the dispersed and continuous phases (i.e., around the oil droplets).

[0102] Indeed, due to the low solubility in water of the mesogenic compound, when added in step (ii), liquid crystals form at the interface between the continuous and internal phases when the two phases are mixed.

[0103] According to certain embodiments, the process comprises the further step of adding the dispersion to a hydrophobic solvent such as ethyl citrate, silicone oil, Neobee, isopropyl myristate, etc. to form an inverse emulsion between step (iii) and step (iv), and the further step of removing the hydrophobic solvent by dilution after step (iv).

[0104] According to one embodiment, the beads as defined in the present invention are in the form of a consumer product, for example in the form of a personal care product such as a shower gel or body lotion, ready for consumer use. According to this embodiment, the beads can be suspended in water or a biopolymer gel, for example made of water, xanthan gum and potassium sorbate, or any cosmetic gel.

[0105] According to this embodiment, the hydrogel matrix and / or internal phase may comprise consumer product base ingredients including ingredients selected from the group consisting of surfactants, thickening polymers, pigments, UV filters, aesthetic particles, emollients, hydrating agents, antimicrobial agents, bioactive agents, preservatives, preferably in an amount of up to 50%, preferably up to 20%, based on the total weight of the continuous phase.

[0106] Another object of the present invention is a method for preparing hydrogel beads comprising a hydrophobic active ingredient dispersed in a biopolymer matrix, said method comprising the following steps: (i) preparing a continuous phase comprising water and a biopolymer; (ii) preparing an internal phase comprising a hydrophobic active ingredient, preferably a perfume or flavor oil; (iii) mixing the continuous phase and the internal phase to form a dispersion; (iv) forming beads by inducing complexation of the dispersion obtained in step (iii); wherein a mesogenic compound is added in step (i) and / or (ii) under conditions that allow the formation of at least one liquid crystalline structured phase in the hydrogel beads.

[0107] All of the embodiments described above for the hydrogel beads also apply to the method for preparing the hydrogel beads.

[0108] Another object of the present invention is hydrogel beads having an internal phase dispersed in a continuous phase, wherein: the internal phase comprises a hydrophobic active ingredient, preferably a perfume or flavor oil, and - the continuous phase comprises biopolymers and water to form a hydrogel matrix; The crystalline beads are characterized by comprising at least one liquid crystalline structured phase.

[0109] Crystalline beads as defined in the present invention comprise an internal phase dispersed in a continuous phase that forms a hydrogel matrix.

[0110] According to a particular embodiment, the continuous phase represents at least 50% by weight, preferably at least 70% by weight, based on the total weight of the beads.

[0111] According to a particular embodiment, the amount of biopolymer represents 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total weight of the beads.

[0112] According to one embodiment, the beads comprise a liquid crystal phase in an amount of 0.0001% to 70%, preferably 1% to 50%, more preferably 3 to 10%, based on the total weight of the beads.

[0113] All of the above embodiments also apply to hydrogel beads.

[0114] Another subject of the present invention is a perfumed composition comprising beads as defined above, at least one ingredient selected from the group consisting of perfume co-ingredients, perfume carriers and mixtures thereof, and optionally at least one perfume adjuvant.

[0115] Non-limiting examples of liquid perfume carriers include emulsifying systems, i.e., solvent and surfactant systems, or solvents commonly used in perfumery. A detailed description of the nature and types of solvents commonly used in perfumery cannot be exhaustive. However, non-limiting examples include solvents such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol, or ethyl citrate, which are the most commonly used. For compositions containing both perfume carriers and perfume co-ingredients, other suitable perfume carriers besides those specified above may be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those known under the trade name Isopar® (manufactured by Exxon Chemical), or glycol ethers and glycol ether esters, such as those known under the trade name Dowanol® (manufactured by Dow Chemical Company). By "perfuming co-ingredient" is meant herein a compound that is used in a perfumed preparation or composition to impart a hedonic effect and is not a microcapsule as defined above. In other words, such a co-ingredient must be recognized by those skilled in the art as being perfuming and capable of at least imparting or adjusting the odor of the composition in a positive or pleasant way, and not merely having an odor.

