Method for preparing microcapsules

Abstract

The present invention relates to a method for preparing microcapsules, in particular vegetable protein-based microcapsules, comprising at least one hydrophobic active ingredient, and dispersions (microcapsule slurries) of such microcapsules, preferably vegetable protein-based microcapsules containing perfumes or flavours, which are more stable than the microcapsules of the prior art, and which are more stable than the microcapsules of the prior art, in particular more stable than the microcapsules of the prior art, in particular more stable than the microcapsules of the prior art, in particular more stable than the microcapsules of the prior art, in particular more stable than the microcapsules of the prior art. And balanced stability and performance are realized. In addition, the invention also relates to microcapsules based on vegetable proteins obtainable by the method according to the invention. In another aspect, the invention relates to the use of microcapsules and dispersions based on vegetable proteins according to the invention as components of household products, textile care products, detergents, fabric softeners, detergents, fragrance enhancers or flavors in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, and the like. The invention also relates to the use of the microcapsules and dispersions based on vegetable proteins according to the invention as components of household products, textile care products, detergents, fabric softeners, detergents, fragrance enhancers or flavors in liquid or solid form. A medical product or paper printing coating. Finally, the invention relates to consumer products comprising such microcapsules or microcapsule dispersions according to the invention.

Description

Technical Field

[0001] The present invention relates to a process for preparing microcapsules, in particular vegetable protein-based microcapsules, comprising at least one hydrophobic active ingredient, and dispersions of such microcapsules (microcapsule slurries), preferably vegetable protein-based microcapsules containing fragrances or aromas, which have a balanced stability and performance compared to the microcapsules of the prior art. In addition, the present invention also relates to vegetable protein-based microcapsules obtainable by the process according to the invention. In another aspect, the present invention relates to the use of vegetable protein-based microcapsules and dispersions according to the invention as components of household products, textile care products, detergents, fabric softeners, cleaning agents, fragrance enhancers or flavor enhancers in liquid or solid form, cosmetics, personal care products, fragrance compositions, agricultural products, pharmaceutical products or paper printing coatings. Finally, the present invention relates to consumer products comprising such microcapsules or microcapsule dispersions according to the invention. Background Art

[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, which is surrounded by a polymeric dense, permeable or semipermeable wall material. During the preparation process, the polymer from the starting components is deposited on the substance to be encapsulated after emulsification and coagulation or interfacial polymerization. The core is also called the inner phase. The wall also uses names such as outer phase, shell or coating. The diameter of the microcapsule usually varies in the range of 1 to 1000 μm. The wall thickness is usually 0.5 to 150 μm, but can be 5×10 -9 m to 5×10 -6 Typically, loadings of 25 to 95 wt % are possible, but loadings of 1 to 99 wt % are also possible.

[0003] Encapsulation of active substances with suitable wall materials (coating materials) can generally be done for several reasons:

[0004] -Conversion of liquids into a manageable powder form (e.g. coating of vegetable oils, fats);

[0005] - Time-controlled release of substances (dose control of drugs, pesticides and fertilizers, depot effect);

[0006] - Taste, odor and color masking (e.g. bitter or spicy flavorings);

[0007] - protection against light, oxidation, heat, acid or alkali (e.g. vitamins, seasonings, etc.);

[0008] - protection from moisture (e.g. hygroscopic salts or minerals);

[0009] - Delay the loss of volatile components (e.g. flavorings);

[0010] - prevent premature chemical reactions with other mixture components;

[0011] - Improved handling before or during processing (flow properties, dust formation);

[0012] - Protection of personnel from harmful or offensive substances (chemicals, fragrance concentrates); or improved solubility or suspension properties through surface modification.

[0013] Hydrophobic active ingredients, such as fragrances or flavorings or aromas or odoriferous substances, respectively, can be easily incorporated into a variety of different application formulations by encapsulation.

