Manufacturing method of microcapsules

Abstract

The present invention relates to a process for preparing microcapsules, in particular plant protein-based microcapsules and dispersions of such microcapsules (microcapsule slurries), which contain at least one hydrophobic active ingredient, preferably perfume- or aroma-containing plant protein-based microcapsules, and which have a balance of stability and performance compared to prior art microcapsules. Furthermore, the present invention relates to plant protein-based microcapsules obtainable by the method according to the present invention. In a further aspect, the present invention relates to the use of the plant protein-based microcapsules and dispersions according to the present invention as a component of household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters or fragrance enhancers in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals, or printing coatings for paper. Finally, the present invention relates to consumer products comprising such microcapsules or microcapsule dispersions according to the present invention.

Description

[Technical field]

[0001] The present invention relates to a process for preparing microcapsules, in particular plant protein-based microcapsules and dispersions of such microcapsules (microcapsule slurries), which contain at least one hydrophobic active ingredient, preferably perfume- or aroma-containing plant protein-based microcapsules, and which have a balance of stability and performance compared to prior art microcapsules. Furthermore, the present invention relates to plant protein-based microcapsules obtainable by the method according to the present invention. In a further aspect, the present invention relates to the use of the plant protein-based microcapsules and dispersions according to the present invention as a component of household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters or fragrance enhancers in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals, or printing coatings for paper. Finally, the present invention relates to consumer products comprising such microcapsules or microcapsule dispersions according to the present invention.

[0002] Microcapsules are particles consisting of a core and a wall material surrounding the core, whereby the core can be a solid, liquid or gaseous substance surrounded by a dense, permeable or semi-permeable wall material of polymer. During production, polymers from the starting components are deposited on the substance to be encapsulated after emulsification and coacervation, or interfacial polymerization. The core is also called the internal phase. Names such as external phase, shell or coating are also used for the wall. The diameter of microcapsules usually varies from 1 to 1000 μm. The wall thickness is usually 0.5 to 150 μm, but can be as large as 5×10 -9 ~5×10 -6 m. Typically, loadings of 25-95% by weight are possible, but loadings of 1-99% by weight are also possible.

[0003] Encapsulating the active substance with a suitable wall material (coating material) can generally be performed for several reasons: · Conversion of liquids into easy-to-handle powder forms (e.g. vegetable oils, fats coatings); Time-controlled release of substances (dosage control, depot effect for medicines, pesticides, fertilizers); · Layering of tastes, odors and colours (e.g. bitter or pungent flavours); · Protection against light, oxidation, heat, acids or bases (e.g. vitamins, flavourings etc.); · Moisture protection (e.g. hygroscopic salts or minerals); Delayed loss of volatile components (e.g. flavours) · Prevention of premature chemical reactions with other mixture components; · Improved handling before or during processing (flow properties, dust formation); ·Protection of workers from harmful or unpleasant substances (chemicals, concentrated aromas) or improving solubility or suspension through surface modification.

[0004] For example, hydrophobic active ingredients such as fragrances or flavorings, or flavors or odorants, respectively, can be readily incorporated into many different application formulations by encapsulation.

[0005] The contents of the microcapsules can generally be released in various ways, in particular based on one of the mechanisms described below: The capsules are mechanically destroyed by crushing or shearing. This mechanism is used for carbonless paper, for example. The capsules are destroyed by melting the wall material. According to this mechanism, ingredients such as leavening agents or flavors in the baking mix are released only during the baking process. The capsules are destroyed by dissolving the wall material. This mechanism is used, for example, in washing powders so that encapsulated ingredients such as enzymes are only released during the washing process. The capsule remains intact and the capsule contents are gradually released by diffusion through the capsule wall. This mechanism can be used, for example, to achieve a slow and uniform release of an active pharmaceutical ingredient in the body.

[0006] Due to their diverse properties, microcapsules are used in various fields including the printing industry, the food industry (vitamins, aromas, plant extracts, enzymes, microorganisms), the agrochemical industry (fertilizers, pesticides), the feed industry (minerals, vitamins, enzymes, drugs, microorganisms), the pharmaceutical industry, the detergent industry, and the cosmetics industry.

[0007] Many everyday products such as detergents, fabric softeners, washing powders, washing liquids, shower gels, shampoos, deodorants, polylotions, etc. are today scented with a fragrance or odorant, or a mixture of fragrances and odorants, respectively. Very often, fragrances or odorants interact with other ingredients in the formulation, or the more volatile components of a perfume evaporate faster than normal. As a result, the scent impression of the perfume changes over time or disappears completely.

[0008] Microencapsulation of such mixtures of perfumes or odorants offers the possibility to reduce or completely prevent the interaction or evaporation of highly volatile perfume ingredients in perfumed products.

[0009] Various capsule wall and coating materials are known for the production of microcapsules. The capsule wall can consist of natural, semi-synthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar, agarose, maltodextrin, alginic acid or its salts, such as sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolysates, sucrose and waxes. Semi-synthetic capsule shell materials include chemically modified celluloses, in particular cellulose esters and cellulose ethers, such as cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, as well as starch derivatives, in particular starch ethers and starch esters. Synthetic shell materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

[0010] Depending on the type of capsule wall material and the manufacturing process, microcapsules are produced with different properties in terms of diameter, size distribution and physical and / or chemical properties.

[0011] Polyurea microcapsules or polyurea / polyurethane microcapsules formed by polymerization between polyisocyanates and polyamines and / or diols or polyols are well known capsules used in various technical fields including the fragrance industry.

[0012] Polyurea microcapsules obtained by reacting two polyisocyanates with a polyamine are described, for example, in WO2011 / 161229 or WO2011 / 160733. According to WO2011 / 161229 or WO2011 / 160733, the polyurea microcapsules are produced in the presence of polyvinylpyrrolidone (PVP) as a protective colloid. WO2012 / 107323 discloses polyurea microcapsules with a polyurea shell comprising the reaction product of a polyisocyanate with guanazole (3,5-diamino)-1,2,4-triazole) and an amino acid in the presence of an anionic stabilizer or surfactant, such as an anionic polyvinyl alcohol. EP 0 537 467 B describes microcapsules prepared from polyisocyanates containing polyethylene oxide groups in the presence of a stabilizer, such as polyvinyl alcohol. According to WO2007 / 096592, microencapsulation can be carried out with an oil phase emulsified in a continuous aqueous phase which is generally stabilized by a surfactant system such as polyvinyl alcohol or its carboxylated and sulfonated derivatives.

[0013] The exemplary prior art delivery systems described above exhibit both good stability, i.e., the ability of the capsules to retain the active ingredient and thus avoid loss of volatile ingredients, as well as good performance, e.g., in the case of fragrance or odorant capsules, release of the fragrance or odorant.

[0014] However, the prior art microcapsules described above have the disadvantage that the polymeric capsule wall or shell material requires a large proportion of polymer to ensure sufficient stability and avoid excessive loss of active ingredients. In addition, microencapsulation introduces plastics into the environment, which can cause problems such as "microplastics" and can cause environmental damage and adverse health effects.

[0015] As plastic particles are increasingly the subject of public criticism regarding their environmental impact and as increasing societal pressure on the environmental front is driving the demand for bio-based and biodegradable solutions, new materials for microencapsulation need to be developed to achieve a reduction in microplastics in the environment, the focus here being on bio-based and biodegradable materials.

[0016] Against this background, there is a need to provide microcapsules that are increasingly being produced using biodegradable capsule wall materials that also have excellent stability and good release properties for the respective applications. It is important that not only is the polymeric material of the capsule wall itself biocompatible, but also each of the fragments generated during degradation. The aim is also to address consumer groups that wish to avoid animal-based ingredients in the final product.

[0017] However, this task of reducing the amount of microplastics in the environment with the help of biodegradable materials is not trivial in the case of microcapsules since the desired functionalities of microcapsules, such as olfactory properties and positive secondary properties such as high stability and toxicological harmlessness, conflict with the requirement of rapid biodegradability in many applications.

[0018] It is particularly difficult to produce microcapsules that have both good stability and good drug release. The ability of the capsule to retain the active ingredient and thus to avoid the loss of volatile ingredients depends particularly on the stability of the capsule on a product basis. However, capsules with good stability do not automatically have good biodegradability.

[0019] As the degree of cross-linking increases, the stability of the microcapsules increases, but at the same time the ability of the capsule shell to biodegrade decreases. Very stable microcapsules will break under pressure, friction, etc., and the number of microcapsules that release the active ingredient will decrease, resulting in reduced performance, for example in sensory performance. If they are too unstable, they will break down during storage and will no longer perform.

[0020] Recently, the demand for vegan products has also increased, partly due to the rise in consumer awareness. Veganism is a diet and lifestyle that originates from vegetarianism, and vegans are known to avoid all food of animal origin. In relation to veganism, counterarguments from the fields of animal ethics, environmental protection, world hunger, health and religion must also be taken into account. As veganism spreads to other areas of daily life and needs, there is an increasing demand for vegan microcapsules that cover the above-mentioned advantages and application fields. For the purposes of the present invention, vegan microcapsules may be understood and described as plant protein-based microcapsules. They do not contain any animal components, in particular animal protein components. This may also be understood and described as meaning that the plant protein-based microcapsules according to the present invention do not contain protein components of animal origin.

[0021] In particular, the present invention should be understood and described in such a way that the plant protein-based microcapsules, i.e. vegan microcapsules, do not contain any animal protein components or any other components of animal origin. Thus, the plant protein-based microcapsules according to the present invention consist exclusively of proteins or protein components of plant origin in terms of the proteins used. Animal proteins or protein components, e.g. gelatin, are expressly excluded in relation to the microcapsules according to the present invention. This applies analogously to the microcapsule slurries according to the present invention.

[0022] Thus, the present invention preferably satisfies the following requirements: · Improved biodegradability; Non-toxic effects on humans and the environment; · Maintain sufficient stability; · suitability for a wide variability in terms of the active ingredient to be encapsulated; Excellent release behavior of the encapsulated active ingredients; and Accessibility by known processes for the production of microcapsules; and · The ingredients are accessible, i.e. can be made from bio-based or sustainably produced raw materials; The present invention is based on the complex challenge of providing vegan microcapsules, i.e., plant protein-based microcapsules, which satisfy one, several, or preferably all of the above.

[0023] Surprisingly, it has been found that this problem can be solved by producing plant protein-based microcapsules from plant proteins and crosslinkers in aqueous emulsion by interfacial polymerization. Crosslinking allows the formation of very stable capsule shells or capsule walls that can be used to encapsulate a wide range of hydrophobic or lipophilic active ingredients. It is crucial that in the first step of the process according to the invention, an internal non-aqueous phase is provided that comprises at least one aliphatic polyisocyanate as crosslinker and at least one hydrophobic active ingredient. In particular, the use of at least one aliphatic polyisocyanate is crucial to obtain plant protein-based microcapsules with excellent stability together with a significantly improved release behavior of one or more encapsulated active ingredients(s). Summary of the Invention

[0024] This problem is solved by the object of the independent patent claims. Preferred and further embodiments result from the dependent patent claims and from the wording of the following description.

[0025] In a first aspect, the present invention therefore provides a method for producing a pharmaceutical composition comprising the steps of: (i) providing an internal non-aqueous phase comprising at least one aliphatic polyisocyanate as a crosslinker, at least one hydrophobic active ingredient, and optionally at least one further crosslinker; (ii) providing an external aqueous phase comprising at least one plant protein and, optionally, at least one first polysaccharide and / or at least one further cross-linking agent and / or at least one polyhydroxyphenol and / or at least one protective colloid, and optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the plant protein; (iii) emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase, optionally in the presence of at least one stabilizer and / or at least one emulsifier, to obtain an oil-in-water emulsion or oil-in-water dispersion; (iv) optionally adding at least one further polysaccharide and / or at least one further plant protein; (v) performing a first cross-linking step to obtain a microcapsule slurry; (vi) hardening the microcapsule slurry at a temperature of at least 60° C., optionally adding further polysaccharides and / or further plant proteins; (vii) cooling and optionally further crosslinking by adding at least one additional crosslinking agent; (viii) optionally separating the microcapsules from the microcapsule slurry and, if necessary, drying the microcapsules or adjusting the viscosity of the microcapsule slurry by adding at least one thickening agent. The present invention relates to a process for preparing plant protein-based microcapsules, comprising the steps of:

[0026] In a second aspect, the present invention relates to a microcapsule or a microcapsule slurry produced by the method according to the invention.

[0027] (a) a core comprising or consisting of at least one hydrophobic active ingredient; It is also an object of the present invention to provide a plant protein-based microcapsule comprising or consisting of (b) a crosslinked matrix or crosslinking units of at least one plant protein, at least one aliphatic polyisocyanate as crosslinking agent and optionally at least one polysaccharide; and optionally at least one protective colloid and / or optionally at least one further crosslinking agent; and a capsule shell comprising or consisting of the same.

[0028] Finally, in a further aspect, the present invention relates to the use of the plant protein-based microcapsules according to the invention or a dispersion comprising the plant protein-based microcapsules according to the invention for the manufacture of household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters in liquid or solid form, scent lotions or scent enhancers, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals or printing coatings for paper.

[0029] Furthermore, the present invention is directed to household products, fabric care products, detergents, fabric softeners, cleaning agents, scent boosters and fragrance enhancers, cosmetics, personal care products, perfume compositions, agricultural products, or pharmaceutical products comprising the plant protein-based microcapsules according to the present invention or the corresponding slurries.

[0030] Surprisingly, it has been found in the preparation of vegetable protein-based microcapsules according to the invention that the combination of vegetable proteins with subsequent cross-linking with aliphatic polyisocyanates leads to stable vegetable protein-based microcapsules, thus allowing efficient encapsulation of lipophilic active ingredients and subsequent targeted release of these active ingredients to be ensured.

[0031] Thus, the plant protein-based microcapsules according to the invention, and thus the vegan microcapsules, have excellent stability as well as excellent organoleptic properties. Furthermore, due to their bio-based and biodegradable components, they can be biodegradable. A particular advantage of the process according to the invention is that the amount of aliphatic polyisocyanates used as crosslinking agents can be reduced compared to the prior art.

[0032] As a result, it is also possible to reduce the amount of polyisocyanate in the capsule wall material or capsule shell material, i.e. to replace it with bio-based capsule wall components, without adversely affecting the very good stability properties of the microcapsule wall, and thus to increase the proportion of bio-based capsule wall components.

[0033] These and other aspects, features, and advantages of the present invention will become apparent to those skilled in the art from a review of the following detailed description and claims. Any feature or variation from one aspect of the present invention may be used in another aspect of the present invention or may be interchanged. Furthermore, it is understood that the examples contained herein illustrate and explain the present invention, but are not intended to limit the present invention, and in particular the present invention is not limited to these examples.

[0034] Unless otherwise specified, all percentages are percent by weight, also referred to as wt%. Numerical examples given in the form "x to y" are inclusive of the stated values. When several preferred numerical ranges are given in this format, it is understood that all ranges resulting from combining the various endpoints are also included.

[0035] The terms "at least one," or "less than one," or "one or more," as used herein, refer to one or more, for example, 2, 3, 4, 5, 6, 7, 8, or 9 or more.

[0036] The term "and / or" indicates that combinations are present or alternatives are provided. Those skilled in the art can independently determine which "and" or "or" combinations appear feasible and practical and which combinations are not. [Brief description of the drawings]

[0037] [Figure 1] FIG. 2 shows a comparison of the stability in fabric softeners of some plant protein-based microcapsules according to the present invention with previously known microcapsules made of gelatin, with respect to different polyisocyanates used as crosslinking agents.

[0038] [Diagram 2] FIG. 2 shows the sensory performance of microcapsules according to the invention in fabric softeners with respect to different polyisocyanates used as crosslinkers.

[0039] [Diagram 3] FIG. 1 shows the sensory performance of different plant protein-based microcapsules according to the present invention.

[0040] [Figure 4] FIG. 2 shows a further comparison of the stability of plant protein-based microcapsules according to the present invention in fabric softeners.

[0041] [Diagram 5] FIG. 1 shows a comparison of the stability of plant protein-based microcapsules according to the present invention in fabric softener with respect to the amount of polyisocyanate used and the effect of hyaluronic acid.

[0042] [Figure 6] FIG. 2 shows the sensory evaluation of microcapsules according to the invention with regard to the amount of polyisocyanate used and the influence of hyaluronic acid.

[0043] [Figure 7]FIG. 13 shows a further comparison of the stability of plant protein-based microcapsules according to the present invention with respect to the amount of polyisocyanate used and the effect of glycerol and a combination of glycerol and hyaluronic acid.

[0044] [Figure 8] FIG. 1 shows the sensory evaluation of microcapsules according to the invention with respect to the amount of polyisocyanate used and the influence of hyaluronic acid and glycerol. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] In a first aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: (i) providing an internal non-aqueous phase comprising at least one aliphatic polyisocyanate as a crosslinker, at least one hydrophobic active ingredient, and optionally at least one further crosslinker; (ii) providing an external aqueous phase comprising at least one plant protein and optionally at least one (first) polysaccharide and / or at least one further cross-linking agent and / or at least one polyhydroxyphenol and / or at least one protective colloid, and optionally adjusting the pH of the aqueous phase to a pH lower than the isoelectric point of the plant protein; (iii) emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase, optionally in the presence of at least one stabilizer and / or at least one emulsifier, to obtain an oil-in-water emulsion or oil-in-water dispersion; (iv) optionally adding at least one further polysaccharide and / or at least one further plant protein; (v) conducting a first cross-linking while maintaining the slurry of microcapsules; (vi) hardening the slurry of microcapsules at a temperature of at least 60°C, and optionally adding further polysaccharides and / or further plant proteins; (vii) cooling and optionally further crosslinking by adding at least one additional crosslinking agent; (viii) optionally separating the microcapsules from the microcapsule slurry and, if necessary, drying the microcapsules or adjusting the viscosity of the microcapsule slurry by adding at least one thickening agent. The present invention relates to a process for preparing plant protein-based microcapsules, comprising the steps of:

[0046] In the context of the present invention, microcapsules are understood to be microparticles having at least one or more active ingredients as a core material inside the capsule and surrounded by a capsule shell or capsule wall. The active ingredients are preferably hydrophobic or lipophilic active ingredients. Such active ingredients are insoluble or poorly soluble in water, but easily soluble in oils and fats. The terms "microcapsule" and "capsule" or "hydrophobic" and "lipophilic" are used synonymously in the sense of the present invention.

[0047] In the context of the present invention, the capsule shell or capsule wall is preferably composed of several cross-linked matrices or cross-linked units, which preferably have different compositions and are produced during the manufacture of the microcapsules according to the invention by several process steps or process sequences, in particular a cross-linking step. The cross-linked matrix comprises at least one plant protein.

[0048] These capsule wall components are crosslinked, optionally via a specifically catalyzed mechanism, by a crosslinking agent and, optionally, a catalyst by interfacial polymerization, so that a three-dimensional network is formed comprising the plant protein, an aliphatic polyisocyanate as a crosslinking agent, and, optionally, at least one polysaccharide.

[0049] In the first step (i) of the process according to the invention, an internal non-aqueous phase is provided which comprises at least one aliphatic polyisocyanate as crosslinker, at least one hydrophobic active ingredient and, optionally, at least one further crosslinker.

[0050] Polyisocyanates are R-substituted organic derivatives (RN=C=O) of isocyanic acid (HN=C=O). Organic isocyanates are compounds in which an isocyanate group (-N=C=O) is attached to an organic radical. Polyfunctional isocyanates or polyisocyanates are compounds that contain at least two or more isocyanate groups (-N=C=O) in the molecule, i.e., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 100, 200 or even more. Polyisocyanates with two isocyanate groups are also known as diisocyanates.

[0051] According to the present invention, the at least one polyisocyanate used in step (i) is an aliphatic polyisocyanate.

[0052] It may be provided that the at least one polyisocyanate is linear or branched.

[0053] Surprisingly, it has been shown that the use of at least one polyisocyanate is particularly advantageous when using vegetable protein, and thus in the production of vegetable protein-based microcapsules.The reduced reactivity of aliphatic polyisocyanates compared to aromatic polyisocyanates is expected to have a particularly advantageous effect on the stability of vegetable protein-based microcapsules.In any case, the achieved stability of vegetable protein-based microcapsules is significantly lower when aromatic polyisocyanates or mixtures with aromatic polyisocyanates are used than when aliphatic polyisocyanates are used.