[0116] The nature and type of perfuming co-ingredients present in perfuming compositions do not warrant a more detailed description here, which is in any case not exhaustive; those skilled in the art can select them based on their general knowledge and depending on the intended use or application and the desired organoleptic effect. Generally speaking, these perfuming co-ingredients belong to various chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are listed in various reference texts, such as S. Arctander, *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its latest edition, or other similar works, as well as in the abundant patent literature in the field of perfumery. It is understood that said co-ingredients can also be compounds known to control the release of various types of perfuming compounds.

[0117] By "perfuming adjuvant" is meant here an ingredient capable of imparting further additional benefits such as color, particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfumed bases cannot be exhaustive, but it should be mentioned that said ingredients are well known to those skilled in the art.

[0118] The crystalline beads of the present invention are advantageously used in various fields of perfumery, namely fine or functional perfumery.

[0119] Another subject of the present invention is therefore represented by a consumer product, preferably a perfumed consumer product, comprising crystalline beads as defined above.

[0120] For the sake of clarity, it should be mentioned that by "perfumed consumer product" is meant a consumer product that is expected to deliver at least a pleasant perfume effect to the surface to which it is applied (e.g., skin, hair, textiles or household surfaces). In other words, the perfumed consumer product according to the present invention is a perfumed consumer product comprising a functional formulation, as well as optionally additional benefit agents corresponding to the desired consumer product, for example, a detergent or fragrance, and an olfactory-effective amount of at least one compound of the present invention.

[0121] The nature and type of constituents of perfume consumer products do not warrant a more detailed description here, which is in no way exhaustive, and the skilled person can select them based on his general knowledge and depending on the nature of the product and the desired effect. Their formulations do not warrant a more detailed description here, which is in no way exhaustive, and the skilled person who formulates such consumer products is entirely able to select suitable ingredients based on his general knowledge and the available literature.

[0122] In particular, examples of such formulations can be found in patents and patent applications relating to such products, for example WO 2008 / 016684, US 2007 / 0202063, WO 2007 / 062833, WO 2007 / 062733, WO 2005 / 054422, EP 1741775, GB 2432843, GB 2432850, GB 2432851, GB 2432852, WO 9850011, WO 2013174615 or WO 2012084904.

[0123] Non-limiting examples of suitable perfumed consumer products may be perfumes such as fine perfumes, body splashes, colognes, or aftershaves; fabric care products such as liquid detergents, fabric softeners, fabric deodorants, ironing waters, or bleaches; body care products such as hair care products (e.g., shampoos, hair conditioners, colorants, or hair sprays), cosmetics (e.g., vanishing creams, body lotions, or deodorants or antiperspirants), or skin care products (e.g., scented soaps, shower or bath mousses, body washes, oils or gels, bath salts, or hygiene products); air care products such as air fresheners; or home care products such as all-purpose cleaners, liquid dishwashing products, toilet cleaners, or products for cleaning various surfaces, e.g., sprays and wipes for treating / restoring textiles or hard surfaces (floors, tiles, stone floors, etc.).

[0124] According to one embodiment, the perfumed consumer product is in the form of a personal care product, for example in the form of a shower gel or body lotion.

[0125] The beads of the present invention can also be used in a wide variety of edible end products when encapsulating flavors. Consumer products amenable to flavoring with the microcapsules of the present invention can include foods and beverages. For example, food bases in which the powdered microcapsules of the present invention can be used include: Non-alcoholic drinks (e.g., carbonated soft drinks, bottled water, sports / energy drinks, juice drinks, vegetable juices, vegetable juice preparations), Alcoholic beverages (e.g., beer and malt beverages, spirit drinks); Dairy products (e.g. fresh cheese, soft cheese, hard cheese, milk drinks, whey, butter, partially or totally hydrolyzed milk protein-containing products, fermented milk products, condensed milk and similar products), Dairy-based products (e.g. fruit or flavored yogurt, ice cream, fruit ice), Chocolate and compound coatings, Products based on fats or oils or their emulsions (e.g. mayonnaise, spreads, margarines, shortenings, remoulades, dressings, spice preparations), Desserts (e.g., gelatin and pudding) Products made from soy protein or other soy fractions (e.g., soy milk and products made therefrom, soy lecithin-containing preparations, fermented products or products made therefrom such as tofu or tempeh, soy sauces); Vegetarian meat substitutes, vegetarian burgers, Spices or spice preparations (e.g. mustard preparations, horseradish preparations), spice mixtures, in particular condiments used, for example, in the snack sector Includes:

[0126] The crystalline beads defined in the present invention have proven to be particularly and advantageously stable in difficult media, whilst having a pleasant texture.

[0127] The present invention will now be further illustrated by examples, it will be understood that the invention as claimed is not intended to be limited in any way by these examples.

[0128] Example Example 1 Flavored alginate beads containing a liquid crystalline structured phase dispersed in a continuous phase. In the first step, a suspension of liquid crystals was prepared in alginate solution (phase A). Glyceryl stearate citrate (Dermofeel GSC) was added to the alginate solution and heated to 65°C in a water bath while stirring. After cooling phase A to room temperature, the fragrance (phase B) was added and the mixture was stirred for 5 / 10 minutes at 500 / 600 rpm using a stirring motor RW 11 basic "Lab egg" IKA and a paddle stirrer R1001 (d=34 mm).

[0129] The second step consisted of forming spherical beads in a calcium solution (phase C): the alginate solution containing the liquid crystals and fragrance was added dropwise to a water bath containing calcium ions.

[0130] After 20 minutes of contact with the calcium solution, beads containing a liquid crystalline phase dispersed in a continuous phase (i.e., a hydrogel matrix) are obtained (see Figures 1a and 1b, where the liquid crystalline phase can be seen in polarized light). They are then filtered, washed three times, and placed in water (see Figure 2). The resulting beads exhibit a creamy texture.

[0131] [Table 1]

[0132] [Table 2] 1) Manufacturer: Alfa Aesar, Karlsruhe, Germany 2) Glyceryl Stearate Citrate, Manufacturer: Dr Straetmans GmbH, Hamburg, Germany 3) See Table 2a

[0133] [Table 3] 1) 4-Cyclohexyl-2-methyl-2-butanol; manufacturer and trade name from Firmenich SA, Geneva, Switzerland 2) Diethyl 1,4-cyclohexanedicarboxylate; manufacturer and trade name from Firmenich SA, Geneva, Switzerland 3) Methyl dihydrojasmonate; manufacturer and trade name from Firmenich SA, Geneva, Switzerland

[0134] Example 2 Flavored alginate beads containing liquid crystal structured phases and inverse emulsions The internal phase used in this example consists of an inverse emulsion (water-in-oil emulsion) containing a complexing agent, as opposed to Example 1, where the internal phase consists solely of an oil phase.

[0135] The method includes the following steps: 1) The first step is the preparation of an inverse emulsion containing fragrance, emulsifier, water and complexing agent. All ingredients are added in order and mixed at room temperature until completely dissolved (Ultra Turrax can be used). 2) After the biopolymer is dissolved in water, a mesogenic compound is added to the solution to form a liquid crystal phase. The solution can be heated to promote the formation of the liquid crystal phase. 3) The inverse emulsion is added (at room temperature) to a biopolymer solution containing LC. The mixture is vigorously mixed. Microparticles containing the w / o emulsion in the biopolymer solution are formed. 4) The final step consists in forming spherical beads in an aqueous solution of complexing agent by adding dropwise the mixture obtained in step 3). 5) After their formation, the spherical particles are removed from the complexing agent solution, washed three times, and placed in water.