[0014] The contents of the microcapsules can generally be released in different ways and in particular based on one of the following mechanisms:

[0015] - Mechanical destruction of capsules by crushing or shearing. This mechanism is used, for example, for carbonless paper.

[0016] - Destruction of the capsule by melting of the wall material. According to this mechanism, ingredients such as leavening agents or flavorings in the baking mix are only released during the baking process.

[0017] - Destruction of the capsule by dissolution of the wall material. This mechanism is used, for example, in washing powders so that encapsulated ingredients such as enzymes are only released during the wash process.

[0018] -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.

[0019] Due to their diverse properties, microcapsules are used in many fields, including the printing industry, food industry (vitamins, flavors, plant extracts, enzymes, microorganisms), agrochemical industry (fertilizers, pesticides), animal feed industry (minerals, vitamins, enzymes, drugs, microorganisms), pharmaceutical industry, detergent industry and cosmetics industry.

[0020] Many daily necessities, such as detergents, fabric softeners, washing powders, liquid detergents, shower gels, shampoos, deodorants, polymer emulsions, etc., are nowadays perfumed with fragrances or odorants, respectively, or with mixtures of fragrances or odorants. Very often, fragrances or odorants interact with other ingredients in the formulation, or more volatile components of the fragrance evaporate prematurely. This often results in the fragrance impression of the fragrance changing over time, or even disappearing completely.

[0021] Microencapsulation of such mixtures of fragrances or odoriferous substances offers the possibility to reduce or completely prevent interactions or evaporation of highly volatile fragrance components in perfumed products.

[0022] A large number of capsule wall or coating materials are known for preparing microcapsules. The capsule wall can be composed of natural, semisynthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar, agarose, maltodextrin, alginic acid or its salts, for example sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides, for example starch or dextran, polypeptides, protein hydrolysates, sucrose and waxes. Semisynthetic capsule wall materials include chemically modified cellulose, in particular cellulose esters and cellulose ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and starch esters. Synthetic shell materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

[0023] Depending on the type of capsule wall material and the manufacturing process, the prepared microcapsules have different properties in terms of diameter, size distribution, and physical and / or chemical properties.

[0024] Polyurea microcapsules or polyurea / polyurethane microcapsules formed by polymerization between polyisocyanates and polyamines and / or diols or polyols are known capsules used in a large number of technical fields including the perfume industry.

[0025] Polyurea microcapsules obtained by reacting two polyisocyanates and polyamines are described, for example, in WO 2011 / 161229 or WO 2011 / 160733. According to WO 2011 / 161229 or WO 2011 / 160733, polyurea microcapsules are prepared in the presence of polyvinylpyrrolidone (PVP) as a protective colloid. WO 2012 / 107323 discloses polyurea microcapsules with a polyurea shell, which comprises a reaction product formed by polyisocyanates with guanazole (3,5-diamino)-1,2,4-triazole) and an amino acid in the presence of an anionic stabilizer or surfactant (e.g. anionic polyvinyl alcohol). EP 0537467B describes microcapsules prepared from polyisocyanates containing polyethylene oxide groups in the presence of a stabilizer such as polyvinyl alcohol. According to WO 2007 / 096592, microencapsulation can be carried out in an oil phase emulsified in a continuous aqueous phase, which is usually stabilized by a surfactant system (eg polyvinyl alcohol or its carboxylated and sulfonated derivatives).

[0026] The exemplary prior art delivery systems described above exhibit both good stability, i.e. the ability to retain the active ingredient and hence the ability of the capsule to avoid loss of volatile components, and good performance, e.g. release of the fragrance or odorant in the case of fragrance or odorant capsules.

[0027] However, the prior art microcapsules described above have the following disadvantages: In order to ensure adequate stability and to avoid excessive loss of active ingredients, the polymeric capsule wall or capsule shell material requires a large proportion of polymer. In addition, microencapsulation introduces plastics into the environment, which can cause problems such as "microplastics" there, which can lead to environmental damage or adverse health effects.