[0054] In this respect, a reduced reactivity with respect to the at least one polyisocyanate used as crosslinker is particularly preferred in the production of plant protein-based microcapsules, i.e. in the process according to the invention, whereby accelerated reactivity of the polyisocyanates used, and thus also the production time of the microcapsules per se, is not a priority.

[0055] It is particularly preferred to use at least difunctional, preferably polyfunctional, polyisocyanates in the process according to the invention, i.e. aliphatic and cycloaliphatic, i.e. cycloaliphatic, isocyanates are all suitable, provided that the polyisocyanate has at least one, preferably two or more reactive isocyanate groups.

[0056] Particularly preferred are aliphatic, cycloaliphatic, or heterocyclic polyisocyanates, substitution products and mixtures of the aforementioned monomeric or oligomeric compounds.

[0057] In a preferred embodiment of the process according to the invention, the polyisocyanates contain on average 2 to 5 functional -N=C=O groups. These include, for example, aliphatic or cycloaliphatic diisocyanates, triisocyanates and higher polyisocyanates.

[0058] Among the above mentioned polyisocyanates, diisocyanates and polyisocyanates having three functional -N=C=O groups are particularly preferred and can therefore primarily be used in the practice of the invention. Preferably, diisocyanates having the general structure O=C=NRN=C=O, where R represents an aliphatic or cycloaliphatic radical, can be used. Preferably, the radical has 5 or more carbon atoms.

[0059] In a preferred embodiment of the process according to the invention, at least one of the aliphatic polyisocyanates or one of the aliphatic polyisocyanates is a cycloaliphatic polyisocyanate having two or more isocyanate groups.

[0060] Due to the number of functional groups, optimal cross-linking or networking of the capsule wall is achieved, providing plant protein-based microcapsules with long-term, slow release of active ingredients and good stability in consumer products.

[0061] The term "aliphatic polyisocyanate" refers to any polyisocyanate that is not aromatic, and in addition, whose molecule contains at least two isocyanate groups directly bonded to a corresponding number of different C atoms of the same aliphatic molecule and derivatives of such compounds, i.e. at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 100, 200 or more isocyanate groups.

[0062] Aliphatic polyisocyanate molecules having at least two isocyanate groups, i.e., at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 100, 200 or more isocyanate groups, may further be linear, branched or cyclic and may have, for example, aliphatic substituents, including one or more heteroatoms such as nitrogen, oxygen, phosphorus and / or sulfur, halogens such as fluorine, chlorine, bromine and / or iodine, and / or other functional groups such as alkoxy groups.

[0063] The linear aliphatic polyisocyanate molecule may be selected from C2-C20 linear alkyl, preferably C3-C15 linear alkyl, C4-C12 linear alkyl, C5-C10 linear alkyl, C6-C9 linear alkyl, or C7-C8 linear alkyl. In any case, the linear aliphatic molecule does not contain an aromatic structure.

[0064] The branched aliphatic polyisocyanate molecules may be preferably selected from C2-C20 branched alkyl, preferably C3-C15 branched alkyl, C4-C12 branched alkyl, C5-C10 branched alkyl, C6-C9 branched alkyl, C7-C8 branched alkyl.

[0065] For the purposes of the present invention, cycloaliphatic polyisocyanates are also to be understood and described as aliphatic polyisocyanates.

[0066] The cycloaliphatic polyisocyanate molecule may contain at least one, i.e. 1, 2, 3, 4 or more non-aromatic ring structure, the ring structure itself preferably consisting of only C atoms. Of course, the C atoms of the ring structure may carry suitable substituents. At least one ring structure preferably consists of a 3-, 4-, 5-, 6-, 7- or 8-membered ring, independently of each other. Preferably, the cycloaliphatic molecule contains 2-20 C atoms, e.g. 3-15 C atoms, 4-12 C atoms, 5-10 C atoms, 6-9 C atoms, or 7-8 C atoms.

[0067] Linear, branched or cyclic aliphatic polyisocyanates can exist as monomers or polymers. Monomeric polyisocyanates are molecules that are not linked to another molecule, in particular not linked to another molecule by one or more crosslinkers. Polymeric polyisocyanates contain at least two monomers linked together by one or more crosslinkers. The at least two monomers do not have to be the same monomer, but can be different. Polymeric polyisocyanates preferably contain at least two or more monomers linked together by at least one crosslinker, i.e. at least 2, 3, 4, 5, 10, 20, 30, 40, 50, 100 or more monomers.

[0068] The linear, branched or cycloaliphatic polyisocyanates preferably have a defined size / molecular weight that allows for reactivity with one or more crosslinking agents. Examples of suitable molecular weights preferably range from approximately 100 g / mol to 5×10 4 g / mol, preferably 120 g / mol to 2×10 4 g / mol, 140g / mol~10 4 g / mol, 160g / mol~5×10 3 g / mol, 180g / mol~2×10 3 g / mol, 200g / mol~10 3g / mol, 220 g / mol to 900 g / mol, 240 g / mol to 800 g / mol, 260 g / mol to 700 g / mol, 280 g / mol to 600 g / mol, 300 g / mol to 500 g / mol, 320 g / mol to 450 g / mol, or 340 g / mol to 400 g / mol.

[0069] Any number of different linear, branched and / or cyclic aliphatic polyisocyanates can be used within the scope of the present invention. For example, at least one or more, i.e., at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different linear aliphatic polyisocyanates can be used. For example, at least one or more, i.e., at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different branched aliphatic polyisocyanates can be used. For example, at least one or more, i.e., at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different branched cyclic polyisocyanates can be used as crosslinkers.

[0070] Preferably, derivatives of linear, branched and / or cyclic aliphatic polyisocyanates are used. Derivatives, as used herein, are understood in a broad sense as compounds derived from compounds by chemical reaction. Examples of derivatives include oligomers and / or adducts of the linear or branched aliphatic polyisocyanates mentioned above. Preferred oligomers are biurets, isocyanurates, uretdiones, iminooxadiazinediones, and preferred adducts are trimethylolpropane adducts. These oligomers / adducts are well known in the prior art and are disclosed, for example, in US4855490A or US4144268A.

[0071] Preferably, the aliphatic polyisocyanates are present only in monomeric and / or dimerized (as isocyanates) or oligomeric form.

[0072] Derivatives of linear, branched or cyclic polyisocyanates and / or mixtures thereof can also be obtained by reacting polyisocyanates with polyhydric alcohols (eg glycerol), polyamines, polythiols (eg dimercaprol).

[0073] Isocyanate compounds as defined above expressly include various isomers, if any, either alone or in combination, for example, methylenebis(cyclohexylisocyanate) (H12MDI) includes 4,4'-methylenebis(cyclohexylisocyanate), 2,4'-methylenebis(cyclohexylisocyanate), and / or 2,2'-methylenebis(cyclohexylisocyanate).

[0074] Exemplary aliphatic polyisocyanates include those commercially available, such as BAYHYDUR N304 and BAYHYDUR N3Q5, which are water-dispersible aliphatic polyisocyanates based on hexamethylene diisocyanate; DESMODUR N3400, DESMODUR N3600, DESMODUR N3700, and DESMODUR N3900, which are low viscosity multifunctional aliphatic polyisocyanates based on hexamethylene diisocyanate; multifunctional aliphatic polyisocyanates based on hexamethylene diisocyanate; and DESMODUR 3600 and DESMODUR N100, which are aliphatic polyisocyanates based on hexamethylene diisocyanate, each of which is available from Bayer Corporation, Pittsburgh, PA.

[0075] According to another preferred variant of the invention, the linear or branched aliphatic and / or cycloaliphatic polyisocyanate is selected from the group consisting of pentamethylene diisocyanate (PDI, e.g. Stabio D-370N or D-376N from Mitsui Chemicals Inc, Japan), hexamethylene diisocyanate (HDI), ethyl ester lysine triisocyanate, lysine diisocyanate ethyl ester and derivatives thereof, preferably wherein each of said derivatives contains more than one isocyanate group, optionally further comprising one or more groups selected from the group consisting of biuret, isocyanurate, uretdione, iminooxadiazinedione and trimethylolpropane adducts, and / or wherein the cycloaliphatic polyisocyanate(s) is / are selected from the group consisting of isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI, e.g. Takenate) or from Mitsui Chemicals Inc, Japan. Inc., Japan), 1,2-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanato-methyl)cyclohexane, methylene bis(cyclohexyl isocyanate) (H12MDI) and derivatives thereof, preferably wherein each of said derivatives contains more than one isocyanate group, and optionally further contains one or more groups selected from the group consisting of biuret, isocyanurate, uretdione, iminooxadiazinedione and trimethylolpropane adducts (e.g. TMP adducts) of H6XDI, particularly Takenate D-120N from Mitsui Chemicals Inc, Japan.

[0076] Aliphatic polyisocyanates derived from renewable raw materials, such as PDI (Stabio D-370N or D-376N from Mitsui Chemicals Inc., Japan), are particularly preferred. It has been found that such aliphatic polyisocyanates derived from renewable raw materials do not adversely affect the quality / properties of the core-shell capsules.

[0077] In a variant of the process according to the invention, the polyisocyanate used in the preparation of the plant protein-based microcapsules according to the invention is used as the only polyisocyanate component, i.e. without the admixture of another polyisocyanate component different therefrom.

[0078] Examples of monomeric polyisocyanates which can be used according to the invention and which contain at least two polyisocyanate groups are ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethyl diisocyanate, ethylene diisothiocyanate, tetramethylene diisothiocyanate, hexamethylene diisothiocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate or mixtures of the aforementioned compounds.

[0079] As polymerizable compounds containing at least two polyisocyanate groups, industrially produced di- and polyisocyanates are preferred, such as HDI: hexamethylene diisocyanate-(1,6) and / or IPDI: isophorone diisocyanate.

[0080] Other particularly preferred monomeric polyisocyanate compounds are diisocyanates such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1-polyisocyanato-3,3,5-trimethyl-5-polyisocyanatomethylcyclohexane (isophorone diisocyanate), 4,4'-diisocyanato-dicyclohexylmethane, 2,4- and 2,6-diisocyanatomethylcyclohexane and mixtures thereof.

[0081] Other specific examples of diisocyanates include, for example, 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclo-hexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, tetra-methoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate.

[0082] In particular, the use of long chain aliphatic diisocyanates having 6, 7, 8, 9, 10 or more carbon atoms can lead to the formation of a more stable capsule shell or capsule wall.

[0083] In a particularly preferred embodiment, the internal non-aqueous phase comprises two or more different polymerizable polyisocyanates, for example a mixture of polyisocyanates of different chain lengths capable of forming a mixed polymer.

[0084] The process according to the invention may provide for the use of a combination of at least two different aliphatic polyisocyanates.

[0085] Such combinations take advantage of the different reaction rates of the polyisocyanates: short chain aliphatic polyisocyanates, i.e., aliphatic polyisocyanates having 1-5 carbon atoms, preferably 3-5 carbon atoms, can allow for higher reaction rates compared to their longer chain analogues.

[0086] In a further preferred further development of the invention, the various aliphatic polyisocyanates therefore also have various chain lengths. In this context, long-chain polyisocyanates preferably have 6, 7, 8, 9, 10, 11, 12, 13, 14, 20, 25 or more carbon atoms, but even more preferably they have 6 to 12 carbon atoms, particularly preferably 6 to 8 carbon atoms. By short-chain polyisocyanates is meant polyisocyanates with 1 to 5 carbon atoms, preferably with 3 to 5 carbon atoms.

[0087] It is possible to use combinations of short chain aliphatic polyisocyanates (C1, C2, C3, C4, C5) and long chain aliphatic polyisocyanates (C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C20, C25 or higher).

[0088] Particularly preferred in this context is the use of mixtures of various aliphatic polyisocyanates carrying two or more isocyanate groups with a chain length of 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms, particularly preferably 4 to 7 carbon atoms, in the chain for the production of vegetable protein-based microcapsules according to the invention.

[0089] Aliphatic polyisocyanates are particularly preferred in this context, especially because of their chemical relationship with bio-based systems: for example, both lysine and 1,5-diiso-cyanato-pentane exhibit the same decomposition product 1,5-diaminopentane, which is particularly suitable for improving the biodegradability of microcapsules, taking environmental aspects into account.

[0090] Initial embodiments include mixtures of long-chain and short-chain diisocyanates in any desired mixing ratio, preferably in the range of 4:1 to 1:4 of long-chain to short-chain diisocyanates, particularly preferably 2:1 to 1:2.

[0091] Preferably, the process according to the invention can provide the previously described combination of short chain aliphatic polyisocyanates and long chain aliphatic polyisocyanates, the polyisocyanates being present in a mixture of monomeric or oligomeric or polymeric forms.

[0092] Preferably, this results in the following combination for use in the method according to the invention: With the previously stated definitions for short and long chains · Short-chain aliphatic polyisocyanates (monomeric or oligomeric or polymeric) and short-chain aliphatic polyisocyanates (monomeric or oligomeric or polymeric); · Short-chain aliphatic polyisocyanates (monomeric or oligomeric or polymeric) and long-chain aliphatic polyisocyanates (monomeric or oligomeric or polymeric); · Long-chain aliphatic polyisocyanates (monomeric or oligomeric or polymeric) and short-chain aliphatic polyisocyanates (monomeric or oligomeric or polymeric); ·Long chain aliphatic polyisocyanates (monomers or oligomers or polymers) and long chain aliphatic polyisocyanates (monomers or oligomers or polymers).

[0093] Due to the different reaction rates, dissociation and crosslinking structures of the polyisocyanate components, the selection of at least two aliphatic polyisocyanates of different chain lengths and different degrees of polymerization can result in significant increases in stability and performance (perfume or perfume release in the case of perfume capsules).

[0094] The above-mentioned polyisocyanate combinations or polyisocyanate mixtures of two different aliphatic polyisocyanates can be used to produce particularly stable and better, ie more densely branched crosslinks within the capsule shell.

[0095] Therefore, the method described herein can be used to produce high-performance (perfume or odorant release) plant protein-based microcapsules made from two different aliphatic polyisocyanates. Such plant protein-based microcapsules are very stable and feature excellent perfume preservation properties, which in turn is reflected in better capsule performance (perfume or odorant release) in the field of, for example, perfume or odorant encapsulation.

[0096] The use of two different aliphatic polyisocyanates can result in microcapsules with greater stability than those from a single polyisocyanate system.

[0097] Microcapsules made from a mixture of aliphatic-aliphatic polyisocyanates are significantly improved compared to microcapsules made from a mixture of aliphatic-aromatic polyisocyanates, at least in terms of stability, as illustrated in the following embodiment examples. Thus, the present invention essentially provides the use of aliphatic polyisocyanates in the combinations described above. The use of any aromatic polyisocyanates is expressly excluded in any case by the present invention.

[0098] The proportion of crosslinker(s), preferably polyisocyanate(s), in the internal non-aqueous phase is in the range of 0.1-5% by weight, preferably in the range of 0.2-4% by weight, based on the total weight of the non-aqueous phase. Most preferably, the crosslinker is used in the internal non-aqueous phase in the range of 0.5-2% by weight, based on the total weight of the non-aqueous phase. The total weight of the non-aqueous phase is made up of all the components of the non-aqueous phase.

[0099] The cross-linking agent is added neat, for example as a solid, or in the form of an aqueous solution to the internal non-aqueous phase.

[0100] In order to obtain plant protein-based microcapsules which have a very good balance between stability and organoleptic properties (fragrance or odorant release) and which also have the prospect of being biodegradable, a particularly advantageous embodiment of the process according to the invention may provide that the total amount of polyisocyanate, based on the amount of wall-forming agent, is 15 to 70% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 35% by weight, or that the total amount of polyisocyanate used together as crosslinker is 0.5% to 4%, preferably 1% to 3%, particularly preferably 1.5% to 2.5%, based on the total amount of hydrophobic active ingredient, preferably fragrance or odorant, used in the capsule core.

[0101] Wall-forming materials within the meaning of the present invention are all solid components of the internal and external phases, as well as optionally added polyisocyanates, in particular further crosslinkers and / or polyhydroxyphenols, and / or catalysts, and all other suitable substances according to the present disclosure.

[0102] In a further advantageous further development of the process according to the invention, it may be proposed that in step (i) a non-internal non-aqueous phase is provided which comprises an aliphatic polyisocyanate as crosslinker and a cycloaliphatic polyisocyanate as crosslinker, wherein the aliphatic polyisocyanate and the cycloaliphatic polyisocyanate are used in a respective molar ratio of 85:15 to 15:85.

[0103] Surprisingly, vegetable protein-based microcapsules can be produced in this way that have particularly good stability properties in combination with very good organoleptic properties (perfume or odorant release).In addition, the total content of polyisocyanates used as crosslinking agents can be reduced, which has a positive impact on the environment.

[0104] In a further advantageous further development of the process according to the invention, it may be proposed that in step (i) a non-internal non-aqueous phase is provided which comprises two different aliphatic polyisocyanates as crosslinkers, the two aliphatic polyisocyanates being used in a respective molar ratio of 85:15 to 15:85.

[0105] With regard to the two aliphatic polyisocyanates, reference is made, where appropriate, to the detailed explanations in the overall context of the present disclosure which apply equally with regard to the stated molar ratios.

[0106] Surprisingly, it has been found that when two aliphatic polyisocyanates are used in the respective molar ratios of 85:15 to 15:85, the plant protein-based microcapsules produced in this manner exhibit very good stability properties and very good organoleptic properties (fragrance or odorant release), respectively.

[0107] In order to obtain vegetable protein-based microcapsules which are optimized both with regard to their stability behavior and their sensory properties, a particularly preferred embodiment of the process according to the invention may provide that in step (i) an internal non-aqueous phase is provided which comprises three crosslinkers, the three crosslinkers being different from one another aliphatic or cycloaliphatic polyisocyanates, preferably at least one cycloaliphatic polyisocyanate and at least one aliphatic polyisocyanate being present, the three crosslinkers being used together in an amount of 20% to 60%, respectively, based on the total weight of the three polyisocyanates.

[0108] Preferably, three cycloaliphatic polyisocyanates can be used.

[0109] In this context, it can also be particularly advantageous to use one cycloaliphatic and two aliphatic polyisocyanates which are different from one another.

[0110] With regard to the three polyisocyanates, reference is made, where appropriate, to the detailed explanations in the overall context of the present disclosure which apply equally with regard to the ratios stated.

[0111] In a further advantageous further development of the process according to the invention it may be proposed that three cycloaliphatic polyisocyanates are used in equal proportions respectively.

[0112] It may further be proposed that one cycloaliphatic polyisocyanate and two aliphatic polyisocyanates which are different from each other are used in equal proportions.

[0113] It has surprisingly been found that in this way optimized polyisocyanate mixtures can be provided which have a particularly advantageous effect on the stability of the resulting microcapsules and on their organoleptic properties (perfume or odorant release), thereby allowing the total amount of polyisocyanates used to be reduced.

[0114] In addition, the benefits or advantages of the polyisocyanates described throughout this disclosure apply additionally and / or supplementally to the molar and / or amount ratios described herein, where appropriate.

[0115] To improve cross-linking of the at least one polysaccharide and / or the at least one plant protein, at least one further cross-linking agent can be added to the internal non-aqueous phase. In one embodiment, the further cross-linking agent is different from the (first) cross-linking agent. In another embodiment, the at least one further cross-linking agent is the same as the cross-linking agent. It is also possible that the cross-linking agent comprises at least one further cross-linking agent.

[0116] It may be provided that at least one further cross-linking agent is added in step (i) and / or a further cross-linking agent is added in step (ii) and / or step (iii).

[0117] The at least one further cross-linking agent, when added in step (i) or when added in step (ii) and / or step (vii), is selected from the group consisting of transglutaminase, peroxidase, polyphenols, polyhydroxyphenols, in particular minor plant substances selected from the group consisting of tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned cross-linking agents. In this respect, the at least one further cross-linking agent can be a polyphenol and / or a polyhydroxyphenol.