[0136] [Table 4] 1) See Table 2a 2) Polyoxyethylene (2) oleyl ether 3) Ethyl lauroyl arginate HCl; Manufacturer: Vedeqsa Inc, Spain 4) Manufacturer: Alfa Aesar, Karlsruhe, Germany 5) Glyceryl Stearate Citrate, Manufacturer: Dr Straetmans GmbH, Hamburg, Germany

[0137] [Table 5] 1) See Table 2a 2) Polyoxyethylene (2) oleyl ether 3) Ethyl lauroyl arginate HCl; Manufacturer: Vedeqsa Inc, Spain 4) Manufacturer: Alfa Aesar, Karlsruhe, Germany 5) Glyceryl Stearate Citrate, Manufacturer: Dr Straetmans GmbH, Hamburg, Germany

[0138] Example 3 (Comparative Example) Flavored alginate beads without liquid crystals In the first step, the alginate solution was prepared (phase A). Then the fragrance (phase B) was added and the mixture was stirred for 5 / 10 minutes at 500 / 600 rpm with a stirring motor RW 11 basic "Lab egg" IKA and a paddle stirrer R1001 (d=34 mm).

[0139] The second step consisted of forming spherical beads in the calcium solution (phase C): the alginate solution and fragrance were added dropwise to a water bath containing calcium ions.

[0140] [Table 6] 1) Manufacturer: Alfa Aesar, Karlsruhe, Germany 2) See Table 2a [Table 7] 1) Manufacturer: Alfa Aesar, Karlsruhe, Germany 2) See Table 2a

[0141] Example 4 Flavored alginate beads containing a liquid crystalline structured phase (at the interface between the continuous and internal phases) This type of bead is prepared from a direct oil-in-water (o / w) emulsion composed of an aqueous phase (phase A) and an oil phase containing the fragrance (phase B). The main difference with the above beads of Example 1 is the position of the LCs: they cover the fragrance droplets instead of being dispersed in the alginate phase.

[0142] In a first step, the two phases A and B are heated to 50° C. in order to dissolve the mesogenic compounds in the fragrance. The emulsion is obtained by mixing A and B under mechanical stirring with a stirring motor RW 11 Basic "Lab egg" and a paddle stirrer (1500 rpm, 15 minutes at room temperature).

[0143] The second step consisted of forming spherical beads in a calcium solution (phase C): the alginate solution and the fragrance containing liquid crystals were added dropwise to a water bath containing calcium ions.

[0144] After 20 min of contact with the calcium solution, beads containing a liquid crystalline phase at the interface between the internal and continuous phase are obtained (see Figure 3 b, where the liquid crystalline phase can be seen in polarized light).

[0145] [Table 8] 1) Manufacturer: Alfa Aesar, Karlsruhe, Germany 2) See Table 2a 3) Glyceryl stearate and Polyglyceryl-6 palmitate / succinate and Cetearyl alcohol. Manufacturer: Croda Inc.

[0146] [Table 9]

[0147] Example 5 Flavored agar beads containing a liquid crystalline structured phase. In the first step, a solution was prepared using the ingredients in Phase A (Table 9 below). Then, an inverse emulsion was prepared using the ingredients in Phase B. All compounds were added and mixed to form this W / O emulsion. Phase B was then added to Phase A to form a dispersion. The dispersion was heated to boiling (90°C).

[0148] The second step is to form spherical beads in oil (phase C). The dispersion (phase A+B) was added dropwise to a cold oil bath (10°C).

[0149] After 5 minutes in phase C, the resulting beads were removed.

[0150] [Table 10] 1) Manufacturer: AppliChem GmbH 2) Manufacturer: Vedeqsa Inc,Spain [Table 11]

[0151] Example 6 Shower gel in the form of crystalline alginate flavored beads In the first step, the first five compounds of Phase A, which represent examples of personal care formulations, are mixed together.

[0152] In the second step, an alginate solution is prepared using compounds 6 and 7 in the continuous phase: alginate solution and dermofeel GSC in the desired ratio. Dermofeel GSC and alginate hydrogel are stirred at 65°C for 1 hour. The sample is then cooled to room temperature while stirring.