[0028] As plastic particles are increasingly becoming the subject of public criticism regarding their environmental impact, and as social pressure on the environment increases, the demand for bio-based and biodegradable solutions is also growing, so there is a need to develop new materials for microencapsulation in order to reduce microplastics in the environment. Here, the focus is on bio-based and biodegradable materials.

[0029] Against this background, there is therefore a need to provide microcapsules that are increasingly manufactured using biodegradable capsule wall materials, which also have outstanding stability and excellent release properties for various applications. It is important that not only the macromolecular material of the capsule wall itself is biocompatible, but also each fragment generated during the disintegration process is biocompatible. Furthermore, the aim is also to take into account consumer groups that wish to exclude animal-based ingredients in the final product.

[0030] However, in the case of microencapsulation, the task of reducing the amount of microplastics in the environment with the help of biodegradable materials is not trivial, since the desired functions (e.g. olfactory properties) and positive secondary properties of the microcapsules (e.g. high stability and toxicological harmlessness) conflict with the requirements of rapid biodegradability in many applications.

[0031] It is particularly difficult to prepare microcapsules that have both good stability and good drug release. The ability to retain the active ingredient and therefore the ability of the capsule to avoid loss of volatile components depends in particular on the stability of the capsule in the product matrix. However, in particular, capsules with good stability do not automatically have good biodegradability.

[0032] As the degree of crosslinking increases, the stability of the microcapsules increases, but at the same time the biodegradability of the capsule shell decreases. Very stable microcapsules have lower performance (e.g. organoleptic properties) because fewer microcapsules break and release the active ingredient due to pressure, friction, etc. If they are too unstable, they will be damaged during storage and will not work.

[0033] Recently, the demand for vegan products has also increased, which may be attributed in particular to the growing awareness of consumers. Veganism is a diet and lifestyle derived from vegetarianism, whereby it is well known that vegans avoid all foods of animal origin. Regarding veganism, corresponding arguments from the fields of animal ethics, environmental protection, world hunger, health and religion must also be considered. As veganism also expands to other areas of daily life and needs, the demand for vegan microcapsules covering the above-mentioned advantages and application areas increases. For the purposes of the present invention, vegan microcapsules can be understood and described as microcapsules based on plant proteins. They do not contain any animal components, in particular animal protein components. This can 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.

[0034] In particular, the present invention is to be understood and described in the following manner: microcapsules based on vegetable proteins, i.e. vegan microcapsules, do not contain any animal protein components or any other components of animal origin. Thus, the microcapsules based on vegetable proteins according to the invention consist exclusively of proteins or protein components of vegetable origin in terms of the proteins used. Animal proteins or protein components, such as gelatin, are explicitly excluded as far as the microcapsules according to the invention are concerned. This applies in the same way to the microcapsule slurry according to the invention.

[0035] The present invention is therefore based on the complex task of providing vegan, ie vegetable protein-based microcapsules which preferably meet one, several or preferably all of the following requirements:

[0036] - Improvement of biodegradability,

[0037] - No toxicity to humans and the environment;

[0038] - Maintain sufficient stability,

[0039] - adaptability to a wide variety of active ingredients to be encapsulated,

[0040] - excellent release behavior of the encapsulated active ingredients, and

[0041] - can be obtained by known methods for preparing microcapsules, and

[0042] - Components are readily available, i.e. can be prepared from bio-based or sustainably produced raw materials.

[0043] Surprisingly, it has been found that this task can be solved by preparing microcapsules based on vegetable proteins by interfacial polymerization of vegetable proteins and crosslinkers in aqueous emulsions. Crosslinking makes it possible to form very stable capsule shells or capsule walls, which can be used to encapsulate a wide range of hydrophobic or lipophilic active ingredients. It is essential that, in the first step of the method according to the invention, an internal non-aqueous phase is provided, which comprises at least one aliphatic polyisocyanate as crosslinker and at least one hydrophobic active ingredient. The use of at least one aliphatic polyisocyanate is essential for obtaining microcapsules based on vegetable proteins, which in particular have excellent stability and a significantly improved release behavior of one or more encapsulated active ingredients. Summary of the invention

[0044] This problem is solved by the subject matter of the independent claims. Preferred embodiments and further embodiments result from the wording of the dependent claims and the following description.