[0118] Transglutaminase is an enzyme that catalyzes the cross-linking of two amino acids, glutamine and lysine, through isopeptide bonds. The phenolic groups of the secondary plant substances cross-link peptides through hydrogen bonds. The aldehydes, cinnamaldehyde and vanillin, react covalently with the free amino groups of proteins through their reactive aldehyde groups.

[0119] Cinnamaldehyde, tannin, ferulic acid and gallic acid are particularly preferred among the other crosslinking agents mentioned above.

[0120] Tannins are particularly preferred. Advantageously, the organoleptic properties of the microcapsules according to the invention can be significantly improved.

[0121] Very preferably, tannin is added as at least one further cross-linking agent in step (i) and / or as one further cross-linking agent in step (ii) and / or step (vii).

[0122] Particularly advantageous combinations of crosslinkers with further crosslinkers are: Polyisocyanate + transglutaminase; Polyisocyanate + peroxidase; Polyisocyanates + polyphenols; Polyisocyanate + tannin; Polyisocyanate + gallic acid; Polyisocyanate + Ferulic Acid; Polyisocyanate + Hesperidin; Polyisocyanate + Cinnamaldehyde; Polyisocyanate + vanillin; Polyisocyanate + carvacrol; or Mixtures of polyisocyanates + two or more of the other crosslinkers listed above It is.

[0123] The additional cross-linking agent can be added neat, for example as a solid, or in the form of a solution to the internal non-aqueous phase.

[0124] The combined use of at least one crosslinking agent different from one another and at least one further crosslinking agent results in microcapsules with significantly improved stability and thus a reduced rate of leakage of the hydrophobic active ingredient.

[0125] In the process step (i) according to the invention, at least one crosslinking agent is first substantially dissolved together with at least one or more active ingredient(s) to be encapsulated, if appropriate, in an inert non-aqueous solvent or a solvent mixture of inert non-aqueous solvents. The term "substantially dissolved" is understood to mean that at least 90% by weight, preferably at least 98% by weight, even more preferably 99.9% by weight, of said components are dissolved in the solvent or solvent mixture to enable their use in the process. Preferably, the at least one polyisocyanate and the at least one active ingredient to be encapsulated are completely dissolved in the solvent or solvent mixture. If the solvent does not ensure sufficient solubility of the isocyanate, this drawback can be overcome by using a suitable dissolution promoter.

[0126] Preferred solvents for the internal non-aqueous phase are immiscible with water, do not react with the isocyanate component(s) or active ingredient(s), and have little or no odor in the amounts used.

[0127] The term "solvent" in the context of the present invention includes all kinds of oil bodies or oil components, in particular vegetable oils such as, for example, rapeseed oil, sunflower oil, soybean oil, olive oil, etc., modified vegetable oils, for example alkoxylated sunflower oil or soybean oil, synthetic (tri)glycerides, for example technical mixtures of mono-, di- and triglycerides of C6 to C22 fatty acids, fatty acid alkyl esters, for example the methyl or ethyl esters of vegetable oils (Agnique® ME 18 RD-F, Agnique® ME 18 SD-F, Agnique® ME 12C-F, Agnique® ME1270), fatty acid alkyl esters based on these C6 to C22 fatty acids, mineral oils and mixtures thereof.Examples of suitable and preferred lipophilic solvents are Guerbet alcohols, which are based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6 to C22 fatty acids with linear or branched C6 to C22 fatty alcohols or esters of branched C6 to C13 carboxylic acids with linear or branched C6 to C22 fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, allyl, stearyl oleate, stearyl stearate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate, and erucyl erucate.

[0128] Also suitable are esters of linear C6-C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18-C38 alkylhydroxycarboxylic acids with linear or branched C6-C22 fatty acids, in particular dioctylarates, esters of linear or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, liquid mono- / di- / triglyceride mixtures of C6-C18 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. These are esters with polyols, vegetable oils, branched primary alcohols, substituted cyclohexanes, carbonates of linear or branched C6-C22 fatty alcohols, such as dicaprylyl carbonate (Cetiol® CC); Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, benzoic acid esters with linear or branched C6-C22 alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicone methicone grades, etc.), aliphatic or naphthenic hydrocarbons, such as squalane, squalene, or dialkylcyclohexanes and / or mineral oils.

[0129] Preferred solvents are also in particular esters of linear C6-C22 fatty acids with branched alcohols, esters of C18-C38 alkylhydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, linear or branched C6-C22 fatty alcohols, in particular dioctyl maleate, esters of linear or branched fatty acids with polyhydric alcohols, such as propylene glycol, dimer diol or trimer diol and / or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-C18 fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, linear or branched alcohols of C2-C12 dicarboxylic acids having 1 to 22 carbon atoms or esters of C2-C12 dicarboxylic acids having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. esters with polyols having a carbon number of 6 to 18, preferably 8 to 10, carbon atoms, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6 to C22 fatty alcohol carbonates, such as dicaprylyl carbonate (Cetiol® CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear or branched C6 to C22 alcohols, linear or branched symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether (Cetiol® CE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicone methicone type, etc.) and / or aliphatic or naphthenic hydrocarbons, such as squalane, squalene or dialkylcyclohexanes.

[0130] Furthermore, in the context of the present invention, liquid linear or branched and / or saturated or unsaturated hydrocarbons or any desired mixtures thereof can be used as solvents, which can be, for example, alkanes having from 4 to 22, preferably from 6 to 18, carbon atoms, or any desired mixtures thereof.

[0131] Particularly suitable inert solvents for the internal non-aqueous phase are alkyl aromatic hydrocarbons such as diisopropyl naphthalene or substituted biphenyls, chlorinated diphenyls, paraffins, chlorinated paraffins, natural vegetable oils such as cottonseed oil, peanut oil, palm oil, tricresyl phosphates, silicone oils, dialkyl phthalates, dialkyl adipates, partially hydrogenated terphenyls, alkylated biphenyls, alkylated naphthalenes, diaryl ethers, aryl alkyl ethers and higher alkylated benzenes, benzyl benzoate, isopropyl myristate, as well as any mixtures of these hydrophobic solvents and mixtures of these hydrophobic solvents with one or more of kerosene, paraffins and / or isoparaffins.

[0132] Preferably, vegetable oil triglycerides, benzyl benzoate or isopropyl myristate are used as the solvent to provide the internal non-aqueous phase.Most preferred are vegetable oils selected from the group consisting of palm oil, soybean oil, rapeseed oil, sunflower oil, palm kernel oil, cottonseed oil, peanut oil, corn oil, coconut oil, olive oil, sesame oil, linseed oil, safflower oil, modified vegetable oils and mixtures thereof.

[0133] The above mentioned solvents may be used individually or as a mixture of two or more solvents in the process according to the invention.

[0134] In an alternative and preferred variant of the process according to the invention, at least one polyisocyanate is dissolved directly in a solution of at least one active ingredient, preferably one or more fragrances or flavorings or perfume oils, so that the core of the plant protein-based microcapsules according to the invention is essentially free of solvents as described above. The avoidance of solvents in the core of the microcapsules is advantageous in terms of reducing production costs and taking into account environmental aspects.

[0135] The fragrance or flavoring is particularly dissolved in a solvent commonly used in the perfume or flavoring industry. The solvent is preferably not alcohol, since alcohol reacts with isocyanates. Examples of suitable 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 highly hydrophobic. Preferably, the fragrance or flavoring solution contains less than 30% solvent. More preferably, the fragrance or flavoring solution contains less than 20% solvent, even more preferably, less than 10% solvent, all these percentages being defined by weight relative to the total weight of the fragrance or flavoring solution. Most preferably, the fragrance or flavoring is substantially free of solvent.

[0136] If the at least one hydrophobic active ingredient is already present in a mixture with a solvent or solvent mixture, the use of an inert solvent or solvent mixture is not necessary. In such cases, the at least one crosslinker can be mixed directly with the hydrophobic active ingredient to obtain the internal non-aqueous phase.

[0137] In principle, any material suitable for inclusion in microcapsules can be used as the active ingredient to be encapsulated or as the core material for producing the microcapsules according to the present invention. The active substances to be encapsulated are preferably hydrophobic and are suspensions as well as water-insoluble or water-immiscible liquids or solids. These are mostly non-polar substances. Such hydrophobic substances are almost always lipophilic, i.e., they are well soluble in oils and fats.

[0138] In the context of the present invention, the core material is a hydrophobic active ingredient, ie a substance which has a particular effect or which induces a particular reaction, such as, for example, a medicinal substance, a plant protection agent, a cosmetic active ingredient, a food active ingredient, etc.

[0139] At least one active ingredient to be encapsulated used in the method according to the invention is a hydrophobic or lipophilic active ingredient. This ensures that the active ingredient to be encapsulated is in the internal non-aqueous phase during the preparation of the microcapsules according to the invention and does not mix with the external aqueous phase, since otherwise it would be impossible to form an emulsion and cause deposition of the capsule wall material on the droplet surface. As a result, the lipophilic active ingredient is completely trapped in the microcapsules as a core material during the subsequent emulsification and crosslinking of the capsule wall components. The internal non-aqueous phase thus formed is characterized by an organic hydrophobic and oily nature.

[0140] As described above, it may be proposed that in step (ii) a further cross-linking agent is added, which may be a cross-linking agent selected from the group consisting of transglutaminase, peroxidase, polyphenols, polyhydroxyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and minor plant substances selected from the group consisting of: and mixtures of two or more of the aforementioned cross-linking agents.

[0141] The amount of further cross-linking agent optionally added in step (ii) is expected to be between 0.1% and 1.0%, preferably between 0.15% and 0.5%, particularly preferably between 0.17% and 0.23%, relative to the total amount of the external aqueous phase.

[0142] In an advantageous embodiment of the invention, the at least one lipophilic or hydrophobic active ingredient is in particular a lipophilic or hydrophobic fragrance or flavoring or a lipophilic or hydrophobic perfume oil or flavor (a fragrance or flavoring mixture), a cooling agent, a TRPV1 or TRPV3 modulator, a substance which causes a sharp taste or a warming or burning sensation on the skin or mucous membranes or a substance which causes a fizzing or tingling sensation in the mouth or throat, or an active ingredient with an astringent effect, a substance from the insecticide, biocide, insecticide, water repellent group, food additive, cosmetic active ingredient, pharmaceutical active ingredient, dye, dye precursor, pesticide, dye, luminous paint, optical brightener, solvent, wax, silicone oil, lubricant, printing coating for paper, or a mixture of two or more of the aforementioned active ingredients.

[0143] In a preferred variant of the invention, the hydrophobic or lipophilic active ingredient is in particular a hydrophobic fragrance or odorant or a mixture of two or more fragrances or odorants (fragrance oils), or a hydrophobic flavorant or a flavorant mixture of two or more flavorants (flavors), or also a basic ingredient essential for vital activity.

[0144] In a preferred embodiment of the first and / or second aspect of the invention, the microcapsules comprise a core material in the form of a hydrophobic monofragrance or monoodorant, wherein the core material is selected from the following groups: extracts of natural raw materials and also fractions thereof or components isolated therefrom; hydrocarbons; aliphatic alcohols; aliphatic aldehydes and acetals; aliphatic ketones and oximes; aliphatic sulfur-containing compounds; aliphatic nitriles; esters of aliphatic carboxylic acids; formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglates and 3-methyl-2-butanoates of acyclic terpene alcohols; acyclic terpene aldehydes and ketones and their dimethyl acetals and dimethyl acetals; formates, acetates, propionates, isobutyrates, butyrates of cyclic terpene alcohols. and cycloaliphatic esters, isovaleric acid esters, pentanoic acid esters, hexanoic acid esters, crotonic acid esters, tiglic acid esters and 3-methyl-2-butanoic acid esters; cyclic terpene aldehydes and ketones; cyclic alcohols; cyclic and alicyclic ethers; cyclic and macrocyclic ketones; alicyclic aldehydes; alicyclic ketones; esters of cyclic alcohols; esters of alicyclic alcohols; esters of alicyclic carboxylic acids; aromatic hydrocarbons; araliphatic alcohols; esters of araliphatic alcohols and aliphatic carboxylic acids; araliphatic ethers; aromatic and araliphatic aldehydes; aromatic and araliphatic ketones; aromatic and araliphatic carboxylic acids and their esters; nitrogen-containing aromatic compounds; phenyl ethers and phenyl esters; heterocyclic compounds; lactones; and at least one single fragrance or single odorant selected from one or more of the single fragrances from the group of the mixtures of the aforementioned active ingredients or mixtures thereof.

[0145] Fragrances and flavors suitable for the preparation of capsules according to the invention are described, for example, in “Fragrances”, in Steffen Arctander, in “Perfume and Flavor Chemicals”, self-published, Montclair, NJ 1969; H. Surburg, J. Panten, in “Common Fragrance and Flavor Materials”, 5th edition, Wiley-VCH, Weinheim, 2006.

[0146] Preferably, the plant protein-based microcapsules according to the invention comprise a core material in the form of a hydrophobic mono-perfume or mono-flavoring agent, wherein the core material is selected from the following groups: Hydrocarbons such as 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; famecene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; Aliphatic alcohols such as, for example, hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methylheptanol, 2-methyloctanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3,4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol, 4-methyl-3-decen-5-ol; Aliphatic aldehydes and their acetals, such as, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-5,9-undedecadienal, heptanal diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde; Aliphatic ketones and their oximes, such as, for example, 2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime, and 2,4,4,7-tetramethyl-6-octen-3-one; Aliphatic sulfur-containing compounds such as, for example, 3-methylthio-hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol; Aliphatic nitriles such as 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 2,12-tridecenoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; 3,7-dimethyl-6-octenoic acid nitrile; For example, (E)- and (Z)-3-hexenyl formate;Ethyl acetoacetate;Isoamyl acetate;Hexyl acetate;3,5,5-trimethylhexyl acetate;3-methyl-2-butenyl acetate;(E)-2-hexenyl acetate;(E)- and (Z)-3-hexenyl acetate;Octyl acetate;3-octyl acetate;1-octene-3-acetate;Ethyl butyrate;Butyl butyrate;Isoamyl butyrate;Hexyl butyrate;(E)- and (Z)-3-hexenyl isobutyrate Aliphatic carboxylic acids and their esters such as ethyl 3,7-dimethyl-2,6-octadienoate;Hexyl crotonate;Ethyl isovalerate;Ethyl 2-methyl pentanoate;Ethyl hexanoate;Allyl hexanoate;Ethyl heptanoate;Allyl heptanoate;Ethyl octanoate;Ethyl (E,Z)-2,4-decadienoate;Methyl 2-octynate;Methyl 2-nonynate;Allyl 2-isoamyloxyacetate;Methyl 3,7-dimethyl-2,6-octadienoate; For example, citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; acyclic terpene alcohols such as 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their esters with formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, pentanoic acid, hexanoic acid, crotonic acid, tiglic acid and 3-methyl-2-butenoic acid; Aldehydes and ketones of acyclic terpenes, such as geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranylacetone, and the dimethyl acetals and diethyl acetals of geranial, neral, and 7-hydroxy-3,7-dimethyloctanal; Cyclic terpene alcohols such as, for example, menthol, isopulegol, α-terpineol, terpinenol-4, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambulinol, vetiverol, guaiol, and their esters with formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, pentanoic acid, hexanoic acid, crotonic acid, tiglic acid, 3-methyl-2-butenoic acid; For example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; β-irone; α-damascenone; β-damascenone; δ-damascenone; d-damascenone; 1-(2,4,4-trimethyl (ethyl-2-cyclohexen-1-yl)-2-buten-1-one;1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one;nootkatone;dihydronootkatone;α-sinensal;β-sinensal;aldehydes and ketones of cyclic terpenes such as acetylated cedarwood oil (methyl cedryl ketone); Cyclic alcohols such as, for example, 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; For example, α-3,3,3-trimethyl-cyclohexylmethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten alicyclic alcohols such as 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; Cyclic and alicyclic ethers such as, for example, cineole; cedryl methyl ether; cyclododecyl methyl ether; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodeca-hydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane; For example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3 -Methyl-5-cyclopentadecenone;3-Methylcyclopentadecanone;4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;4-tert-pentylcyclohexanone;5-Cyclohexadecen-1-one;6,7-Dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;9-Cycloheptadecen-1-one;Cyclopentadecanone;Cyclohexadecanone and other cyclic ketones; Alicyclic aldehydes such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; Alicyclic ketones such as, for example, 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 1-(5,5-dimethyl-2-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone; Esters of cyclic alcohols such as, for example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate; 4,7-methanooctahydro-5- or 6-indenyl acetate; Esters of alicyclic carboxylic acids such as, for example, allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmate; methyl jasmate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate; Aromatic hydrocarbons, such as styrene and diphenylmethane; Aromatic aliphatic alcohols such as, for example, benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenylethyl acetate, α,α-dimethylphenyl-ethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, and 4-methoxybenzyl acetate; Aromatic aliphatic ethers such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaldehyde dimethyl acetal; phenylacetaldehyde-glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxine; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine; For example, benzaldehyde;phenylacetaldehyde;3-phenylpropanal;hydratropaldehyde;4-methylbenzaldehyde;4-methylphenylacetaldehyde;3-(4-ethylphenyl)-2,2-dimethylpropanal;2-methyl-3-(4-isopropylphenyl)propanal;2-methyl-3-(4-tert-butylphenyl)propanal;3-(4-tert-butylphenyl)propanal;cinnamaldehyde;α-butylcinnamaldehyde;α Aromatic and araliphatic aldehydes such as -amylcinnamaldehyde;α-hexylcinnamaldehyde;3-methyl-5-phenylpentanal;4-methoxybenzaldehyde;4-hydroxy-3-methoxybenzaldehyde;4-hydroxy-3-ethoxybenzaldehyde;3,4-methylenedioxybenzaldehyde;3,4-dimethoxybenzaldehyde;2-methyl-3-(4-methoxyphenyl)propanal;2-methyl-3-(4-methylenedioxyphenyl)propanal; Aromatic and araliphatic ketones such as, for example, acetophenone, 4-methyl-acetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthalenyl)ethanone, benzophenone, 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone, 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone, 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; Aromatic and aromatic aliphatic carboxylic acids and their esters, such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenylethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate; Nitrogen-containing aromatic compounds such as, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamic acid nitrile; 5-phenyl-3-methylpentenoic acid nitrile; methyl anthranilate; methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; 4-(4,8-dimethyl-3,7-nonadienyl)-pyridine; Phenols, phenyl ethers and phenyl esters such as, for example, estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresylphenyl acetate; For example, 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1,15-pentadecanolide; cis- and trans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen-1,15-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1, 16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; lactones such as octahydrocoumarin; as well as at least one single fragrance or single flavoring selected from one or more of the stereoisomers, enantiomers, positional isomers, diastereomers, cis / trans isomers or epimers of the above mentioned substances.

[0147] Of the aforementioned individual fragrances or individual odorants which can be encapsulated in the sense of the present invention, fragrances or odorants having aldehyde, carboxylic acid or ester functionality are particularly preferred for use.

[0148] The aldehyde-based fragrance or odorants, including the esters and lactones as well as the corresponding acetals, are classified into the following groups: (i) Aliphatic aldehydes and their acetals; (ii) alicyclic aldehydes; (iii) aromatic or araliphatic aldehydes; (iv) aliphatic, aromatic or araliphatic esters; and (v) lactones; and mixtures thereof.