[0153] Finally, the resulting mixture of phases A and B is stirred with a stirring motor RW 11 basic "Lab egg" IKA and a paddle stirrer R1001 (d=34 mm) at 500 / 600 rpm at room temperature for 5-10 minutes.

[0154] In the final step, crystalline beads are formed by prilling the mixture of phases A and B in a 0.5% aqueous CaCl solution. Once the beads are produced, they are filtered, washed three times with distilled water, and retained in water or in water containing a desired thickening agent, such as a biopolymer or other polymer used for this purpose.

[0155] The crystalline beads prepared by the process described in this example are ready for consumer use as a shower gel.

[0156] [Table 12] 1) Acrylates copolymer; Manufacturer: Lubrizol Corp. 2) Sodium laureth sulfate; Manufacturer: BASF 3) Cocamidopropyl Betaine; Manufacturer: Evonik Industries 4) See Table 2a [Table 13]

[0157] Example 7 Body lotion in the form of crystalline alginate flavored beads [Table 14]

[0158] [Table 15]

[0159] Preparation process: I. To prepare Phase A, a 2% by weight aqueous solution of sodium alginate is mixed with a 7% aqueous solution of Carbopol Aqua SF and all remaining ingredients of Phase A. The mixture is heated to 67°C with stirring at 600 rpm and cooled to room temperature to form a liquid crystal. II. Preparation of Phase B All compounds are mixed to obtain a homogeneous mixture. III. Mix Phase A and Phase B while stirring at 500 rpm at room temperature for 1 hour. IV. Crystalline beads are formed by prilling a mixture of phases A and B with a 0.5% aqueous CaCl2 solution. V. Rinse the beads and store them in water or in a gel with the following composition: [Table 16]

[0160] Example 8 Fragrance release performance The perfume release from a solution containing phases A and B as defined in Example 2 (Sample A) was measured by gas chromatography coupled with mass spectrometry at a temperature of 37°C before forming spherical beads in calcium and compared with the perfume release from a solution containing phases A and B as defined in Example 3 (Comparative B).

[0161] Fragrance leakage is measured by extracting the aqueous phase in which the crystalline hydrogel beads are stored and analyzing it using a GC-MS instrument.

[0162] For the analysis, 5 g of sample and 5 ml of ISTD (internal standard compound) solution are used. The sample is stirred at 400 rpm in an IKA incubator for 10 minutes, then centrifuged at 5000 rpm for 5 minutes. Then, 1.5 ml is injected into the GC-MS system.

[0163] An Agilent GC equipped with a split / splitless inlet and helium as the carrier gas is used. Samples are analyzed with a split ratio of 10:1. The analysis is performed at a constant flow rate with an initial flow rate of 1 mL / min (corresponding to an average velocity of 37 cm / s). The oven program starts at 80°C; a first gradient temperature of 10°C / min reaches 200°C, followed by another gradient temperature of 20°C / min reaches 260°C. This final temperature is held for 1 minute.

[0164] The GC-MS instrument allows working with SIM analysis: two or three ions per compound are selected and analyzed in the gas chromatogram after a 2-minute solvent delay.

[0165] Perfume release was measured for two perfume raw materials (benzyl acetate and dihydromyrcenol), with the release from comparative sample B considered to be 100%.

[0166] The results are shown in Figures 4a and 4b.

[0167] From these figures it can be concluded that the crystalline beads according to the invention provide better retention of fragrance in the beads compared to comparative sample B, which does not contain liquid crystals, since a lower gas concentration of fragrance is observed in sample A (according to the invention).

[0168] Example 9 Mechanical properties The effect of the liquid crystal (LC) phase on bead stiffness was investigated by measuring the normal force required to deform alginate particles prepared according to Example 2. A Texture Analyzer TA-XT2 was used for this purpose. The normal force as a function of the concentration of mesogenic compound (Dermofeel GSC) is shown in Figure 5.

[0169] From this example, it can be concluded that the beads are strengthened by the presence of the LC phase, since the normal force against deformation is greater than that without the LC phase.