[0045] In a first aspect, the present invention therefore relates to a method for preparing microcapsules based on vegetable proteins, the method comprising the following steps carried out in sequence:

[0046] (i) providing an inner non-aqueous phase comprising at least one aliphatic polyisocyanate as crosslinking agent and at least one hydrophobic reactive ingredient and optionally at least one further crosslinking agent;

[0047] (ii) providing an external aqueous phase comprising at least one vegetable protein,

[0048] and optionally at least one first polysaccharide and / or at least one additional cross-linking agent and / or at least one polyhydroxyphenol and / or at least one protective colloid, and further optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the vegetable protein;

[0049] (iii) emulsifying or dispersing the inner non-aqueous phase in the outer aqueous phase to obtain an oil-in-water emulsion or dispersion, the emulsification or dispersing optionally being carried out in the presence of at least one stabilizer and / or at least one emulsifier;

[0050] (iv) optionally, adding at least one additional polysaccharide and / or at least one additional vegetable protein;

[0051] (v) performing a first crosslinking to obtain a microcapsule slurry;

[0052] (vi) curing the microcapsule slurry at a temperature of at least 60° C. and optionally adding additional polysaccharide and / or additional vegetable protein;

[0053] (vii) cooling and optionally further cross-linking by adding at least one additional cross-linking agent; and

[0054] (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 thickener.

[0055] In a second aspect, the present invention relates to microcapsules or microcapsule slurries prepared by the method according to the present invention.

[0056] The present invention also aims to provide a microcapsule based on vegetable protein, which comprises or consists of the following substances:

[0057] (a) a core comprising or consisting of at least one hydrophobic active ingredient;

[0058] (b) a capsule shell comprising or consisting of a crosslinking matrix or crosslinking units of at least one vegetable protein and 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.

[0059] Finally, in another aspect, the present invention relates to the use of the vegetable protein-based microcapsules according to the invention or dispersions comprising the vegetable protein-based microcapsules according to the invention for the manufacture of household products, textile care products, detergents, fabric softeners, cleaning agents, fragrance boosters, fragrance emulsions or fragrance enhancers in liquid or solid form, cosmetics, personal care products, fragrance compositions, agricultural products, pharmaceutical products or paper printing coatings.

[0060] Furthermore, the present invention encompasses household products, textile care products, detergents, fabric softeners, cleaning agents, fragrance boosters and flavor enhancers, cosmetics, personal care products, fragrance compositions, agricultural products or pharmaceutical products comprising the vegetable protein-based microcapsules according to the present invention or the corresponding slurries.

[0061] Surprisingly, it was found that during the preparation of the vegetable protein-based microcapsules according to the invention, the combination of vegetable proteins and subsequent crosslinking with aliphatic polyisocyanates leads to stable vegetable protein-based microcapsules, thus ensuring effective encapsulation of lipophilic active ingredients and subsequently ensuring targeted release of these active ingredients.

[0062] The vegetable protein-based and therefore vegan microcapsules according to the invention thus have excellent organoleptic properties in addition to excellent stability. In addition, since they have bio-based and biodegradable building blocks, biodegradability is possible. 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.

[0063] Thus, the polyisocyanate content of the capsule wall or capsule shell material can also be reduced, ie it can be replaced by biobased capsule wall components and thus the proportion of biobased capsule wall components can be increased without negatively affecting the very good stability properties of the microcapsule wall.

[0064] These and other aspects, features and advantages of the present invention will become apparent to those skilled in the art by studying the following detailed description and claims. Any feature or variation from one aspect of the present invention may be used or interchanged in another aspect of the present invention. In addition, it should be understood that the embodiments contained herein describe and illustrate the present invention, but are not intended to limit the present invention, and in particular, the present invention is not limited to these embodiments.