[0149] The above mentioned fragrance or odor substances having aldehyde, carboxylic acid or ester functionalities and mixtures thereof are included in the following groups: Aliphatic aldehydes and their acetals, such as, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (f)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (f)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-5,9-undecadienal, heptanal diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde; Alicyclic aldehydes such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; For example, benzaldehyde;phenylacetaldehyde;3-phenylpropanal;hydratropaldehyde;4-methylbenzaldehyde;4-methylphenylacetaldehyde;3-(4-ethylphenyl)-2,2-dimethylpropanal;2-methyl-3-(4-isopropylphenyl)propanal;2-methyl-3-(4-tert-butylphenyl)propanal;3-(4-tert-butylphenyl)propanal;Cinnamaldehyde;α-butylcinnamaldehyde;α- Aromatic and araliphatic aldehydes such as amylcinnamaldehyde;α-hexylcinnamaldehyde;3-methyl-5-phenylpentanal;4-methoxybenzaldehyde;4-hydroxy-3-methoxybenzaldehyde;4-hydroxy-3-ethoxybenzaldehyde;3,4-methylenedioxybenzaldehyde;3,4-dimethoxybenzaldehyde;2-methyl-3-(4-methoxyphenyl)propanal;2-methyl-3-(4-methylenedioxyphenyl)propanal; For example, (E)- and (Z)-3-hexenyl formate; Ethyl acetoacetate; Isoamyl acetate; Hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-Methyl-2-butenyl acetate; (f)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; Octyl acetate; 3-Octyl acetate; 1-Octen-3-yl acetate; Ethyl butyrate; Butyl butyrate; Isoamyl butyrate; Hexyl butyrate; (E)- and (Z)-isobutyrate Esters of aliphatic carboxylic acids such as -3-hexenyl;hexyl crotonate;ethyl isovalerate;ethyl 2-methyl pentanoate;ethyl hexanoate;allyl hexanoate;ethyl heptanoate;allyl heptanoate;ethyl octanoate;(E,Z)-2,4-decadienoate;methyl 2-octynoate;methyl 2-nonynoate;allyl 2-isoamyloxyacetate;methyl 3,7-dimethyl-2,6-octadienoate; Esters of cyclic alcohols such as, for example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate; 4,7-methanooctahydro-5- or 6-indenyl acetate; Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenylethyl acetate, α,α-dimethylphenyl-ethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, and 4-methoxybenzyl acetate; Esters of alicyclic carboxylic acids such as, for example, allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmate; methyl jasmate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate; For example, selected from one or more of aromatic and aromatic aliphatic carboxylic acid esters such as methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenylethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate.

[0150] Listed below are aldehydes, acetals, esters and lactones with their trade names which are particularly preferred as representatives of groups (i) to (v) for the purposes of the method according to the invention: Aldehyde: 2-Methylpentanal; Aldehyd C12; MNA HM; Aldehyde; C4; Aldehyde; C5; Aldehyde; C6; Aldehyde; C7; Aldehyde; C8; Aldehyde; C9; Aldehyde; C10; Aldehyde; C11; ISO; Aldehyde; C11; MOA PURE;Aldehyde;C11;UNDECANAL;Aldehyde;C11;UNDEYLENIC;Aldehyde;C12;Aldehyde;C12;MNA;Aldehyde;C13;A LDEHYDE;MADARINE;AMYL;CINNAMIC;ALDEHYDE;ALPHA;ANISALALDEHYDE-O;ANISYL;ALDEHYDE;BENZALDEHYDE;NAT.BERGAMAL; BORONAL; BOURGENOAL; CAMPHONELIC ALDEHYDE; CITRAL; CITRONELLAL HM; CITRONELLYL OXYACET ALDEHYDE; CITRYLAL; CITROYLAL E HM; CORTEX; ALDEHYDE; CORTEX; ALDEHYDE; 50; PCT PEMOSA; CROTONIC; ALDEHYDE; CUMINAL ALDEHYDE; CYCLAMEN; ALDEHYDE; DECADIENAL; TRANS; TRANS-2,4; DECANAL CIS-4; DECANAL TRANS-2; DECANAL TRANS-2 NAT; DECANAL TRANS-4; DECANAL-9,1; DODECANIENAL; 2,6; DODECANAL TRANS-2; DUPICAL; EPOXYDECENAL-4,5-2 10%TRI; ETHYL HEXANAL; FARENAL (registered trademark); FLORHYDRAL; GERALDEHYDE; HELIONAL; HELIOPAN; HELIOTROPIN; HEPTADIENAL TRANS; TRANS,2-4; HEPTENAL; CIS-4; HEPTENAL; TRANS-2; HEXENAL TRANS-2; HEXYL CINNAMIC; ALDEHYDE; ALPHA; HYDRATROPIC ALDEHYDE; HYDROXY CITRONELLAL; INTRELEVEN; ALDEHYDE; SPEC.;ISONONYL;ALDEHYDE;ISOVALERIC;ALDEHYDE;LEMON ALDEHYDE;H&R JS;I;LILIAL;LINOLAL;LYRAL;MAJANTAL;MANDRINAL;MANDRAINE ALDEHYDE;10% IN;TEC BHT;MEFRANAL;MELONAL (Registered Trademark);METHODY CITRONELLAL;METHYL;BUTYRALDEHYDE;METHYL;CINNAMIC;ALDEHYDE;ALPHA;METHYL;PHENYLPENTENAL-4,2,2;METHYL;THIO;PROPANAL-3;METHYL;TRIDECANAL-12;10% VT;METHYL-3-BUTEN-2-AL;METHYL-5-PHENYL-2-HEXEN-2-AL;MUGENAL 50;DPG;NEOCYCLO;CITRAL;NONADIENAL;TRANS;CIS-2,6;NONENAL CIS-6;NONENAL TRANS-2;ONCIDAL (Registered Trademark);3 / 060251;PENTENAL;TRANS-2;PERILLA ALDEHYDE;PHENYLACET;ALDEHYDE;PHENYLBUTENAL TRANS-2,2;PHENYLPROPYL;ALDEHYDE;PINOACET;ALDEHYDE;PROFRANESAL;PROPIONALALDEHYDE 2-(P-TOLYL);PROPIONIC ALDEHYDE;PS-IRALDEIN;X NEU;SAFRANAL;SALICYLIC ALDEHYDE;FG;SILVIAL;TETRAHYDRO;CITRAL;TIGLIC;ALDEHYDE-2,2;TOLYL ALDEHYDE;PARA;FG;TRIDECENAL;TRANS-2;TRIFERNAL;UNDECADIENAL-2,4;UNDECENAL TRANS-2;VERNALALDEHYDE;VERTOCITRAL;VERTOMUGAL;VERTIPRENAL;VETRAL;ROH;ZIMTALDEHYDE;NAT.HM;ACETAL:FLOROPAL;HEPTANAL;DIETHYL ACETAL;NONANDIENAL DIETHYL ACETAL;OKOUMAL;PHENYLACET;ALD.;GLYCERIN;ACETAL;PHENYLACETALDEYHDEDIMETHYLACETAL;Esters:JASMAL;JESSEMAL;KHARISMAL;TIRAMISONE (registered trademark).

[0151] In a further variant of the method according to the invention, flavourants can also be encapsulated in the form of a single flavour as a core material, the core material then comprising at least one single flavourant or a mixture thereof as active ingredient.

[0152] Typical examples of flavouring substances or flavours which may be encapsulated within the meaning of the present invention are acetophenone; allyl caproate; α-ionone; β-ionone; anisaldehyde; anisyl acetate; anisyl formate; benzaldehyde; benzothiazole; benzyl acetate; benzyl alcohol; benzyl benzoate; β-ionone; butyl butyrate; butyl caproate; butylidenephthalide; carvone; camphene; caryophyllene; cineole; cinnamyl acetate; citral; citronellol; citronellal; citronellyl acetate; cyclohexyl acetate; simo ;Damascone;Decalactone;Dihydrocoumarin;Dimethyl anthranilate;Dimethyl anthranilate;Dodecalactone;Ethoxyethyl acetate;Ethyl butyrate;Ethyl butyrate;Ethyl caprate;Ethyl caproate;Ethyl crotonate;Ethyl furaneol;Ethyl guaiacol;Ethyl isobutyrate;Ethyl isovalerate;Ethyl lactate;Ethyl methyl butyrate;Ethyl propionate;Eucalyptol;Eugenol;Ethyl heptylate;4-(p-Hydroxyphenyl)-2-butanone;γ-Decalactone;Geraniol;Geranyl acetate;Geranyl acetate;Gre jasmine;Aldehydes;Methyl dihydrojasmate;(e.g., Hedion®);Heliotropin;2-heptanone;3-heptanone;4-heptanone;trans-2-heptenal;cis-4-heptenal;trans-2-hexenal;cis-3-hexenol;trans-2-hexenoic acid;trans-3-hexenoic acid;cis-2-hexenyl acetate;cis-3-hexenyl acetate;cis-3-hexenyl caproate;trans-2-hexenyl caproate;cis-3-hexenyl formate;cis-2-acetate Hexyl;cis-3-hexyl acetate;trans-2-hexyl acetate;cis-3-hexyl formate;para-hydroxybenzylacetone;Isoamyl alcohol;Isoamyl isovalerate;Isobutyl butyrate;Isobutyraldehyde;Isoeugenol methyl ether;Isopropylmethylthiazole;Lauric acid;Levulinic acid;Linalool;Linalool oxide;Linalyl acetate;Menthol;Mthofuran;Methyl anthranilate;Methylbutanol;Methylbutyric acid;2-Methylbutyl acetate;Methyl caproate;Methyl cinnamate;5-Methylfurfural;3,2,2-Methylcyclopentenolone;6,5,2-Methylheptenolone;Methyl dihydrojasmate;Methyl jasmate;2-Methylmethyl butyrate;2-Methyl;2-Pentenoic acid;Methyl thiobutyrate;3,1-Methylthiohexanol;3-Methylthiohexyl acetate;Nerol;Neryl acetate;trans,trans-2,4-Nonadienal;2,4-Nonadieno;2,6-Nonadieno;2,4-Nonadieno;Nootkatone;δ-Octalactone;γ-Octalactone;2-Octanol;3-Octanol;1,3-Octenoic acid 1-Octyl acetate;3-Octyl acetate;Palmitic acid;Palaldehyde;Phellandrene;Pentanedione;Phenylethyl acetate;Phenylethyl alcohol;Phenylethyl alcohol;Phenylethyl isovalerate;Piperonal;Propionaldehyde;Propyl butyrate;Pulegone;Pulegol;Sinensal;Sulfurol;Terpinene;Terpineol;Terpinolene;8,3-Thiomenthanone;4,4,2-Thiomethylpentanone;Thymol;δ-Undecalactone;γ-Undecalactone;Valencene;Valeric acid;Vanillin;Acetoin ethyl vanillin; ethyl vanillin isobutyrate (3-ethoxy-4-isobutyryloxybenzaldehyde); 2,5-dimethyl-4-hydroxy-3(2H)-furanone and its derivatives (preferably homofuraneoll (2-ethyl-4-hydroxy-5-methyl-3(2H)-furanone), homofuranol (2-ethyl-5-methyl-4-hydroxy-3(2H)-furanone and 5-ethyl-2-methyl-4-hydroxy-3(2H)-furanone); maltol and maltol derivatives (preferably ethyl maltol); coumarin and coumarin derivatives; γ-Lactones (preferably γ-undecalactone, γ-nonalactone, γ-decalactone); δ-Lactones (preferably 4-methyl δ-decalactone, massolactone, δ-decalactone, tuberolactone); methyl sorbate; divanillin; 4-hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2H)furanone; 2-hydroxy-3-methyl-2-cyclopentenone; 3-hydroxy-4,5-dimethyl-2(5H)-furanone; isoamyl acetate; ethyl butyrate; n-butyl butyrate; isoamyl butyrate;3-Methyl-butyric acid ethyl ester;n-Hexanoic acid ethyl ester;n-Hexanoic acid allyl ester;n-Hexanoic acid butyl ester;n-Octanoic acid ethyl ester;3-Methyl-3-phenylglycidic acid ethyl ester;2-trans-4-cis-decadienoic acid ethyl ester;4-(p-Hydroxyphenyl)-2-butanone;1,1-Dimethoxy-2,2,5-trimethyl-4-hexane;2,6-Dimethyl-5-hepten-1-al;Phenylacetaldehyde;2-Methyl-3- (Methylthio)furan;2-Methyl-3-furanthiol;Bis(2-methyl-3-furyl)disulfide;Furfuryl;Mercaptan;Methional;2-Acetyl-2-thiazoline;3-Mercapto-2-pentanone;2,5-Dimethyl-3-furanthiol;2,4,5-Trimethylthiazole;2-Acetylthiazole;2,4-Dimethyl-5-ethylthiazole;2-Acetyl-1-pyrroline;2-Methyl-3-ethylpyrazine;2-Ethyl-3,5-dimethylpyrazine 2-Ethyl-3,6-dimethylpyrazine;2,3-Diethyl-5-methylpyrazine;3-Isopropyl-2-methoxypyrazine;3-Isobutyl-2-methoxypyrazine;2-Acetylpyrazine;2-Pentylpyridine;(E,E)-2,4-Decadienal;(E,E)-2,4-Nonadienal;(E)-2-Octenal;(E)-2-Nonenal;2-Undecenal;12-Methyltridecanal;1-Penten-3-one;4-Hydroxy-2,5-dimethyl -3(2H)-furanone, guaiacol; 3-hydroxy-4,5-dimethyl-2(5H)-furanone; 3-hydroxy-4-methyl-5-ethyl-2(5H)-furanone; cinnamaldehyde; cinnamyl alcohol; methyl salicylate; isopulegol and the stereoisomers, enantiomers, positional isomers, diastereomers, cis / trans isomers or epimers of those substances not expressly mentioned in this specification, as well as mixtures of the aforementioned substances;

[0153] In an alternative embodiment of the invention, in the plant protein-based microcapsules of the invention, a fragrance or odorant mixture, or a fragrance oil or aroma mixture, or an aroma, is used as the encapsulated active ingredient or as the core material. These are compositions containing at least one fragrance or odorant or flavoring. Such compositions, in particular fragrance or odorant mixtures or fragrance oils, preferably contain 2, 3, 4, 5, 6, 7, 8, 9 or more fragrance or odorant substances. The fragrance or odorant mixtures or fragrance oils are preferably selected from the group consisting of, for example, amber tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; cocoa absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; buco leaf oil; cabreuba oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; kale ... Scarilla oil;Cassia oil;Cassie absolute;Castoreum absolute;Cedar leaf oil;Cedarwood oil;Cistus oil;Citronella oil;Citron oil;Copaiba balsam;Copaiba balsam oil;Coriander oil;Costus root oil;Cumin oil;Cypress oil;Davana oil;Dill oil;Dill seed oil;Eau de Blossoms absolute;Oakmoss absolute;Elemi oil;Tragon oil;Eucalyptus citriodora oil;Eucalyptus oil;Fen flannel oil;pine needle oil;galbanum oil;galbanum resin;geranium oil;grapefruit oil;guaiac wood oil;gluyun balsam;gluyun balsam oil;helichrysum absolute;helichrysum oil;ginger oil;iris root absolute;iris root oil;jasmine absolute;calamus oil;blue chamomile oil;roman chamomile oil;carrot seed oil;cascarilla oil;pine needle oil;spearmint oil;caraway oil;labdanum oil ;Labdanum absolute;Labdanum resin;Lavandin absolute;Lavandin oil;Lavender absolute;Lavender oil;Lemongrass oil;Lovage oil;Distilled lime oil;Pressed lime oil;Linal oil;Limongrass oil;Bay leaf oil;Mashi oil;Marjoram oil;Mandarin oil;Massoiabark oil;Mimosa absolute;Musk grain oil;Musk tincture;Muscat sage oil;Nutmeg oil;Myrrh absolute;Myrrh oil;Myrtle oil;Clove leaf oil;Clove flower oil;Neroli oil;Olibanum absolute;Olibanum oil;Opopanax oil;Orange blossom absolute;Orange oil;Oregano oil;Palmarosa oil;Patchouli oil;Perilla oil;Balsam of Peru oil;Parsley leaf oil;Parsley seed oil;Petitgrain oil;Peppermint oil;Pepper oil;Allspice oil;Pine oil;Pauly oil;Rose absolute;Rosewood oil;Rose oil;Rosemary oil;Sage oil Dalmatian;Sage oil Spanish;Sandalwood oil;Celery seed oil;Spike lavender oil;Star anise oil;Styrax oil;Taj The extracts are selected from the group of extracts from natural raw materials such as ethereal oils, concretes, absolutes, resins, resinoids, balsams, tinctures, such as ethereal oil, fir needle oil, tea tree oil, turpentine oil, thyme oil, tolu balsam, tonka absolute, tuberose absolute, vanilla extract, violet leaf absolute, verbena oil, vetiver oil, juniper berry oil, wine yeast oil, mugwort oil, wintergreen oil, ylang oil, hyssop oil, civet absolute, cinnamon leaf oil, cinnamon bark oil and fractions thereof or components isolated therefrom.

[0154] Most preferably, in the process according to the invention, AGRUMEX LC; AGRUNITRIL; ALDEHYD C11 UNDECYLENIC; ALDEHYD C12 LAURIN; ALDEHYD C12 MNA; ALDEHYD C14 SOG; ALDEHYD C16 SOG.; ALLYLAMYLGLYCOLAT; ALLYLCAPRONAT; ALLYLCYCLOHEXYLPROPIONAT; ALLYLHEPTYLAT; AMBROCENIDE (registered trademark), 10, TEC; AMBROCENIDE (registered trademark) Krist.10% IPM; AMBROXIDE; ANETHOL NAT.EX, STERNANIS; ANISALDEHYD REIN; APRIFLOREN (registered trademark); BENZYLACETON; BENZYLSALICYLAT; BORNEOL L / ISOBORNEOL 65 / 35; BUCCOBLAETTEROEL; CITRONELLOL 950; CLONAL; CYCLOHEXYLSALICYLAT; CYMOL PARA, SUPRA; DAMASCONE DELTA; DIHYDROMYRCENOL; DIMETHYLBENZYLCARBINYLBUTYRAT; DYNASCONE; ETHYLENEBRASSYLAT; ETHYLMETHYLBUTYRAT-2; ETHYLSAFRANAT; EUCALYPTOL NAT.; EUKALYPTUSOEL GLOBULUS 80 / 85%; EUGENOL NAT.; FARENAL (registered trademark); FENCHELOEL AROMA TYP SUESS NAT.;FILBERTONE 10% IPM;FILBERTONE;FLOROPAL;GALBASCONE;GERANIOL 60;GLOBANONE(R);HEDION;HERBAFLORAT;HERBANATE;HERBYLPROPIONAT;HEXENYLACETAT CIS-3;HEXENYLSALICYLAT CIS-3;HEXYLACETAT;HEXYLACETAT S;HEXYLISOBUTYRAT;HEXYLSALICYLAT;ISOAMYLBUTYRAT;ISOBORNYLACETAT;ISOPROPYLMETHYLBUTYRAT-2;ISORALDEIN 70;JAVANOL;KAMPFER DL;KRESOLMETHYLETHER P(CR<10, PPM);LEMONILE;LIGUSTRAL;LILIAL;LINALOOL;MANZANATE;MELONAL;METHYLHEPTINCARBONAT;METHYLOCTINCARBONAT;MUSCENONE;NEOCYCLOCITRAL;NEROLIN BROMELIA;NEROLIN YARA, YARA, KRIST.;NEROLIONE;NORLIMBANOL;ORANGENOEL;ORIVONE;OZONIL;PATCHOULIOEL ENTF.;PFLANZENOL TRIGLYCERID;PHELLANDREN FRAKTION EX EUKALYPTUSOEL;PHENIRAT(R);PHENYLETHYLACETAT;ROSENOXID HIGH CIS;SANDRANOL(registered trademark);STYROLYLACETAT;SULTANENE(registered trademark);TERPINEN Use is made of a fragrance or odorant or flavoring selected from the group consisting of GAMMA; TETRAHYDROLINALOOL; TIMBERSILK; TRIETHYLCITRAT; UNDECAVERTOL; VERTOCITRAL; VERTOFIX; YSAMBER® K and mixtures of the above active ingredients.