[0170] Example 10 Alginate beads containing a liquid crystalline structured phase dispersed in a continuous phase and core-shell microcapsules In the first step, a suspension of liquid crystals was prepared in alginate solution (phase A). Glyceryl stearate citrate (Dermofeel GSC) was added to the alginate solution and heated to 65°C in a water bath with stirring. After cooling to room temperature, phase A was added with the capsule slurry (phase B) and the mixture was stirred for 5 / 10 minutes at 500 / 600 rpm using a stirring motor RW 11 basic "Lab egg" IKA and a paddle stirrer R1001 (d=34 mm).

[0171] The second step consisted of forming spherical beads in a calcium solution (phase C): the alginate solution containing the liquid crystals and fragrance was added dropwise to a water bath containing calcium ions.

[0172] After 5 minutes of contact with the calcium solution, beads containing a liquid crystalline phase dispersed in a continuous phase (i.e., a hydrogel matrix) are obtained. They are then filtered, washed three times, and placed in water. The resulting beads exhibit a creamy texture.

[0173] [Table 17]

[0174] [Table 18] 2) Glyceryl Stearate Citrate, Manufacturer: Dr Straetmans GmbH, Hamburg, Germany 3) See below for how to prepare the microcapsule slurry.

[0175] Preparation of melamine glioxal microcapsules coated with cationic polymers In a round-bottom flask, melamine (0.87 g), 2,2-dimethoxyethanal (60 wt% in water, 1.32 g), glyoxal (40 wt% in water, 1.66 g), and glyoxylic acid (50 wt% in water, 0.56 g) were dispersed in water (1.53 g) at room temperature. The pH value of the dispersion was controlled with sodium hydroxide (30 wt% in water, pH = 9.5). The reaction mixture was heated at 45 °C for 25 minutes to obtain a solution. Water (6.50 g) was then added, and the resin was stirred at 45 °C for 5 minutes.

[0176] The resin was transferred to a 200 mL beaker. Guanazole (0.58 g) was dissolved in a solution of Ambergum 1221 (2% by weight in water, 24.86 g). The resulting solution was introduced into a beaker. An oil solution of Takenate D-110N (2.07 g), Fragrance B (24.72 g)—see Table b below—and Uvinul A plus (1.41 g) was added to the aqueous solution. The biphasic reaction mixture was sheared using an Ultra-turrax at 21,500 rpm for 2 minutes. Acetic acid was added to initiate the polycondensation (pH = 5.35). The emulsion quality was controlled by optical microscopy. The emulsion was transferred to a 200 mL Schmizo reactor and heated at 45°C for 1 hour, then at 60°C for 1 hour, and finally at 80°C for 2 hours. Next, various amounts of solutions of the first cationic copolymer, acrylamidopropyltrimonium chloride / acrylamide copolymer (Salcare® SC60, manufacturer BASF) (3 wt. % in water) and the second cationic copolymer, polygalactomannan 2-hydroxypropyltrimethylammonium chloride ether (Jaguar C13S, manufacturer Rhodia) (1 wt. % in water) were added and the reaction mixture was heated at 80° C. for 30 minutes. A solution of urea (4.90 g, 40 wt. % in water) was finally added to the reaction mixture, which was heated at 80° C. for 30 minutes.

[0177] [Table 19-1] [Table 19-2] 1)Trade name from IFF: 2-tert-butyl-1-cyclohexyl acetate 2) Trade name from Firmenich: 2,2,5-trimethyl-5-pentacyclopentan-1-one 3) Trade name from Symrise; Galbanum oxyacetate

[0178] Example 11 Refreshing beads for oral care In the first step, a suspension of liquid crystals was prepared in an alginate solution (phase A). To prepare this solution, sucrose was added to water. After homogenization, sodium alginate was added and the solution was mixed until homogenous. Sugar ester Ryoto S-970 was added to the alginate solution. The mixture was heated to 75°C in a water bath while stirring. After cooling phase A to room temperature, the flavor (phase B) was added and the mixture was stirred for 10 minutes at 500 / 600 rpm using a stirring motor RW 11 Basic "Lab egg" IKA and a paddle stirrer R1001 (d = 34 mm).