[0065] Unless otherwise indicated, all percentages are weight percentages, also referred to as wt%. Numerical examples given in the form of "from x to y" include the values. If multiple preferred numerical ranges are given in this format, it should be understood that all ranges generated by combinations of different endpoints are also included.

[0066] As used herein, the term "at least one" or "not less than one" or "one or more" means 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more.

[0067] The term "and / or" indicates that a combination exists or an alternative is provided. A person skilled in the art can independently determine which "and" or "or" combination is obviously feasible and reasonable, and which is not. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 is a graph showing the stability of some vegetable protein based microcapsules according to the invention in comparison with known microcapsules made of gelatin in fabric softeners with respect to various polyisocyanates used as crosslinking agents.

[0069] Figure 2 is a graph showing the sensory properties of the microcapsules according to the invention in a fabric softener for various polyisocyanates used as crosslinking agents.

[0070] Figure 3 is a graph showing the sensory properties of various vegetable protein-based microcapsules according to the present invention.

[0071] Figure 4 is a graph showing a further comparison of the stability of vegetable protein based microcapsules according to the invention in fabric softeners.

[0072] Figure 5is a graph showing a comparison of the stability of vegetable protein-based microcapsules according to the present invention in a fabric softener with respect to the amount of polyisocyanate used and the effect of hyaluronic acid.

[0073] Figure 6 is a graph showing the sensory evaluation of the microcapsules according to the present invention with respect to the amount of polyisocyanate used and the influence of hyaluronic acid.

[0074] Figure 7 is a graph showing a further comparison of the stability of the vegetable protein-based microcapsules according to the present invention with respect to the influence of the amount of polyisocyanate used and glycerol and the combination of glycerol and hyaluronic acid.

[0075] Figure 8 is a graph showing the sensory evaluation of the microcapsules according to the present invention with respect to the amount of polyisocyanate used and the effects of hyaluronic acid and glycerol. DETAILED DESCRIPTION

[0076] In a first aspect, the present invention relates to a method for preparing microcapsules based on vegetable proteins, the method comprising the following steps carried out in sequence:

[0077] (i) providing an inner non-aqueous phase comprising at least one aliphatic polyisocyanate as crosslinking agent and at least one hydrophobic reactive ingredient and optionally at least one further crosslinking agent;

[0078] (ii) providing an external aqueous phase comprising at least one vegetable protein,

[0079] 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 further optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the vegetable protein;

[0080] (iii) emulsifying or dispersing the inner non-aqueous phase in the outer aqueous phase to obtain an oil-in-water emulsion or dispersion, the emulsification or dispersing optionally being carried out in the presence of at least one stabilizer and / or at least one emulsifier;

[0081] (iv) optionally adding at least one additional polysaccharide and / or at least one additional vegetable protein;

[0082] (v) performing a first crosslinking to obtain a microcapsule slurry;

[0083] (vi) curing the microcapsule slurry at a temperature of at least 60° C. and optionally adding additional polysaccharide and / or additional vegetable protein;

[0084] (vii) cooling and optionally further cross-linking by adding at least one additional cross-linking agent; and

[0085] (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 thickener.

[0086] In the context of the present invention, microcapsules are understood to be microparticles having at least one or more active ingredients as core material inside the capsule and surrounded by a capsule shell or capsule wall. The active ingredient is preferably a hydrophobic or lipophilic active ingredient. Such active ingredients are insoluble or slightly soluble in water, but are readily soluble in fats and oils. The terms "microcapsules" and "capsules" or "hydrophobic" and "lipophilic" are used synonymously in the sense of the present invention.

[0087] In the context of the present invention, the capsule shell or capsule wall preferably consists of several crosslinking matrices or crosslinking units, which preferably have different compositions and are generated during the preparation of the microcapsules according to the invention by several process steps or process sequences, in particular crosslinking steps. The crosslinking matrix comprises at least one vegetable protein.