[0155] Exemplary cooling agents for use as hydrophobic active ingredients in the preparation of the microcapsules of the present invention include menthol and menthol derivatives (e.g., L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), menthyl ethers (e.g., (l-menthoxy)-1,2-propanediol, (l-menthoxy)-2-methyl-1,2-propanediol, l-menthyl-methyl ether), menthyl esters (e.g., menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl lactate, , L-menthyl lactate, L-menthyl D-lactate, (2-methoxy)menthyl acetate, (2-methoxyethoxy)menthyl acetate, menthyl pyroglutamate), menthyl carbonate (e.g., menthyl propylene glycol carbonate, menthyl ethylene glycol carbonate, menthyl glycerol carbonate or mixtures thereof), semiesters of menthol with dicarboxylic acids or derivatives thereof (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinate, cinamide), menthanecarboxamides (e.g., menthanecarboxylic acid-N-ethylamide [WS3], Nα-(menthanecarbonyl)glycine ethyl ester [WS5], menthanecarboxylic acid-N-(4-cyanophenyl)-amide, menthanecarboxylic acid-N-(alkoxyalkyl)amides), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butanoic acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butanoic acid N-methylamide [WS23 ]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), cubebol or cubebol-containing synthetic or natural mixtures, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-methyl-2-(1-pyrrolidinyl)-2-cyclopenten-1-one) or tetrahydropyrimidin-2-ones (e.g., icilin or related compounds as described in WO 2004 / 026840).Further cooling agents are menthol (L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), L-menthyl methyl ether, menthyl formate, menthyl acetate), menthone, isopulegol, L-(-)-isopulegol acetate, vinegar and cubebol, which have a cooling flavor effect. Suitable cooling agents are well known in the art and are described, for example, in US2017 / 216802(A1), US2010 / 273887(A1), EP 2 033 688(A2) and EP 1 958 627(A2).

[0156] In an alternative variant, TRPV1 and TRPV3 modulators are used in the plant protein-based microcapsules according to the invention as encapsulated active ingredients or as core materials. TRPV1 and TRPV3 modulators are known in the art and refer to TRP channels (transient receptor potential channels) of the vanilloid (TRPV) subfamily. TRPV1 modulators confer the tingling and hot sensations associated with capsaicin and piperine. TRPV3 proteins belong to a family of non-selective cation channels that function in various processes including thermosensation and blood pressure regulation. TRPV3 channels are directly activated by various natural compounds such as, for example, carvacrol, thymol and eugenol. Several other monoterpenoids that cause thermal sensation or are skin sensitizers can also open the channel. Monoterpenoids also induce agonist-specific desensitization of TRPV3 channels in a calcium-independent manner.

[0157] In a further variant, in the plant protein-based microcapsules according to the invention, an active substance selected from the group consisting of substances which cause a sharp taste, or a warming or burning sensation on the skin or mucous membranes, or a tingling or effervescent sensation in the mouth or throat, or active substances which have a pungent, stimulating or astringent effect, is used as the encapsulated active substance or as the core material.

[0158] The heat-inducing or pungent active ingredient is preferably paprika powder, chili powder, an extract from paprika, an extract from pepper, an extract from chili pepper, an extract from ginger root, an extract from grain of paradise (Aframomum melegueta), an extract from Jambu oleoresin (Spilanthes acmella, resp. Spilanthes oleracea), an extract from Japanese pepper (Zanthoxylum piperitum), an extract from Kaempferia galanga, an extract from Alpinia galanga, an extract from Polygonium hydropiper), capsaicinoids, in particular capsaicin, dihydrocapsaicin or nonivamide; gingerols, in particular gingerol[6], gingerol[8], gingerol

[10] ; shogaols, in particular shogaol[6], shogaol[8], shogaol

[10] ; gingerediones, in particular gingerediones[6], gingerediones[8], gingerediones

[10] ; paradols, in particular paradol[6], paradol[8], paradol

[10] ; dehydrogingerediones, in particular dehydrogingerediones-[6], dehydrogingerediones-[8] or dehydrogingerediones-

[10] ; piperine, piperine derivatives; ethyl 2-(4-hydroxy-3-methoxy-phenyl)acetate and 3-phenylpropyl-2-(4-hydroxy-3-methoxy-phenyl)acetate and mixtures thereof.

[0159] The active ingredient that may be perceived as hot or pungent is preferably selected from the group consisting of aromatic isothiocyanates, in particular phenylethyl isothiocyanate, allyl isothiocyanate, cyclopropyl isothiocyanate, butyl isothiocyanate, 3-methylthiopropyl isothiocyanate, 4-hydroxybenzyl isothiocyanate, 4-methoxybenzyl isothiocyanate, and mixtures thereof.

[0160] The tingling agent is preferably 2E,4E-decadienoic acid-N-isobutyramide (trans-pellitrin), in particular as described in WO 2004 / 043906; 2E,4Z-decadienoic acid-N-isobutyramide (cis-pellitrin), in particular as described in WO 2004 / 000787; 2Z,4Z-decadienoic acid-N-isobutyramide; 2Z,4E-decadienoic acid-N-isobutyramide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; Acid-N-([2S]-2-methylbutyl)amide;2E,4E-Decadienoic acid-N-([2R]-2-methylbutylamide);2E,4Z-Decadienoic acid-N-(2-methylbutyl)amide;2E,4E-Decadienoic acid-N-piperid(Athileamide);2E,4E-Decadienoic acid-N-piperid(Sarmentin);2E-Decanoic acid-N-isobutyramide;3E-Decanoic acid-N-isobutyramide;3E-Nonenoic acid-N-isobutyramide;2E,6Z,8E-Decatrienoic acid-N-isobutyramide(Spira 2E,6Z,8E-Decatrienoic acid-N-([2S]-2-methylbutyl)amide (Homospilanthol);2E,6Z,8E-Decatrienoic acid-N-([2R]-2-methylbutyl)amide;2E-Decen-4-ioniic acid-N-isobutyramide;2Z-Decen-4-ioniic acid-N-isobutyramide;2E,6Z,8E,10E-Dodecatetraenoic acid-N-(2-methylpropyl)amide (α-sanshool);2E,6Z,8E,10E-Dodecatetraenoic acid-N-(2-hydroxy-2-methyl)amide propyl)-amide (α-hydroxysanshool);2E,6E,8E,10E-dodecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (γ-hydroxysanshool);2E,4E,8Z,10E,12E-tetradeca-pentaenoic acid-N-(2-hydroxy-2-methylpropyl)amide (γ-hydroxysanshool);2E,4E,8E,10E,12E-tetradeca-pentaenoic acid-N-(2-hydroxy-2-methylpropyl)-amide-(γ-hydroxyisosanshool);The compound is selected from the group consisting of 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N-(2-methyl-2-propenyl)amide (γ-dehydrosanshool); 2E,4E,8Z,10E,12E-tetradecapentanoic acid-N-(2-methylpropyl)amide (γ-sanshool); 2E,4E,8Z,11Z-tetradecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (bungeanol); 2E,4E,8Z,11E-tetradecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (isobungeanol); 2E,4E,8Z-tetradecatrienoic acid-N-(2-hydroxy-2-methylpropyl)amide (dihydrobungeanol) and 2E,4E-tetradecadienoic acid-N-(2-hydroxy-2-methylpropyl)amide (tetrahydrobungeanol) and mixtures thereof. ;

[0161] The active ingredient having an astringent effect is preferably selected from the group consisting of catechins, in particular epicatechin, gallocatechin, epigallocatechin as well as their respective gallic acid esters, in particular epigallocatechin gallate or epicatechin gallate, their oligomers (procyanidins, proanthocyanidins, prodelphinidins, procyanilins, thearbigenins, theogallins) as well as their C- and O-glycosides; dihydroflavonoids, for example dihydromyricetin, taxifolin, and their C- and O-glycosides; flavonols, for example myricetin, quercetin, and their C- and O-glycosides, for example quercetrin, rutin, gallic acid esters of carbohydrates such as tannins, pentagalloylglucose or their reaction products, for example erigatannins; aluminum salts, for example alum, and mixtures thereof.

[0162] In a further variation of the first and / or second aspect of the invention, essential vital components may also be encapsulated in the core material, where the core material comprises at least one essential vital component or a mixture thereof.

[0163] Essential vital components are biologically active ingredients, such as tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, carnotine, carnosine, caffeine, (deoxy)ribonucleic acid and its fragmentation products, β-glucan, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

[0164] In a further variant of the process according to the invention, substances for paper printing coatings are also used as active ingredients to be encapsulated or as core materials, as described in US 2,800,457 A, the disclosure of which is hereby incorporated by reference in its entirety into the present description.

[0165] The internal non-aqueous phase may contain, for example, 20 to 80% by weight, preferably 25 to 75% by weight, and even more preferably 33 to 50% by weight of the active ingredient to be encapsulated, 0.1 to 5% by weight, preferably 0.15 to 3.5% by weight, and even more preferably 0.5 to 2.5% by weight of a crosslinker, and further up to 100% by weight of a hydrophobic solvent, based on the total weight of the internal non-aqueous phase.

[0166] It is therefore possible to achieve high loading of the plant protein-based microcapsules according to the invention with active ingredients using the process according to the invention.

[0167] In a further step (ii) of the process according to the invention, an outer aqueous phase is provided which comprises at least one plant protein and optionally at least one first polysaccharide and / or at least one further crosslinker and / or at least one polyhydroxyphenol and / or at least one protective colloid, and optionally further adjusting the pH of the aqueous phase to a pH lower than the isoelectric point of the plant protein.

[0168] The polyhydroxyphenol optionally added in step (ii) may also be a further cross-linking agent. The polyhydroxyphenol may also be a cross-linking agent itself. Optionally, the polyhydroxyphenol may be added instead or in addition in step (i). The polyhydroxyphenol is preferably tannin.

[0169] In a preferred embodiment of the invention, in step (ii) an external aqueous phase may be provided which comprises at least one plant protein and at least one first polysaccharide.

[0170] When an external aqueous phase comprising at least one plant protein and at least one first polysaccharide is provided in step (ii), particularly preferred is a plant protein, wherein the plant protein is preferably selected from the group consisting of pea protein, sunflower protein, hemp protein, pumpkin protein or soy protein.

[0171] Particularly preferably, when an external aqueous phase is provided in step (ii) comprising at least one plant protein and at least one first polysaccharide, the at least one first polysaccharide is carboxymethylcellulose (CMC) and / or pectin.

[0172] The pectin is preferably a highly esterified pectin, which preferably has a degree of esterification of at least 50%, particularly preferably >68%.

[0173] A suitable solvent for preparing the external aqueous phase is water or a mixture of water with at least one water-miscible organic solvent. Suitable organic solvents are, for example, glycerol, 1,2-propanediol, 1,3-propanediol, ethanediol, diethylene glycol, triethylene glycol and other similar. However, preferably, the solvent is water.

[0174] According to the invention, the at least one plant protein or the at least one further plant protein is selected from the group consisting of proteins, in particular plant proteins from the group consisting of cereals, in particular wheat, barley, rye, spelt, gluten, in particular wheat gluten, rapeseed, rice, potato, maize, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, broad bean, pea, hemp, pumpkin and sunflower, protein isolates produced by physico-chemical processes or by fermentation or enzymatic treatment of other proteins from edible plants, plant proteins in the form of fractions, partial or complete hydrolysates or intermediates, chitosan and mixtures thereof.

[0175] Particularly preferred is at least one plant protein selected from the group consisting of hemp protein, pumpkin protein, soybean protein, sunflower protein and pea protein. Particularly preferred is at least one plant protein, hemp protein or pumpkin protein, which have particularly good stability.Alternatively, soybean protein and pumpkin protein are also preferred due to their organoleptic properties.

[0176] Among the abovementioned proteins, pea, hemp, pumpkin, soybean and sunflower are particularly preferred, as in combination with aliphatic polyisocyanates as crosslinkers they are particularly suitable for obtaining vegan microcapsules which are characterized by a particularly high stability and good organoleptic properties.

[0177] The amino acids may be proteinogenic L-amino acids, which may be selected from the group consisting of L-alanine, L-arginine, L-asparagine, L-aspartic acid, L-cysteine, L-glutamine, L-glutamic acid, L-glycine, L-histidine, L-isoleucine, L-leucine, L-lysine, L-methionine, L-phenylalanine, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, and L-valine.

[0178] The above mentioned proteins also have the advantageous effect that they have an emulsifying effect. Due to their emulsifying effect, they contribute to the stabilization of emulsions. Due to their more or less flexible structure in the molecule and their differently charged regions, proteins are amphiphilic and therefore surface active. By modifying the protein, for example by physical or chemical modification, the secondary and / or tertiary structure of the molecule can be changed. By changing the spatial availability of the charged regions of the molecule or by exposing amino acid side chains, this can affect the emulsifying properties. Due to these advantageous properties, additional emulsifiers or protective colloids can be omitted in the process according to the invention.

[0179] The proportion of the at least one protein, preferably pea protein, pumpkin protein, hemp protein, soy protein or sunflower protein, in the external aqueous phase is in the range of 0.01 to 7.0 wt.-%, preferably in the range of 0.05 to 5.0 wt.-%, particularly preferably in the range of 0.07 to 2.5 wt.-%, based on the total weight of the external aqueous phase.

[0180] According to a further aspect of the invention, the at least one first polysaccharide and / or the at least one further polysaccharide is · Resistant fibres and dietary fibres, in particular insoluble dietary fibres, in particular cellulose, hydroxyethylcellulose, in particular quaternized hydroxyethylcellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), cellulose derivatives such as hemicellulose, lichenin, chitin, chitosan, lignin, xanthan gum, vegetable fibres, in particular cereal fibres, potato fibre, apple fibre, citrus fibre, bamboo fibre, extracted sugar beet fibre; oat fibre and soluble dietary fibres, in particular inulin, in particular native inulin, highly soluble inulin, granular inulin, high performance inulin, pectins, alginates, agar, carrageenan, tragacanth, gum arabic, konjac gum, gurdran (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, polydextrose and lactulose; starches, in particular starches from wheat, potato, corn, rice, tapioca and oats, chemically, mechanically and / or enzymatically modified starches; and starch derivatives, such as dextrins or maltodextrins, in particular dextrins and maltodextrins from wheat, potato, corn, rice and oats, in particular maltodextrins DE8-10, DE17-20, DE18-20, cyclodextrins, oligosaccharides, in particular oligofructose; and Sugar alcohols, in particular sorbitol, mannitol, isomalt, maltitol, maltitol syrup, lactitol, xylitol, erythritol; Gellin; glucose; Glycosaminoglycans, especially hyaluronic acid as well as mixtures of the foregoing polysaccharides.

[0181] Of the aforementioned polysaccharides, gum arabic and maltodextrin are particularly preferred. Most preferred are maltodextrins DE8-10 potato; DE17-20 corn; DE8-10 corn; DE17-20 potato and DE18-20 wheat.

[0182] In a particularly advantageous further development of the invention, it may be provided that the at least one first polysaccharide and / or the at least one further polysaccharide is selected from the group consisting of hyaluronic acid, carrageenan, gellan gum, agar, alginates, xanthan gum. In this way, vegetable protein-based microcapsules with very good organoleptic properties are obtained.

[0183] In particular, it may be provided that the first polysaccharide and / or the at least one further polysaccharide comprises at least hyaluronic acid and / or carrageenan and / or gellan gum and / or agar and / or alginate and / or xanthan gum.

[0184] The proportion of the at least one polysaccharide in the external aqueous phase is in the range of 0.1 to 3.0% by weight, preferably in the range of 0.2 to 1.0% by weight, based on the total weight of the external aqueous phase. Most preferably, the at least one polysaccharide is used in the range of 0.25 to 0.75% by weight, based on the total weight of the external aqueous phase.

[0185] Preferably, both of the main components of the capsule shell, i.e., at least one protein and at least one polysaccharide, are provided in the external aqueous phase. The combination of protein and polysaccharide results in the formation of a soluble or insoluble protein-polysaccharide complex. The emulsion thus formed is not prone to flocculation, so that the addition of protective colloids or additional emulsifiers is not required in the process according to the invention.

[0186] The following combinations of proteins and polysaccharides are particularly preferred for constructing the capsule wall or capsule shell: pea protein and maltodextrin; hemp protein and maltodextrin; pumpkin protein and maltodextrin; sunflower protein and maltodextrin; soy protein and maltodextrin.

[0187] Proteins and polysaccharides, previously described and exemplary components of the capsule wall structure, are readily available from biological sources. As such, they are readily biodegradable.

[0188] In an alternative variation of the process according to the invention, only one of the major components of the capsule shell, protein or polysaccharide, is provided in the external aqueous phase, with the optional addition of the other major component, polysaccharide or protein, in process step (iv) and / or process step (vi) after emulsification / dispersion and before or together with the optional addition of a catalyst in process step (v).

[0189] By using at least one protein and at least one polysaccharide, the content of crosslinking agent polyisocyanate in the capsule shell can be reduced compared to prior art microcapsules having a high content of polyisocyanate.

[0190] Surprisingly, however, this low degree of cross-linking leads to stable microcapsules on the one hand and to microcapsules that are better biodegradable on the other hand, as illustrated in the embodiment examples below.

[0191] Optionally, a protective colloid can be added to the external aqueous phase.

[0192] Protective colloids are polymeric systems that prevent clumping (aggregation, coagulation, flocculation) of emulsified, suspended or dispersed components in a suspension or dispersion. During solvation, protective colloids bind large amounts of water depending on the concentration, producing high viscosity in aqueous solutions. During the formation of an oil-in-water emulsion, the hydrophobic part of the protective colloid attaches itself to the primary particles and orients the polar, i.e., hydrophilic, part of its molecule towards the aqueous phase. By thus adhering to the interface, it reduces the interfacial tension and prevents the aggregation of the primary particles. It also stabilizes the emulsion and promotes the formation of relatively small droplets and thus the corresponding microcapsules.

[0193] In the process according to the invention, the protective colloid also has emulsifying properties in addition to the above-mentioned properties, for example, protective colloids such as carboxymethylcellulose (CMC), acid modified starch, polyvinyl alcohol, ammonium derivatives of polyvinyl alcohol, polystyrene sulfonates, polyvinylpyrrolidone, polyvinyl acrylate, have sufficient emulsifying properties, so that the process according to the invention can even advantageously dispense with the use of emulsifiers in the downstream emulsification / dispersion step (iii).

[0194] The protective colloids used in the process according to the invention are Diols, in particular ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, the isomeric butanediols, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, as well as polyols, preferably triols, in particular glycerol and its ethoxylated and propoxylated products, trimethylolpropane and its ethoxylated and propoxylated products, polyvinyl alcohol (PVOH) and its derivatives, in particular ammonium- or sulfonate-functionalized polyvinyl alcohols, polyphenols, preferably 1,3,5-trihydroxybenzene, polysaccharides, in particular glucose, starch or chemically, mechanically and / or enzymatically modified starches, hydroxyethylcellulose, in particular quaternized hydroxyethylcellulose, and cellulose derivatives such as carboxymethylcellulose, Polyvinylpyrrolidone, vinyl maleate copolymer, sodium lignosulfonate, maleic anhydride / styrene copolymer, ethylene / maleic anhydride copolymer, copolymers of ethylene oxide, propylene oxide and polyethoxylated sorbitol acid esters, sodium dodecyl sulfate, Vegetable polymers, especially gum arabic (Senegal and seyal types), olibanum resin, shellac, lignin, chitosan, saponin, and mixtures of the foregoing compounds.

[0195] Starch, especially modified starch or vegetable polymers, are naturally occurring substances that are biodegradable. In combination with the polyisocyanates described herein, the process can thus provide a bio-based and biodegradable capsule shell. In the process according to the invention, starch and vegetable polymers therefore act as so-called bio-crosslinkers.

[0196] The starch used in the process according to the invention is selected from the group consisting of corn starch, potato starch, rye starch, wheat starch, barley starch, oat starch, rice starch, pea starch, tapioca starch, and mixtures thereof.

[0197] The chemically modified starch is preferably an acid-modified starch, an alkali-modified starch, an oxidized starch, an acetylated starch, a succinated starch, or an octyl-succinated starch.

[0198] Preferably, the external aqueous phase comprises at least one protective colloid selected from polyvinylpyrrolidone, polyvinyl alcohol, a polyol, a polyphenol, or starch, and mixtures thereof.

[0199] Even more preferably, polyols, polyphenols or starches, in particular modified starches, are used as protective colloids.Polyvinyl alcohol or its ammonium derivatives, 1,3,5-trihydroxybenzene, modified starches or carboxymethylcellulose are particularly preferably used as protective colloids in the preparation of the microcapsules according to the invention.

[0200] According to the invention, a combination of two or more different protective colloids may also be used to prepare the microcapsules according to the invention.

[0201] It has been found to be particularly advantageous to use in the process according to the invention a combination of one of the above-mentioned protective colloids and starch as further protective colloid in the external aqueous phase.Due to the large number of functional hydroxyl groups, such a combination stabilizes the emulsion, and on the other hand promotes the reaction between protective colloid and polyisocyanate(s), so that the reaction equilibrium in the reaction of protective colloid with polyisocyanate(s) shifts towards the product, i.e. polyurethane.The large number of functional hydroxyl groups in starch also allows the formation of particularly pronounced spatial crosslinks.