[0179] The second step consisted of forming spherical beads in a calcium solution (phase C): the alginate solution containing the liquid crystals and fragrance was added dropwise to a water bath containing calcium ions.

[0180] After 10 minutes of contact with the calcium solution, beads containing a liquid crystalline phase dispersed in a continuous phase (i.e., a hydrogel matrix) were obtained. They were then filtered, washed three times, and placed in water. The resulting beads exhibited a creamy texture.

[0181] [Table 20]

[0182] [Table 21] 1) Sucrose, manufactured by Sigma-Aldrich, Switzerland 2) Glyceryl Stearate Citrate, Manufacturer: Dr Straetmans GmbH, Hamburg, Germany 3) Sucrose stearate, Manufacturer: Mitsubishi-Kagaku Foods Corporation, Japan 4) Manufacturer and trade name from Firmenich SA, Geneva, Switzerland

[0183] Example 12 Flavor Beads In the first step, a suspension of liquid crystals was prepared in an alginate solution (phase A). To prepare this solution, sucrose was added to water. After homogenization, sodium alginate was added and the solution was mixed until homogenous. Sugar ester Ryoto S-970 was added to the alginate solution. The mixture was heated to 75°C in a water bath while stirring. After cooling to room temperature, phase A was added with the flavor (phase B) and stirred for 10 minutes at 500 / 600 rpm using a stirring motor RW 11 Basic "Lab egg" IKA and a paddle stirrer R1001 (d = 34 mm).

[0184] The second step consisted of forming spherical beads in a calcium solution (phase C): the alginate solution containing the liquid crystals and fragrance was added dropwise to a water bath containing calcium ions.

[0185] After 10 minutes of contact with the calcium solution, beads containing a liquid crystalline phase dispersed in a continuous phase (i.e., a hydrogel matrix) were obtained. They were then filtered, washed three times, and placed in water. The resulting beads exhibited a creamy texture.

[0186] [Table 22]

[0187] [Table 23] 1) Sucrose, manufactured by Sigma-Aldrich, Switzerland 2) Glyceryl Stearate Citrate, Manufacturer: Dr Straetmans GmbH, Hamburg, Germany 3) Sucrose stearate, Manufacturer: Mitsubishi-Kagaku Foods Corporation, Japan 4) Flavor, manufacturer and product name from Firmenich SA, Geneva, Switzerland

[0188] Example 13 Shampoo compositions containing hydrogel beads according to the present invention 1) Shampoo Compositions Containing Hydrogel Beads 25 g of hydrogel beads prepared according to Example 1 were added to 100 g of shampoo base A having the following composition: [Table 24]

[0189] [Table 25] 1) Acrylates copolymer; Manufacturer: Lubrizol Corp. 2) See Table 2a [Table 26]

Claims

1. Steps below: (i) preparing a continuous phase comprising water and a biopolymer; (ii) preparing an internal phase comprising a hydrophobic active ingredient; (iii) mixing the continuous phase and the internal phase to form a dispersion; (iv) inducing complexation of the dispersion obtained in step (iii) to form beads.

1. A method for preparing hydrogel beads, comprising: adding a mesogenic compound in step (i) under conditions that allow the formation of at least one liquid crystalline structured phase in said hydrogel beads; the biopolymer is selected from the group consisting of alginate, pectin, and mixtures thereof; the mesogenic compound is selected from the group consisting of glyceryl stearate citrate; sucrose stearate; sucrose distearate; myristyl alcohol; palmityl alcohol; stearyl alcohol; oleyl alcohol; behenyl alcohol; lauric acid; myristic acid; palmitic acid; stearic acid; oleic acid; linoleic acid; behenic acid; polyglyceryl-10 myristate; lecithin; a mixture of steareth-2 and PEG-8 distearate; glyceryl distearate; ethylene glycol distearate; a mixture of ceteth-20, glyceryl stearate, PEG-6 stearate, and steareth-20; a mixture of glyceryl stearate, polyglyceryl-6 palmitate, and cetearyl alcohol; and mixtures thereof; a solution containing a liquid crystal phase formed by the mesogenic compound is heated and then cooled to form the liquid crystal structured phase; A method wherein step (iv) comprises adding the dispersion of step (iii) to a water bath containing water-soluble complexing agent ions selected from the group consisting of calcium, barium, magnesium ions and mixtures thereof.