[0202] According to the number of functional groups and / or the size of the protective colloid, the above-mentioned protective colloid has different reaction speed with the isocyanate group of at least one polyisocyanate.For example, glycerol reacts faster with the isocyanate group than starch due to its size.Therefore, by selecting the protective colloid, the crosslinking of the protective colloid by the isocyanate group of the polyisocyanate can be controlled.

[0203] The combination of glycerol with starch or with modified starch or with quaternized hydroxyethylcellulose or gum arabic Seyal type has proven to be a particularly advantageous combination; such a combination takes advantage of the above-mentioned properties of both protective colloids: on the one hand, the fast reaction rate of glycerol and, on the other hand, the number of polymerizable functional groups of the other protective colloid.

[0204] The protective colloids used in the process according to the invention have a dual function in that on the one hand they act as protective colloids, preventing aggregation of the emulsified, suspended or dispersed components, stabilising the subsequently formed emulsion, promoting the formation of small droplets and finally stabilising the microcapsules formed.

[0205] The external aqueous phase is preferably prepared with agitation by sequentially adding the polysaccharide and / or protein and optionally the protective colloid to the external aqueous phase, or vice versa, or by adding the ingredients simultaneously to the external aqueous phase.

[0206] To improve the solubility of the protein, the pH value of the external aqueous phase is optionally adjusted to a pH value below the isoelectric point of the protein, ie a pH value lower than the isoelectric point of the protein used.

[0207] The isoelectric point is the pH value at which the isoelectric state is reached, i.e. the positive and negative charges of ampholytes or zwitterions (e.g. amino acids and proteins) are in equilibrium. This value is a constant characteristic of each amino acid and is determined by the pK a In addition to amino acids, peptides and proteins also have an isoelectric point. Amino acids, and therefore proteins, have the lowest water solubility at their isoelectric points.

[0208] Preferably, the pH value of the aqueous phase is adjusted to a slightly acidic pH value in the range of 2.0 to 7.0, even more preferably to a pH value in the range of 2.0 to 6.0, most preferably to a pH value in the range of 3.0 to 5.0, depending on the isoelectric point of the protein used. Adjusting the pH to a pH value below the isoelectric point, i.e. below the isoelectric point of the protein, has the advantage that the emulsifying properties and solubility of the protein are maximum at such pH values.

[0209] The pH value of the external aqueous phase is adjusted by adding an organic acid. For this purpose, an organic acid, such as formic acid or acetic acid, is added to the external aqueous phase before the emulsification step to set the pH value in the ranges mentioned above.

[0210] The internal non-aqueous phase comprising at least one crosslinker and at least one hydrophobic active ingredient is emulsified or dispersed in the external aqueous phase in a further process step (iii) to form an oil-in-water emulsion / dispersion.

[0211] The oil-in-water emulsion is prepared by mixing an internal non-aqueous phase and an internal aqueous phase. The weight ratio of the internal non-aqueous phase to the internal aqueous phase is preferably in the range of 70:30 to 60:40, preferably in the range of 30:70 to 60:40.

[0212] Stabilizers and / or emulsifiers or co-emulsifiers are optionally added to the emulsion or dispersion in the process according to the invention to facilitate the formation of the emulsion or dispersion from the internal non-aqueous phase and the internal aqueous phase, to stabilise the emulsion or dispersion formed, and to prevent separation of the internal non-aqueous (oily / organic / hydrophobic) phase and the external aqueous (hydrophilic) phase.

[0213] Preferably, a stabilizer is added to the external aqueous phase to stabilize the emulsion or dispersion to prevent separation of the internal non-aqueous (oil) phase and the external aqueous phase.

[0214] Stabilizers preferred for producing the polysaccharide-based and protein-based microcapsules according to the invention are in particular acrylic acid copolymers with sulfonate groups.Suitable are also copolymers of acrylamide and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as LUVISKOL® K15, K30, K90 (BASF); sodium polycarboxylates, sodium polystyrenesulfonate, vinyl and methyl vinyl ether maleic anhydride copolymers, as well as ethylene, isobutylene or styrene maleic anhydride copolymers, microcrystalline celluloses sold under the name VIVAPUR®, such as diutan gum, xanthan gum or carboxymethylcellulose.

[0215] The amount of stabilizer used can be in each case in the range from 0.01 to 10% by weight, preferably in the range from 0.1 to 3% by weight, based on the external aqueous phase.

[0216] Optionally, an emulsifier is used in the process according to the invention, preferably an O / W emulsifier, which allows a homogeneous distribution of the oil droplets of the internal non-aqueous phase in the external aqueous phase and stabilizes the emulsion. The same applies to the incorporation of a solid insoluble active ingredient in the external aqueous phase in order to stabilize the resulting dispersion.

[0217] In particular, the addition of an emulsifier is optional if the protein or protective colloid has no or only slight, i.e. insufficient, emulsifying properties. If an emulsifying protein or protective colloid is used, the use of an emulsifier can advantageously be omitted in the process according to the invention.

[0218] Suitable emulsifiers include those from the following groups: Addition products of 2-30 mol of ethylene oxide and / or 0-5 mol of propylene oxide onto fatty alcohols having 8-22 C atoms in the alkyl group, fatty acids having 12-22 C atoms, alkylphenols having 8-15 C atoms and alkylamines having 8-22 carbon atoms in the alkyl radical; · Alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alkyl / alkenyl radical and their ethoxylated analogues; · addition products of 1 to 15 moles of ethylene oxide onto castor oil and / or hydrogenated castor oil; · addition products of 15 to 60 moles of ethylene oxide onto castor oil and / or hydrogenated castor oil; partial esters of glycerol and / or sorbitan with unsaturated linear or saturated branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms, and their adducts with 1 to 30 moles of ethylene oxide; partial esters of polyglycerol (average degree of self-condensation 2-8), polyethylene glycol (molecular weight 400-5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose) with saturated and / or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms, as well as their adducts with 1 to 30 moles of ethylene oxide, preferably Cremophor®; mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglucose and a polyol, preferably glycerol or polyglycerol; Mono-, di- and trialkyl phosphates, as well as mono-, di- and / or tri-PEG-alkyl phosphates and their salts; Lanolin alcohol; Polysiloxane polyalkyl polyether copolymers or corresponding derivatives; Block copolymers, such as polyethylene glycol 30 dipolyhydroxystearate; Polymeric emulsifiers, such as Pemulen types (TR1, TR2) from Goodrich or Cosmedia® SP from Cognis; Polyalkylene glycols and glycerol carbonate Examples of nonionic surfactants include those derived from at least one of the following:

[0219] Typical anionic emulsifiers which can be used in the process according to the invention for producing isocyanate-based microcapsules are aliphatic fatty acids having 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, such as azelaic acid or sebacic acid.

[0220] Furthermore, zwitterionic surfactants can be used as emulsifiers in the process according to the invention for producing polysaccharide-based and protein-based microcapsules. Zwitterionic surfactants are surface-active compounds which have at least one quaternary ammonium group, at least one carboxylate group and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, for example N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, for example cocosacylaminopropyldimethylammonium glycinate with 8 to 18 C atoms in the alkyl or acyl group, respectively, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines and cocosacylaminoethylhydroxyethylcarboxymethyl glycinate. Particularly preferred are fatty acid amide derivatives known under the CTFA designation cocamidopropyl betaine.

[0221] Amphoteric surfactants are also suitable emulsifiers. Amphoteric surfactants are understood to be surface-active compounds that contain at least one free amino group and at least one -COOH or -SO3H group in addition to a C8 / 18 alkyl or acyl group in the molecule and can form inner salts. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyl-taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having about 8 to 18 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionates, cocoacylaminoethylaminopropionates and C12 / 18 acylsarcosines.

[0222] Finally, cationic surfactants may also be considered as emulsifiers, accordingly those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, quaternized hydroxyethylcellulose, chitosan modified with propylene glycol and quaternized with epichlorohydrin, distearyldimethylammonium chloride (DSDMAC), benzalkonium chloride, benzethonium chloride, cetylalkonium chloride, cetylpyridinium chloride, cetyltrimethylammonium bromide (cetrimonium bromide), dequalinium chloride are particularly preferred.

[0223] The emulsifier may be added to the external aqueous phase in an amount of from about 0.1 to about 10% by weight, preferably from about 1 to about 5% by weight, in each case based on the total weight of the external aqueous phase.

[0224] Emulsion formation (for liquid active ingredients) or dispersion formation (for solid active ingredients), i.e. emulsification or dispersion of an internal non-aqueous or oily phase with an external aqueous or hydrophilic phase, is carried out under high turbulence or high shear forces, and the intensity of the turbulence or shear forces determines the diameter of the resulting microcapsules. Microcapsules can be produced continuously or discontinuously. The size of the capsules generally decreases as the viscosity of the aqueous phase increases or the viscosity of the oily phase decreases.

[0225] The process according to the invention for producing polysaccharide-based and protein-based microcapsules can be carried out, for example, using the "in-line" technique, in which the internal non-aqueous phase and the external aqueous phase are first fed separately to an emulsification turbine by forced metering pumps and then mixed just before entering the emulsification turbine at a throughput rate of 1200-1500 l / h or mixed in the emulsification turbine. In addition, the process according to the invention for producing polysaccharide-based and protein-based microcapsules can also be carried out in conventional dispersion or emulsification devices.

[0226] The emulsification or dispersion of the external aqueous phase and the internal non-aqueous phase is carried out for example by means of an emulsifying turbine (IKA Eurostar 20 high speed stirrer) for the preparation of the microcapsules according to the invention.

[0227] The emulsifying or dispersing process in the method according to the present invention is advantageously carried out at a stirring speed of 1000 rpm to 5000 rpm, preferably 2000 rpm to 4000 rpm, for a time period of 30 seconds to 20 minutes, preferably 1 to 7 minutes, most preferably 1 to 5 minutes, until a capsule size of 10 to 75 μm ± 5 μm (D50) or 75 to 155 ± 10 μm (D90) is achieved.

[0228] After completion of the emulsifying or dispersing step (iii), an oil-in-water emulsion or dispersion exists, in which the internal oil phase containing the active ingredient to be encapsulated is finely emulsified or dispersed in the external aqueous phase in the form of droplets.

[0229] In an alternative variant of the process according to the invention, after the emulsifying or dispersing step (iii) as described above, at least one polysaccharide or at least one protein is optionally added in process step (iv). If an external aqueous phase with only at least one major protein component is provided in process step (ii), at least one polysaccharide is added in process step (iv). On the other hand, if an external aqueous phase with only at least one major polysaccharide component is provided in process step (ii), at least one protein is added in process step (iv). Separate addition leads to the formation of multiple layers ("layer by layer"), the individual layers of which are cross-linked to each other in a subsequent process step (v). This makes it possible, for example, to control the charge of the emulsion and thus the flocculation stability.

[0230] Alternatively, further proteins and / or polysaccharides can be optionally added in process step (iv) that are the same or different from the at least one protein and / or at least one polysaccharide from process step (ii), or that have a different charge or change their charge when the pH is changed. By adding further proteins and / or polysaccharides, further layers ("layer by layer") are built up, the individual layers of which are subsequently cross-linked to each other in process step (v). This leads to a denser and more stable network of capsule wall components, and thus to a more stable capsule shell, which increases the stability of the microcapsules.

[0231] A further preferred embodiment of the present invention may therefore provide for adding at least one polysaccharide and / or at least one protein in process step (iv).

[0232] The further protein and / or further polysaccharide is selected from the group of plant proteins and / or polysaccharides as already defined in detail above for process step (ii). The same applies with respect to the preferred variants or preferred combinations of plant proteins and / or polysaccharides described herein.

[0233] In a further preferred embodiment of the present invention, an external aqueous phase comprising at least one plant protein and at least one first polysaccharide may be provided in step (ii), and the at least one polysaccharide and / or the at least one protein may be further added in step (iv).

[0234] Particularly preferably, it can be provided that in step (ii) an external aqueous phase is provided comprising at least one plant protein and at least one first polysaccharide, and further in process step (iv) at least one polysaccharide and / or at least one protein is added, wherein the at least one protein in steps (ii) and (iv) is preferably selected from the group consisting of pea protein, hemp protein, pumpkin protein, soy protein or sunflower protein, and the at least one polysaccharide in steps (ii) and (iv) is pectin and / or carboxymethylcellulose (CMC).

[0235] The pectin is preferably a highly esterified pectin, which preferably has a degree of esterification of at least 50%, particularly preferably a degree of esterification of >68%.

[0236] In a subsequent process step (v) of the process according to the invention, a first cross-linking of the capsule shell or capsule wall material is also carried out with stirring.

[0237] In order to crosslink the above-mentioned layers ("layer by layer") of capsule wall components and to stabilize the resulting capsule shell, a first crosslinking is carried out after emulsification or dispersion, optionally by adding a catalyst. By interfacial polymerization at the interface between the outer aqueous phase and the dispersed inner phase, i.e. the interface of the emulsified or dispersed oil droplets encapsulating the active ingredient to be encapsulated, a catalyzed polymerization reaction is formed between the carboxyl and / or sulfo and / or hydroxyl groups of the polysaccharide and the amino groups of the protein on the one hand, and the isocyanate groups of the crosslinker on the other hand.

[0238] In a further embodiment of the present invention, it may therefore be provided that in step (v) the first crosslinking is carried out by adding at least one catalyst to obtain a slurry of microcapsules; wherein the at least one catalyst is selected from the group consisting of diazobicyclo[2.2.2]octane (DABCO), bismuth catalysts and tin catalysts, and mixtures of two or more of the aforementioned catalysts.

[0239] Due to the catalyzed cross-linking between the functional groups of at least one polysaccharide and / or at least one plant protein of the above-described layers and the functional groups of the cross-linking agent, a first cross-linking unit or a first cross-linking matrix is ​​formed for the construction of the capsule shell or capsule wall.

[0240] The formation of the first crosslinking units in the process according to the invention is based on a polyaddition reaction between the polysaccharide and the crosslinking agent and / or the plant protein and the crosslinking agent, in which the hydroxyl groups of the polysaccharide react with the isocyanate groups of the crosslinking agent to form polyurethanes and the amino groups of the protein react with the isocyanate groups of the crosslinking agent to form polyureas. In addition to polyurethanes and polyureas, soluble or insoluble complexes of the plant protein and the polysaccharide are also formed during the first crosslinking step (v) to form the capsule wall matrix or capsule shell.

[0241] The more crosslinking functional groups of the capsule wall components, the more spatial crosslinking occurs, and the denser and more stable the resulting capsule shell or capsule wall of the microcapsule becomes. In addition to the number of functional groups, the chain length of the individual capsule wall components also significantly affects the mechanical properties, i.e., stability, of the microcapsule. For example, the large number of hydroxyl groups in starch allows the formation of particularly significant spatial crosslinking; long-chain capsule wall components, such as polyisocyanates, lead to the formation of a more stable capsule wall.

[0242] By forming a first cross-linked matrix or a first cross-linking unit, the core material, i.e., the emulsified or dispersed oil droplets with the active ingredient to be encapsulated, are encapsulated by the cross-linked matrix or cross-linking unit at the outer interface, thus generating a capsule wall, thereby making the diffusion of the encapsulated active ingredient more difficult.

[0243] The addition of at least one catalyst to the emulsion or dispersion accelerates the cross-linking reaction between the polysaccharides and / or plant proteins and the cross-linking agent and catalyzes the reaction that favors the formation of a first cross-linked matrix or first cross-linking units.

[0244] The catalyst that may be added in the process according to the invention may preferably be triethylenediamine (TEDA), diazobicyclo[2.2.2]octane (DABCO), also known as bicyclic tertiary amine. DABCO is commonly used as a catalyst in the production of polyurethane plastics. Tertiary amines with a free electron pair favor the reaction between the isocyanate groups of the crosslinker and the hydroxyl groups of the polysaccharide.

[0245] In addition to DABCO, catalysts based on bismuth or tin can also be used to catalyze the first crosslink, for example, catalysts based on bismuth (II) or bismuth (III) salts as described in KC Frasch & LP Rumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5:1, pages 103-149, DOI:10.1080 / 15583727008085365, the disclosure of which is incorporated herein in its entirety in this regard.

[0246] Preferably, a combination of DABCO with one of the above catalysts can be used, such mixtures leading to increased reactivity as described in KC Frasch & LPRumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5:1, pages 103-149, DOI:10.1080 / 15583727008085365, the disclosure of which is incorporated herein in its entirety.

[0247] DABCO and the aforementioned catalysts preferably catalyze the polyurethane reaction between at least one polymerizable aliphatic polyisocyanate having two or more isocyanate groups and a diol or polyol in the process according to the present invention.

[0248] In one embodiment of the process according to the invention, a catalyst can be added to the external aqueous phase. It may be proposed that the amount of catalyst added to the external aqueous phase is in the range of 0.001 to 2 wt.%, preferably in the range of 0.02 to 1.0 wt.%, particularly preferably in the range of 0.05 to 0.8 wt.%, based on the total weight of the external aqueous phase.

[0249] However, larger amounts of catalyst can be added if desired.

[0250] Preferably, the catalyst is added as such, for example as a solid, or in the form of an aqueous solution, preferably in water, to the emulsion or dispersion under stirring. It may be proposed that the amount of catalyst is in the range of 0.001 to 2% by weight, preferably in the range of 0.02 to 1.0% by weight, particularly preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the external aqueous phase.

[0251] It may be proposed that the catalyst is preferably present in aqueous solution in a concentration of 0.5 to 2 mol / l, preferably 1 mol / l.

[0252] The catalyst is added at a temperature in the range of 20° C. to 30° C., preferably 22° C. to 26° C., and at a stirring speed of 500 rpm to 2000 rpm, preferably 1000 rpm to 1500 rpm.

[0253] Even more preferably, in process step (v) the first crosslinking is carried out by heating the emulsion or dispersion stepwise to a temperature in the range of 60° C. to 90° C., preferably to a temperature in the range of 65° C. to 85° C., most preferably to a temperature in the range of 70° C. to 80° C. The first crosslinking in the process according to the invention is carried out for a period of about 30 minutes to 90 minutes, preferably for a period of 40 minutes to 70 minutes, most preferably for a period of 60 minutes.

[0254] In a further embodiment of the process, the first crosslinking may be carried out at a temperature between 20° C. and 40° C., preferably between 20° C. and 30° C., in particular at room temperature.

[0255] After the first cross-linking and formation of the capsule shell or wall, the capsules produced according to the method of the present invention exist as raw microcapsules in the form of an aqueous dispersion or slurry.

[0256] After crosslinking, the microcapsules in the slurry have a shell that is not particularly stable yet flexible and therefore easily cracks. For this purpose the shell is hardened. The hardening in process step (vi) is preferably carried out by gradually raising the microcapsule slurry to a temperature of at least 60°C, preferably in the range of 60°C to 90°C, preferably in the range of 65°C to 80°C up to the boiling point of the microcapsule slurry. The hardening is usually carried out for a period of at least 1.5 hours, preferably between 2 and 5 hours, most preferably 3 hours.

[0257] It is also advantageous to add a hardening substance to the microcapsule slurry. For this purpose, natural vegetable tanning agents of the tannin type are used, which from a chemical point of view are proanthocyanidins found in shrubs, bushes and leaves of dicotyledonous plants, especially in the tropics and subtropics. Terpenes generally have a molecular weight in the range of 500 to 3000 kDa. A preferred example of a suitable tannin is corigalin. For hardening, an aqueous preparation of tannin is added to the aqueous dispersion containing the raw microcapsules. Usually, the tannin is added in an amount of about 0.1 to about 2% by weight, preferably about 0.5 to about 1.5% by weight, based on the microcapsules.

[0258] In order to optimise the cross-linking of the capsule wall matrix, in an alternative variant of the process according to the invention, further vegetable protein and / or further polysaccharides can optionally be added to the microcapsule slurry in process step (vi).

[0259] The further plant protein and / or further polysaccharides are selected from the group of proteins and / or polysaccharides as already defined in detail above for process step (ii). The same definitions and preferred embodiments and / or preferred combinations for the plant proteins and / or polysaccharides are also fully valid for the further plant protein and / or further polysaccharides.

[0260] The further plant protein and / or further polysaccharides may be the same as or different from the plant protein and / or polysaccharides of process step (ii).

[0261] The addition of additional plant proteins and / or additional polysaccharides results in additional cross-linking by the cross-linking agent, contributing to the formation of a particularly dense and stable network of capsule wall components.

[0262] The hardening step (vi) of the process according to the invention involves cooling the microcapsule slurry to room temperature, optionally followed by a second cross-linking of the capsule wall components by adding further cross-linking agent.

[0263] At least one further crosslinking agent selected from the group consisting of transglutaminase, peroxidase, polyphenols, polyhydroxyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, as well as secondary plant substances selected from the group consisting of: polyphenols, polyhydroxyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, as well as mixtures of two or more of the aforementioned crosslinking agents, are used as further crosslinking agents in the process according to the invention for further crosslinking in conjunction with the first and further crosslinking agents. The same definitions and preferred embodiments as for the first and further crosslinking agents are also fully valid for the further crosslinking agents.

[0264] Cinnamaldehyde, tannin, ferulic acid and gallic acid are particularly preferred among the other cross-linking agents mentioned above.

[0265] At least one further cross-linking agent may be added to the non-aqueous phase. Alternatively, or in addition, at least one further cross-linking agent may be added to the aqueous phase.

[0266] The content of the further crosslinker is in the range of 0.1 to 5 wt.%, preferably in the range of 0.15 to 2.5 wt.%, based on the total weight of the non-aqueous phase. Most preferably, the crosslinker is used in the internal non-aqueous phase in the range of 0.1 to 1 wt.%, based on the total weight of the non-aqueous phase.

[0267] The further crosslinking agent may be added neat to the emulsion or dispersion, for example as a solid, or in the form of an aqueous solution.

[0268] Even more preferably, the further crosslinking in process step (vii) is carried out by stepwise heating the emulsion or dispersion to a temperature in the range of from 20° C. to 50° C., preferably from 30° C. to 40° C. The further crosslinking in the process according to the invention is carried out for a period of from about 20 minutes to 10 hours, preferably from 30 minutes to 8 hours.

[0269] To optimize the first cross-linking in process step (v) and / or the further cross-linking in process step (vii) of the process according to the invention, the pH value of the emulsion or dispersion is optionally adjusted to a pH value above or below the isoelectric point of the protein used, below which the protein has a positive net charge and above which the protein has a negative net charge.

[0270] Preferably, the pH is adjusted to a range of pH 2.0 to pH 4.0, even more preferably to a range of pH 2.5 to pH 3.5, and most preferably to a range of pH 2.9 to pH 3.3 to obtain a positively charged protein. To obtain a negatively charged protein, the pH is preferably adjusted to a range of pH 8.0 to pH 12.0, even more preferably to a range of pH 9.0 to pH 10.0, and most preferably to a range of pH 9.3 to 9.6.

[0271] For this purpose, an organic acid, such as formic acid or acetic acid, or a base, such as caustic soda, is added to the emulsion or dispersion to set a pH value in the ranges mentioned above.

[0272] Carrying out the first and / or further crosslinking at pH values ​​above or below the isoelectric point has the advantage that the charge of the proteins is altered so that electrostatic interactions can have a positive effect on capsule formation. In addition, such modifications of proteins have a positive effect on their emulsifying ability.

[0273] During the first crosslinking step and any further crosslinking steps, the stirring power is reduced, for example to a stirring speed of around 800-1400 rpm, to prevent the microcapsules from breaking again immediately.

[0274] An important criterion for the usefulness of microcapsules is the weight ratio of core material to capsule wall material: on the one hand, the aim of the core material is to achieve the highest possible ratio in order to maximize the usefulness of the capsule, but on the other hand, it is necessary that the capsule has a sufficient ratio of capsule wall material to ensure capsule stability.

[0275] According to the invention, it has proven to be particularly advantageous to design the microcapsules in such a way that they have a weight ratio of core material to capsule wall material of 50:50 to 98:2, preferably 80:20 to 97.5:2.5.

[0276] After completing the curing, the microcapsules produced by the process of the present invention are available as a dispersion in water, also known as a microcapsule dispersion or microcapsule slurry, in which form the microcapsules are essentially ready for sale.

[0277] In order to prevent such a suspension from separating or from becoming creamy and thus to achieve a high storage stability, it has proven advantageous for the suspension to have a viscosity of 12 to 2000 mPas. In order to obtain the desired viscosity of the suspension, a thickening agent is preferably used.

[0278] Xanthan gum, diutan gum, carboxymethylcellulose (CMC), microcrystalline cellulose (MCC) or guar gum are preferably used as thickening agents.

[0279] To improve shelf life, one or more preservatives can optionally be added to the microcapsule slurry or the microcapsule slurry can be dried.

[0280] Preservatives preferably used are 1,2-hexanediol, 1,2-octanediol, phenoxyethanol-based products, products derived from a mixture of 1,2-benzisothiazolin-3-one (2.5%) and 2-methyl-4-isothiazolin-3-one (2.5%), benzyl benzoate, etc.

[0281] Alternatively, for storage purposes, the microcapsule slurry is preferably dried.

[0282] The microcapsule slurry can be dried using processes such as freeze-drying, but is preferably spray-dried, for example in a fluidized bed. It has been found to be advantageous to add to the suspension an additional polysaccharide, preferably a dextrin, in particular a maltodextrin, at a temperature of about 20 to about 50° C., preferably about 40° C., which aids in the drying process and protects the capsules during this process. The amount of polysaccharide used can be about 50 to about 150% by weight, preferably about 80 to about 120% by weight, based on the capsule mass in the dispersion.

[0283] The spray drying itself can be carried out in a conventional spray system either continuously or batchwise, with the inlet temperature being about 170 to about 200°C, preferably about 180 to 185°C, and the outlet temperature being about 70 to about 80°C, preferably about 72 to 78°C.

[0284] The catalyzed cross-linking of polysaccharides and / or proteins by the cross-linking agent and optionally further cross-linking agents introduces large molecules into the network of the capsule shell, which increases the proportion of natural components in the capsule shell or microcapsules, and thus enhances the biodegradability of the capsule shell, as illustrated in the examples of the embodiments below.

[0285] The process according to the invention is further characterized by the fact that vegetable proteins, polysaccharides and aliphatic polyisocyanate(s) are polymerized and / or crosslinked as main components, thus allowing the production of very stable vegan microcapsules with excellent organoleptic properties based on biocompatible polymers. Another particularly advantageous feature of the process according to the invention is that the polyisocyanates no longer act as the main material of the vegetable protein-based microcapsules according to the invention, but instead mainly serve as crosslinkers for the amino acids and the other abovementioned components. The reduction in the amount of polyisocyanates used is characterized as a further advantage of the process according to the invention.

[0286] The process according to the invention allows replacing part of the polyisocyanate with biodegradable wall materials such as proteins and / or polysaccharides, thereby allowing the polyisocyanate content to be reduced without losing or reducing the functionality of the microcapsules, e.g. olfactory properties and beneficial secondary properties, e.g. high stability, i.e. the ability to retain active ingredients. Thus, using the process according to the invention, microcapsules can be produced which on the one hand have excellent functionality and at the same time are readily biodegradable.

[0287] In order to obtain vegetable protein-based microcapsules having excellent stability properties, which also have excellent organoleptic properties and which further make it possible to reduce the amount of aliphatic polyisocyanates, it may be proposed in a highly preferred embodiment of the process according to the invention that the polysaccharide or the at least one further polysaccharide is hyaluronic acid or that the polyhydroxyphenol is a tannin.

[0288] The polysaccharide may here be a first polysaccharide according to step (ii). Alternatively or additionally, the polysaccharide may be a further polysaccharide according to step (iv) and / or step (vi).

[0289] Surprisingly, it has been found that it can be particularly advantageous if the amount of hyaluronic acid relative to the amount of wall-forming material is 1-15% by weight, preferably 2-13% by weight, particularly preferably 2.5-6% by weight.

[0290] It is particularly preferred that the hyaluronic acid be added after the emulsion is formed.

[0291] In particular, the content of hyaluronic acid is in the range of 0.1 to 5 wt. %, preferably in the range of 0.15 to 2.5 wt. %, particularly preferably in the range of 0.2 to 1.0 wt. %, based on the total weight of the non-aqueous internal phase, and / or in the range of 0.1 to 5 wt. %, preferably in the range of 0.15 to 2.5 wt. %, particularly preferably in the range of 0.25 to 1.0 wt. %, based on the total weight of the aqueous external phase.

[0292] On the one hand, this can reduce the amount of aliphatic polyisocyanates used for crosslinking, which can have a positive impact on the environment. On the other hand, a reduction in the amount of polyisocyanates can have a positive effect on the biodegradability of the plant protein-based microcapsules. Another advantage is that neither the stability nor the sensory properties of the microcapsules are adversely affected.

[0293] In a further preferred embodiment of the process according to the invention, in addition to the addition of hyaluronic acid, it may be proposed to add at least one catalyst after the emulsion has been formed.

[0294] This makes it possible to obtain particularly stable plant protein-based microcapsules with very good organoleptic properties (odour or aroma release) in a total reaction time of less than 7 hours.

[0295] In a second aspect, the present invention relates to plant protein-based microcapsules prepared according to the method of the present invention or the corresponding microcapsule slurry.

[0296] The plant protein-based microcapsules according to the present invention are (a) a core comprising or consisting of at least one hydrophobic active ingredient; (b) characterized in that it comprises or consists of at least one plant protein and at least one aliphatic polyisocyanate as crosslinker and optionally at least one polysaccharide, as well as optionally at least one protective colloid and / or a capsule shell which comprises or consists of a crosslinked matrix or crosslinking units of optionally at least one further crosslinker.

[0297] The microcapsules of the present invention comprise a core surrounded or enveloped by a capsule shell or capsule wall. Any material suitable for inclusion in a microcapsule can be used as the core material for producing the microcapsules of the present invention. The material to be encapsulated is preferably a hydrophobic, water-insoluble, or water-immiscible liquid or solid as well as a suspension.

[0298] In the context of the present description, the core material is a hydrophobic active ingredient, i.e. a substance that has a particular effect or causes a particular reaction, such as drugs, plant protection agents, cosmetic active ingredients, food active ingredients, etc., as described above. The term "hydrophobic active ingredient" means that the active ingredient that is encapsulated during the preparation of the microcapsules is in an internal non-aqueous phase and is not miscible with the external aqueous phase.

[0299] Polymerization and / or crosslinking of functional groups of plant proteins and / or polysaccharides with polyisocyanates results in an alternating and dense, and therefore stable, crosslinked matrix or stable capsule walls of crosslinked units based on soluble or insoluble complexes of proteins and polysaccharides, as well as polyureas and polyurethanes.

[0300] In a preferred embodiment, the capsule shell comprises or consists of a cross-linked matrix or cross-linking unit comprising polymerization and / or cross-linking of at least one plant protein with a first cross-linking agent and optionally further cross-linking agents, and / or a cross-linked matrix or cross-linking unit comprising polymerization and / or cross-linking of at least one polysaccharide with a first cross-linking agent and optionally further cross-linking agents.

[0301] The crosslinked matrix or crosslinked units resulting from the polymerization and / or crosslinking of at least one plant protein with a first crosslinker and optionally further crosslinkers are primarily polyurea-based networks, and the crosslinked matrix or crosslinked units resulting from the polymerization and / or crosslinking of at least one polysaccharide with a first crosslinker and optionally further crosslinkers are primarily polyurethane-based networks as well as soluble or insoluble complexes of proteins and polysaccharides.

[0302] In addition to the polyurea formation and / or polyurethane formation described above, due to the reactivity of polyisocyanates as described in M.F. Sonnenschein, Introduction to Polyurethane Chemistry, Polyurethanes: Science, Technology, Markets, and Trends, First Ediiton, 2015, John Wiley & Sons, pages 105-126, the disclosure of which is incorporated herein by reference in its entirety, the crosslinking process described above produces by-products such as, for example, ureas, allophanates, biurets, uretidione, carbodiimides, uretonimines, etc. These by-products are part of the capsule shell or capsule wall.

[0303] The structure of the capsule wall, based on several individual defined and alternating crosslinked matrices or crosslinking units, makes it possible to produce particularly stable microcapsules with excellent organoleptic properties while at the same time significantly reducing the number of shell components.

[0304] In addition to the main components listed above, the capsule shell may optionally contain a protective colloid and / or an optional further cross-linking agent.

[0305] It is particularly advantageous if the plant protein-based microcapsules contain hyaluronic acid.Surprisingly, it has been found that this can significantly improve the stability properties of the plant protein-based microcapsules.In addition, such plant protein-based microcapsules surprisingly show improved sensory properties.It has also been found that the amount of polyisocyanate used in the manufacture of these plant protein-based microcapsules containing hyaluronic acid can be reduced.

[0306] In a preferred variant of the second aspect, the microcapsules according to the invention are in the form of a dispersion or slurry in which the microcapsules are dispersed in an external aqueous phase, the weight proportion of the microcapsules in the dispersion or slurry being about 20-60% by weight, in particular about 25-55% by weight, more preferably about 33-50% by weight.

[0307] Surprisingly, the vegetable protein based microcapsules produced according to the method of the present invention have a stability comparable to that of prior art microcapsules and have an equivalent content of unintentional leakage of perfume oils, despite a reduced polyisocyanate content in the microcapsule wall.

[0308] Due to the excellent stability and excellent release capacity of the microcapsules as well as the possibility of encapsulating a wide spectrum of hydrophobic active ingredients by the microcapsules according to the invention, the plant protein-based microcapsules according to the invention can be used in a wide range of applications for perfuming and flavoring.

[0309] Furthermore, the microcapsules according to the invention are universal capsules with no restrictions on individual active ingredients since they can be used to encapsulate a wide spectrum of fragrances or flavours, even fragrances or flavours with aldehyde, carboxylic acid or ester functionality.

[0310] Due to their advantageous properties, in particular their stability and targeted release of the active ingredients, the plant protein based microcapsules according to the invention are suitable for a wide range of applications, and in particular for use in household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters, scent lotions and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceuticals or printing coatings for paper, etc.

[0311] The present invention therefore relates in a further aspect to the use of the plant protein based microcapsules according to the invention or a dispersion of the plant protein based microcapsules according to the invention (microcapsule slurry) for producing household products, fabric care products, detergents, fabric softeners, cleaning agents, scent boosters in liquid or solid form, scent lotions and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceuticals or printing coatings for paper. The microcapsules according to the invention are particularly suitable for the encapsulation of hydrophobic perfumes or flavorings which can be used in various household and fabric care products.

[0312] Finally, the present invention relates to household products, textile care products, laundry detergents, fabric softeners, cleaning products, scent boosters, scented lotions and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceuticals or printing coatings for paper, etc., comprising the plant protein based microcapsules according to the present invention or a dispersion of the plant protein based microcapsules according to the present invention.

[0313] The proportion of microcapsules in the above-mentioned products is between 0.05 and 15% by weight, preferably between 0.2 and 5% by weight, based on the total weight of the product.

[0314] The present invention further relates to a microcapsule slurry comprising the microcapsules according to the invention in combination with a thickening agent and / or a preservative. EXAMPLES

[0315] The plant protein-based microcapsules according to the invention and their advantageous properties are explained in more detail with reference to the following examples.

[0316] The following stability data refers to testing at 40° C. in commercial formulations such as fragrance boosters or fabric softeners.

[0317] Vegan microcapsules according to the invention have been produced using different plant proteins, namely pea protein, hemp protein, soy protein, sunflower protein and pumpkin protein, the production with pea protein being described below as an example.

[0318] The pea protein can be Pea protein Nutralys® F858F (Roquette). The soy protein may or may not be Soya Protein Isolate SolPro 921 (Solbar Ningbo Technology Co., Ltd.). The hemp protein may or may not be Hemp Protein 50 (All Organic Treasures GmbH). The pumpkin protein may or may not be Pumpkin Protein 60 (All Organic Treasures GmbH).

[0319] The non-aqueous internal phase contained a polyisocyanate mixture consisting of TAKENATE™ D-120N, STABIO D370N and Desmodur N 3400. The three polyisocyanates were used in equal proportions. In addition to pea protein, the aqueous external phase contained tannin, CMC and glycerol (86.5% in water). The pH of the aqueous external phase was adjusted to 3.3 using formic acid. After formation of the emulsion, hyaluronic acid, maltodextrin and DABCO were added. The final step involved curing at 70° C. for 3 hours.

[0320] Particularly stable microcapsules can be obtained by curing at a temperature between 70° C. and 80° C. for 2 to 4 hours.

[0321] In particular, a curing time of 2 hours at 80° C. may be expected to obtain particularly stable microcapsules with very good organoleptic properties.

[0322] The amount of free oil was measured in isopropanol, i.e. a defined amount of microcapsule slurry was mixed with isopropanol, stirred for 30 seconds and a sample was taken. The sample taken was measured using GC-MS. The result indicates how much of the encapsulated oil was transferred to the isopropanol or how much oil was not fully encapsulated. The free oil content therefore provides an indication of whether the process itself is working, i.e. whether the perfume oil is fully encapsulated and / or whether the capsule shell is stable enough to prevent the perfume oil from bleeding into the isopropanol. A value below 1% is considered an indication of successful encapsulation and a stable capsule shell.

[0323] Example 1: In-use stability of plant protein-based microcapsules according to the invention

[0324] The stability of the microcapsules according to the invention and of prior art microcapsules produced as described above or similarly was determined in the target application. Stability tests were carried out using each fabric softener incorporating the microcapsule slurry in an amount of 1% by weight in each case and stored at room temperature and at 40°C. Samples were taken at defined intervals and the stability was determined. The identity of the perfume ingredients was based on an in-house database and on an analytical database of commercial perfume formulations. This gives the percentage of perfume oil remaining in the capsule. A result of 98% means, for example, that 2% of the amount of perfume oil originally used is no longer in the capsule.

[0325] In the tables and figures below, the common abbreviations "d" for "days" and "w" for "weeks" are used.

[0326] Table 1 below shows that the vegetable protein-based microcapsules according to the present invention made using only aliphatic polyisocyanates as crosslinkers have significantly better stability than vegetable protein-based microcapsules using aromatic and aliphatic polyisocyanates.

[0327] [Table 1]

[0328] The results according to Table 1 are also shown in FIG.

[0329] In addition, it can be seen from the stability data and comparisons shown in Table 1 that, without exception, all the plant proteins used, namely pea protein, sunflower protein, pumpkin protein and hemp protein, result in plant protein-based microcapsules with very good stability properties. This is not the case when animal proteins are used, as can be shown using the example of gelatin. When exclusively aliphatic polyisocyanates are used, the stability of the gelatin-containing microcapsules is reduced compared to the microcapsules according to the present invention.

[0330] [Table 2]

[0331] In Table 2 above, "Polyisocyanate 1" is TAKENATE™ D-120N; "Polyisocyanate 2" is STABIO D370N; "Polyisocyanate 3" is Desmodur N 3400 and "Polyisocyanate 4" is 100741 Desmodur 44 M Flakes. As is known, the latter is an aromatic polyisocyanate. The indicated stabilities are all based on pea proteins obtained as described above.

[0332] From the data in Table 2, it can be inferred that when only one and exclusively aromatic polyisocyanate is used as crosslinker (Polyisocyanate 4), the vegetable protein-based microcapsules have extremely poor stability. In contrast, a significantly improved stability of the vegetable protein-based microcapsules according to the invention can be achieved when using an aliphatic polyisocyanate (Polyisocyanate 2 or Polyisocyanate 3). Surprisingly, the best results in terms of stability can be achieved when using an alicyclic polyisocyanate (Polyisocyanate 1) as crosslinker for the production of vegetable protein-based microcapsules. This is especially true for long-term stability, i.e. stability over 4 weeks.

[0333] Further investigations were carried out on the stability of the plant protein-based microcapsules according to the invention with respect to the use of polyisocyanate mixtures as crosslinkers, the data and results of which are shown in Table 3 below. As in the above description, "Polyisocyanate 1" designated in Table 3 is TAKENATE™ D-120N. "Polyisocyanate 2" is STABIO D370N. "Polyisocyanate 3" is Desmodur N 3400 and "Polyisocyanate 4" is 100741 Desmodur 44 M Flakes. All stability shown is for pea protein-based microcapsules.