2. 10. The method of claim 1, wherein step (ii) comprises preparing a water-in-oil emulsion or a microcapsule slurry.

3. 3. The method of claim 1, wherein in step (iv), a water-soluble complexing agent is used, and the weight ratio of said water-soluble complexing agent to said biopolymer is from 0.01:1 to 1:0.

2.

4. Based on the total weight of the dispersion, - the amount of said biopolymer is between 0.1 and 10% by weight, the amount of said hydrophobic active ingredient is between 0.001 and 50% by weight, the amount of said mesogenic compounds is between 0.0001 and 50% by weight, 4. The method according to any one of claims 1 to 3.

5. The method according to any one of claims 1 to 4, wherein the beads are macroscopic and have a size between 1 mm and 10 mm.

6. 6. The method of any one of claims 1 to 5, wherein the continuous phase and / or the internal phase comprises additional ingredients selected from the group consisting of surfactants, thickening polymers, pigments, UV filters, aesthetic particles, emollients, hydrating agents, antimicrobial agents, bioactive agents, cooling agents, preservatives and mixtures thereof.

7. 1. Hydrogel beads having an internal phase dispersed in a continuous phase, comprising: - the internal phase comprises a hydrophobic active ingredient, and - the continuous phase comprises biopolymers and water to form a hydrogel matrix; the beads comprise at least one liquid crystalline structured phase; the liquid crystal structured phase is dispersed in the continuous phase; The hydrogel beads are characterized in that the biopolymer is selected from the group consisting of alginate, pectin, and mixtures thereof.

8. 1. A method for preparing hydrogel beads comprising a hydrophobic active ingredient dispersed in a biopolymer matrix, the method comprising the steps of: (i) preparing a continuous phase comprising water and a biopolymer; (ii) preparing an internal phase comprising a hydrophobic active ingredient; (iii) mixing the continuous phase and the internal phase to form a dispersion; (iv) inducing complexation of the dispersion obtained in step (iii) to form beads. wherein a mesogenic compound is added in step (i) under conditions that allow the formation of at least one liquid crystalline structured phase in said hydrogel beads; the biopolymer is selected from the group consisting of alginate, pectin, and mixtures thereof; the mesogenic compound is selected from the group consisting of glyceryl stearate citrate; sucrose stearate; sucrose distearate; myristyl alcohol; palmityl alcohol; stearyl alcohol; oleyl alcohol; behenyl alcohol; lauric acid; myristic acid; palmitic acid; stearic acid; oleic acid; linoleic acid; behenic acid; polyglyceryl-10 myristate; lecithin; a mixture of steareth-2 and PEG-8 distearate; glyceryl distearate; ethylene glycol distearate; a mixture of ceteth-20, glyceryl stearate, PEG-6 stearate, and steareth-20; a mixture of glyceryl stearate, polyglyceryl-6 palmitate, and cetearyl alcohol; and mixtures thereof; a solution containing a liquid crystal phase formed by the mesogenic compound is heated and then cooled to form the liquid crystal structured phase; A method wherein step (iv) comprises adding the dispersion of step (iii) to a water bath containing water-soluble complexing agent ions selected from the group consisting of calcium, barium, magnesium ions and mixtures thereof.

9. 10. A consumer product comprising or consisting of the hydrogel beads of claim 7, said consumer product being in the form of a body care product.

10. 10. A consumer product comprising or consisting of the hydrogel beads of claim 7, said consumer product being in the form of a flavored product.

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