[0334] [Table 3]

[0335] Surprisingly, in the context of the present invention, it has been found that it is also possible to obtain very good stability of the plant protein-based microcapsules according to the invention when using only aliphatic isocyanates (as shown above in Table 2). As soon as aromatic isocyanates are used proportionally or even partially, the stability decreases accordingly. Therefore, it is essential to the present invention to use at least one aliphatic polyisocyanate as crosslinker in step (i), and in particular not to use aromatic polyisocyanates.

[0336] Furthermore, it has surprisingly been found that a particularly good stability of the plant protein-based microcapsules according to the invention is obtained when two aliphatic isocyanates are used, in particular a cycloaliphatic (Polyisocyanate 1) and an aliphatic (Polyisocyanate 2 or Polyisocyanate 3) polyisocyanate.

[0337] Due to the fact that the sensory performance, i.e. the release of perfume or odorant, is not very good with polyisocyanate 1, very good sensory properties and at the same time very good stability can be achieved when using two or more polyisocyanates as crosslinkers, one of which is a cycloaliphatic polyisocyanate and one of which is an aliphatic polyisocyanate. Therefore, taking into account the two factors of stability and sensory properties, the use of two or more polyisocyanates as crosslinkers is preferred in the production of vegetable protein-based microcapsules. A further advantage of using two or more polyisocyanates as crosslinkers compared to only one aliphatic crosslinker is that the vegetable protein-based microcapsules thus produced according to the present invention are more biodegradable and require less polyisocyanate overall.

[0338] As shown in Table 4 below, the use of three polyisocyanates can also result in highly stable vegetable protein-based microcapsules in accordance with the present invention.

[0339] When using mixtures of three polyisocyanates, particularly good stability is achieved if at least one cycloaliphatic polyisocyanate is used, while for improved organoleptic properties and biodegradability at least one aliphatic polyisocyanate is present.

[0340] With a ratio of three polyisocyanates of 60:20:20 as shown in Table 4, improved organoleptic properties and improved biodegradability can be obtained, particularly if equal amounts of cycloaliphatic and aliphatic polyisocyanates are used, and an additional aliphatic polyisocyanate is used in an amount three times that of the cycloaliphatic polyisocyanate (hence the 20:60:20 ratio, seen in the last column of Table 4).

[0341] Within the scope of the present invention, the molar ratios given herein may be replaced by quantity ratios and vice versa.

[0342] Surprisingly, very good results are achieved in terms of stability and organoleptic properties when using equal proportions of the three polyisocyanates based on the amounts of each.

[0343] [Table 4]

[0344] As in the above description, "Polyisocyanate 1" designated in Table 4 is TAKENATE™ D-120N. "Polyisocyanate 2" is STABIO D370N. "Polyisocyanate 3" is Desmodur N 3400 and "Polyisocyanate 4" is 100741 Desmodur 44 M Flakes. All stabilities given are for pea protein based microcapsules.

[0345] The developers have also found that the addition of other substances can have a positive effect on the stability of the plant protein-based microcapsules according to the invention. Surprisingly, it has been found that the addition of hyaluronic acid, especially the addition of hyaluronic acid after the emulsification step, has a significant positive effect on the stability of the produced microcapsules, as shown in Table 5 below. In Table 5, the percentage of isocyanate refers to the total amount of wall-forming material of the plant protein-based microcapsules.

[0346] [Table 5]

[0347] Therefore, the addition of hyaluronic acid has a positive effect on stability, and significantly less polyisocyanate is required as crosslinking agent.Therefore, the use of hyaluronic acid in the process according to the present invention for the preparation of plant protein-based microcapsules is also advantageous in that the resulting microcapsules have improved biodegradability.In addition, the use of hyaluronic acid improves sensory properties.

[0348] The results according to Table 5 are also shown in FIG.

[0349] The results of further tests on the stability behaviour of the plant protein-based microcapsules according to the invention are shown in Table 6.

[0350] [Table 6]

[0351] The results according to Table 6 are also shown in FIG.

[0352] Surprisingly, it has been found that the further addition of glycerol to pea protein-based microcapsules already containing hyaluronic acid has a positive effect on the stability of the microcapsules according to the invention. A particular advantage of the addition of both glycerol and hyaluronic acid is that the amount of polyisocyanate can be reduced. The reduced amount of isocyanate (crosslinker) improves biodegradability.

[0353] Regarding the plant proteins used, in the context of the present invention, pea protein, sunflower protein, hemp protein and pumpkin protein are particularly preferred in terms of the stability of the microcapsules obtained in each case.Compared to other plant proteins, a correspondingly good stability was achieved for these four preferred plant proteins.High stability was also achieved for soybean protein and broad bean protein, as can be seen from Table 7 and Figure 4 below.

[0354] [Table 7]

[0355] Example 2: Sensory evaluation of plant protein-based microcapsules according to the invention

[0356] The sensory evaluation was carried out as follows: The microcapsules mentioned above were each incorporated into a fabric softener at a slurry concentration of 0.4% by weight (perfume Tomcap) and then washed. The capsule loading of 17.5% perfume oil (+17.5% vegetable oil = 35% total loading) and the dosage of 0.4% capsule slurry resulted in a dosage of pure perfume oil of 0.07% perfume oil in the comparative fabric softener. 30 g of fabric softener was used for 2 kg of laundry containing terry towels. The washing instructions were as follows: The laundry items containing terry towels (cotton towels) were placed in the washing machine and the fabric softener was placed in the fabric softener compartment. The washing program "Express20; 900 rpm" was started. The terry towels were then left to dry overnight at room temperature.

[0357] Sixteen test subjects rated the odor intensity of terry towels after washing on a scale from 1 (no odor) to 9 (very strong odor) by examining the towels in pairs against the corresponding level of free perfume oil in the fabric softener.

[0358] The perfume was released in three phases. The first phase describes the odor of the untreated fabric. The second phase describes the odor of the lightly kneaded fabric; for this purpose, the fabric was subjected to a slight mechanical stress by moving it back and forth between the hands several times, so that the capsules broke. The third phase describes the odor after the capsules had broken by vigorously rubbing the fabric. The fragrance intensity was evaluated after each phase.

[0359] The results of the sensory evaluation are shown in Table 8.

[0360] It should be noted that in general the preferably used plant proteins, such as pea protein, pumpkin protein, sunflower protein and hemp protein, respectively, allow the provision of plant protein-based microcapsules according to the invention, always achieving good organoleptic properties (see also FIG. 3), which according to the central idea of ​​the invention are even better when aliphatic polyisocyanates are used as crosslinking agents (see rows 2 and 8 of Table 8).

[0361] [Table 8]

[0362] The results according to Table 8 are also shown in FIG.

[0363] According to the above, it has been surprisingly found that the addition of hyaluronic acid to the preparation of plant protein-based microcapsules according to the invention using at least one aliphatic polyisocyanate as crosslinker has a positive effect on the sensory properties.It is particularly surprising to note that good sensory properties can be achieved by adding hyaluronic acid and at the same time the amount of isocyanate can be reduced (see lines 5 and 6 of Table 9 below).The biodegradability can thus be improved by reducing the amount of polyisocyanate.

[0364] [Table 9]

[0365] The results according to Table 9 are also shown in FIG.

[0366] This was surprisingly found in conjunction with the addition of glycerol and hyaluronic acid (see Table 10, lines 8 and 9).

[0367] According to the above, it has been surprisingly found that the addition of hyaluronic acid and glycerol to the preparation of plant protein-based microcapsules according to the invention using at least one aliphatic polyisocyanate as crosslinker has a positive effect on the sensory properties. It is particularly surprising to note that good sensory properties can be achieved by adding hyaluronic acid and glycerol and at the same time the amount of isocyanate can be reduced (see lines 8 and 9 of Table 10 below). Such reduction of polyisocyanate can improve biodegradability.

[0368] The results according to Table 10 are also shown in FIG.

[0369] [Table 10]

[0370] Example 3: Further results on the stability of plant protein-based microcapsules according to the invention during use and further sensory evaluation of plant protein-based microcapsules according to the invention

[0371] However, plant protein based microcapsules with very good stability properties and very good organoleptic properties are not limited to pea protein. Rather, surprisingly, microcapsules made using soybean protein, hemp protein or pumpkin protein instead of pea protein also have very good organoleptic properties and very good stability properties, which may even exceed the stability, as can be seen from Tables 11 and 12 below.

[0372] [Table 11]

[0373] The results according to Table 11 are also shown in FIG.

[0374] However, plant protein based microcapsules with very good stability properties and very good sensory properties are not limited to pea protein. Rather, surprisingly, microcapsules made using soybean protein, hemp protein or pumpkin protein instead of pea protein also have very good sensory properties and very good stability properties, which may even exceed the stability properties, as can be seen from Tables 11 and 12 below.

[0375] [Table 12]

[0376] The results according to Table 12 are also shown in FIG.

[0377] Surprisingly, it has been found that if the at least one first polysaccharide and / or the at least one further polysaccharide is selected from the group consisting of hyaluronic acid, carrageenan, gellan gum, agar, alginate, xanthan gum, microcapsules with particularly good organoleptic properties can be obtained, as can be seen in the table below.

[0378] [Table 13]

[0379] The results according to Table 13 are also shown in FIG.

Claims

1. A process for preparing plant protein-based microcapsules, comprising: the following steps: (i) providing an internal non-aqueous phase comprising at least one aliphatic polyisocyanate as a crosslinking agent, at least one hydrophobic active ingredient, and optionally at least one further crosslinking agent; (ii) providing an external aqueous phase comprising at least one plant protein, preferably hemp protein, pumpkin protein, soybean protein, sunflower protein, pea protein, and optionally at least one first polysaccharide and / or at least one further crosslinking agent and / or at least one polyhydroxy phenol and / or at least one protective colloid, and further optionally adjusting the pH of the aqueous phase to a pH lower than the isoelectric point of the plant protein; (iii) emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase in the presence of optionally at least one stabilizer and / or at least one emulsifier to obtain an oil-in-water emulsion or an oil-in-water dispersion system; (iv) optionally adding at least one further polysaccharide and / or at least one further plant protein; (v) performing a first crosslinking to obtain a microcapsule slurry; (vi) curing the microcapsule slurry at a temperature of at least 60°C and optionally adding at least one further polysaccharide and / or at least one further plant protein; (vii) cooling and further crosslinking by optionally adding at least one further crosslinking agent; (viii) optionally separating the microcapsules from the microcapsule slurry and drying the microcapsules as required, or adjusting the viscosity of the microcapsule slurry by adding at least one thickening agent; The process as described above, including these steps in this order.

2. The process according to claim 1, wherein at least one of the aliphatic polyisocyanates or one of the aliphatic polyisocyanates is an alicyclic polyisocyanate having two or more isocyanate groups.

3. ​ The total amount of polyisocyanate is 10 to 70% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 35% by weight, based on the amount of the wall-forming material, and the total amount of polyisocyanate used together as a crosslinking agent is 0.5% to 4%, preferably 1% to 3%, particularly preferably 1.5% to 2.5%, based on the total amount of the hydrophobic active ingredient, preferably a fragrance or odorant, particularly used in the core of the capsule, of the process according to claim 1.

4. The process according to claim 1, wherein the polysaccharide or the at least one further polysaccharide is hyaluronic acid and the polyhydroxyphenol is tannin.

5. The process according to claim 4, wherein the amount of hyaluronic acid relative to the amount of the wall-forming material is 1 to 15% by weight, preferably 2 to 13% by weight, particularly preferably 2.5 to 6% by weight.

6. The process according to claim 1, wherein an internal non-aqueous phase containing an aliphatic polyisocyanate as a crosslinking agent and an alicyclic polyisocyanate as a crosslinking agent is provided in step (i), and the aliphatic polyisocyanate and the alicyclic polyisocyanate are each used in a molar ratio of 85:15 to 15:

85.

7. The process according to claim 1, wherein an internal non-aqueous phase containing two different aliphatic polyisocyanates as crosslinking agents is provided in step (i), and the two aliphatic polyisocyanates are each used in a molar ratio of 85:15 to 15:

85.

8. The process according to claim 1, wherein an internal non-aqueous phase containing three crosslinking agents is provided in step (i), the three crosslinking agents are different aliphatic or alicyclic polyisocyanates, preferably at least one alicyclic polyisocyanate and at least one aliphatic polyisocyanate are present, and the three polyisocyanates are each used in an amount of 20% to 60% based on the total amount of the three polyisocyanates.

9. In step (i), at least one additional crosslinking agent and / or in step (ii) and / or in step (vii), an additional crosslinking agent is added, and the at least one additional crosslinking agent and / or the additional crosslinking agent is selected from the group consisting of transglutaminase, peroxidase; polyphenols, polyhydroxy phenols, especially tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, secondary plant substances; and mixtures of two or more of the aforementioned crosslinking agents, the process according to claim 1.

10. The at least one hydrophobic active ingredient is selected from the group consisting of a fragrance or odorant, a flavoring agent, a cooling agent, a TRPV1 or TRPV3 modulator, a substance that causes a sharp taste, a warm or hot sensation on the skin or mucous membranes, or a foaming or tingling sensation in the mouth or throat, or an active ingredient having a pungent, bitter or astringent effect, a pest control agent, a biocide, an insecticide, a water repellent, a food additive, a cosmetic active substance, a pharmaceutical active substance, a pesticide, a dye, a colorant, a dye precursor, a luminous paint, a fluorescent whitening agent, a solvent, a wax, a silicone oil, a lubricant, a printing coating agent for paper, and mixtures of two or more of the aforementioned active ingredients, the process according to claim 1.

11. The at least one first polysaccharide and / or the at least one additional polysaccharide is • indigestible fibers and dietary fibers, especially insoluble dietary fibers, especially cellulose, hydroxyethyl cellulose, especially quaternized hydroxyethyl cellulose, carboxymethyl cellulose (CMC) and microcrystalline cellulose (MCC), cellulose derivatives such as hemicellulose, lichenin, chitin, chitosan, lignin, xanthan gum, vegetable fibers, especially cereal fibers, potato fibers, apple fibers, citrus fibers, bamboo fibers, extracted sugar beet fibers; oat fibers and soluble dietary fibers, especially inulin, especially native inulin, highly soluble inulin, granular inulin, high-performance inulin, pectin, alginate, agar, tragacanth, carrageenan, gum arabic, konjac gum, glucan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, polydextrose and lactulose; - Starch, especially starch from wheat, potato, corn, rice, tapioca and oats, starch modified chemically, mechanically and / or enzymatically; and starch derivatives, such as dextrin or maltodextrin, especially dextrin and maltodextrin from wheat, potato, corn, rice and oats, especially maltodextrin DE8 - 10, DE17 - 20, DE18 - 20, cyclodextrin, oligosaccharides, especially oligofructose; and - Sugar alcohols, especially sorbitol, mannitol, isomalt, maltitol, maltitol syrup, lactitol, xylitol, erythritol; - Gellan; glucose, - Glycosaminoglycans, especially hyaluronic acid The process according to claim 1, selected from the group consisting of mixtures of the aforementioned polysaccharides.

12. The at least one plant protein or the at least one further plant protein is especially a protein from the group consisting of cereals, especially wheat, barley, rye, spelt wheat, gluten, especially wheat gluten, rapeseed, rice, potato, corn, soybean, bean, chickpea, lentil, lupin bean, peanut, alfalfa, broad bean, pea, hemp, pumpkin and sunflower, especially a protein isolate produced by a physicochemical process or fermentation or enzymatic treatment of a plant protein, a plant protein in the form of a fraction, a partial or complete hydrolyzate or intermediate, an edible plant, chitosan and other proteins derived from mixtures thereof, the process according to claim 1.

13. The at least one protective colloid is - Diols, especially ethanediol, 1,2 - propanediol, 1,3 - propanediol, 1,2 - butanediol, isomeric butanediol, 1,2 - pentanediol, 1,2 - hexanediol, 1,2 - octanediol, 1,2 - decanediol, 1,2 - dodecanediol, and - Polyols, preferably triols, especially glycerol and its ethoxylated and propoxylated products, trimethylolpropane and its ethoxylated and propoxylated products, polyvinyl alcohol (PVOH) and its derivatives, especially ammonium-functionalized or sulfonated polyvinyl alcohol, polyphenols, preferably 1,3,5-trihydroxybenzene, polysaccharides, especially glucose, starch, or chemically, mechanically and / or enzymatically modified starch, hydroxyethyl cellulose, especially quaternized hydroxyethyl cellulose, and cellulose derivatives such as carboxymethyl cellulose, - Polyvinylpyrrolidone, vinyl maleate copolymer, sodium lignosulfonate, maleic anhydride / styrene copolymer, ethylene / maleic anhydride copolymer, ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitol copolymer, sodium dodecyl sulfate, - Vegetable polymers, especially gum arabic (Senegal type and Seyal type), proteins, olibanum resin, shellac, lignin, chitosan, saponin, selected from the group consisting of mixtures of the aforementioned compounds; and / or the process according to claim 1, wherein the protective colloid is used in combination with starch.

14. The first crosslinking is carried out by adding at least one catalyst in step (v) to obtain a microcapsule slurry; wherein the at least one catalyst is selected from the group consisting of diazabicyclo[2.2.2]octane (DABCO), bismuth catalysts and tin catalysts and mixtures of two or more of the aforementioned catalysts, the process according to claim 1.

15. In particular, the total amount of the crosslinking agent added as a polyisocyanate in step (i) is 0.5% to 4%, preferably 1% to 3%, particularly preferably 1.5% to 2.5% based on the total amount of the hydrophobic active ingredient used in step (i), especially a fragrance or odorant, the process according to claim 1.

16. Microcapsules or microcapsule slurries obtained by the process according to one or more of claims 1 to 15.

17. Plant protein-based microcapsules, (a) a core containing or consisting of at least one hydrophobic active ingredient, and (b) At least one plant protein, at least one aliphatic polyisocyanate as a crosslinking agent, and optionally at least one polysaccharide crosslinked matrix or crosslinked unit; optionally at least one protective colloid and / or optionally at least one additional crosslinking agent, or a capsule shell comprising or consisting of the same, the plant protein-based microcapsules.

18. The microcapsules according to claim 17, wherein the capsule shell comprises or consists of a crosslinked matrix or crosslinked unit of polymerization and / or crosslinking by a mixture of at least two different crosslinking agents of at least one plant protein and a crosslinked matrix or crosslinked unit of polymerization and / or crosslinking by a mixture of at least two different crosslinking agents of at least one polysaccharide.

19. The microcapsules according to claim 17, wherein the at least two crosslinking agents are different aliphatic or alicyclic polyisocyanates having two or more isocyanate groups.

20. The total amount of the polyisocyanate used together as a crosslinking agent is 0.5% to 4%, preferably 1% to 3%, particularly preferably 1.5% to 2.5%, based on the total amount of the hydrophobic active ingredient, preferably the fragrance or odorant, particularly used in the core of the capsule. The microcapsules according to claim 17.

21. The microcapsules according to claim 17, wherein the microcapsules contain hyaluronic acid.

22. Use of the microcapsules or microcapsule slurry according to claim 16, For the manufacture of household products, fabric care products, detergents, fabric softeners, cleaning agents, fragrance boosters or aroma enhancers in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals, or printing coatings for paper, said use of said microcapsules or microcapsule slurry.

23. Household products, fabric care products, laundry detergents, fabric softeners, cleaning agents, fragrance boosters and aroma enhancers, cosmetics, personal care products, perfume compositions, agricultural products, or pharmaceuticals comprising the microcapsules or microcapsule slurry according to claim 16.

24. Use of the microcapsules according to claim 17, Use of said microcapsules for the manufacture of household articles, textile care products, detergents, fabric softeners, cleaning agents, fragrance boosters or aroma enhancers in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals, or printing coatings for paper.

25. Household articles, textile care products, laundry detergents, fabric softeners, cleaning agents, fragrance boosters and aroma enhancers, cosmetics, personal care products, perfume compositions, agricultural products, or pharmaceuticals, comprising the microcapsules according to claim 17.

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