[0088] These capsule wall components are crosslinked by interfacial polymerization, optionally via a specific catalytic mechanism, with the aid of a crosslinking agent and optionally a catalyst, to form a three-dimensional network comprising vegetable proteins and aliphatic polyisocyanates as crosslinking agents and optionally at least one polysaccharide.

[0089] In the first step (i) of the process according to the invention, an internal nonaqueous phase is provided which comprises at least one aliphatic polyisocyanate as crosslinker and at least one hydrophobic active ingredient and optionally at least one further crosslinker.

[0090] 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 bonded to an organic group. Polyfunctional isocyanates or polyisocyanates are compounds containing at least two or more, i.e. 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 100, 200 or even more isocyanate groups (-N=C=O) in the molecule. Polyisocyanates with two isocyanate groups are also called diisocyanates.

[0091] According to the invention, the at least one polyisocyanate used in step (i) is an aliphatic polyisocyanate.

[0092] It may also be provided that the at least one aliphatic polyisocyanate is linear or branched.

[0093] Surprisingly, it has been shown that the use of at least one aliphatic polyisocyanate is particularly advantageous when using vegetable proteins and therefore in the preparation of microcapsules based on vegetable proteins. The reduced reactivity of aliphatic polyisocyanates compared to aromatic polyisocyanates can have a particularly favorable effect on the stability of the microcapsules based on vegetable proteins. In any case, the stability of the microcapsules based on vegetable proteins achieved is significantly lower when using aromatic polyisocyanates or mixtures with aromatic polyisocyanates than when using aliphatic polyisocyanates.

[0094] In this regard, during the preparation of the vegetable protein-based microcapsules, i.e. in the process according to the invention, a reduced reactivity with respect to the at least one polyisocyanate used as crosslinking agent is particularly preferred. Thus, in the process according to the invention, the accelerated reactivity of the polyisocyanates used and thus the preparation time of the microcapsules themselves are not a priority.

[0095] Particularly preferably, at least difunctional, preferably polyfunctional, polyisocyanates are used in the process according to the invention, ie all aliphatic and cycloaliphatic (ie cycloaliphatic) isocyanates are suitable, provided that they have at least one, preferably two or more, reactive isocyanate groups.

[0096] Particular preference is given to aliphatic, cycloaliphatic or heterocyclic polyisocyanates, their substitution products and mixtures of the abovementioned monomeric or oligomeric compounds.

[0097] In a preferred embodiment of the process according to the invention, the polyisocyanate contains on average 2 to 5 -N=C=O functional groups. These include, for example, aliphatic or cycloaliphatic di-, tri- and higher polyisocyanates.

[0098] Among the above-mentioned polyisocyanates, diisocyanates and polyisocyanates having three -NC=O functional groups are particularly preferred and can therefore be mainly used in the practice of the present invention. Preferably, diisocyanates having the general structure O=C=NRN=C=O can be used, wherein R represents an aliphatic or alicyclic group. Preferably, the group has five or more carbon atoms.

[0099] In a preferred embodiment of the process according to the invention, at least one of the aliphatic polyisocyanates or the one aliphatic polyisocyanate is a cycloaliphatic polyisocyanate having two or more isocyanate groups.

[0100] Due to the number of functional groups, an optimal cross-linking or networking of the capsule wall is achieved, which provides the vegetable protein based microcapsules with a long-term slow release of the active ingredient and good stability in the consumer product.

[0101] The term "aliphatic polyisocyanate" refers to any polyisocyanate molecule which is non-aromatic. In addition, the molecule comprises 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 which are directly bonded to a corresponding number of different C atoms of the same aliphatic molecule, as well as derivatives of these compounds.

[0102] The 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 any substitution including, for example, aliphatic substituents, 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.

[0103] The linear aliphatic polyisocyanate molecules can preferably be selected from C2- to C20-linear alkyl, preferably C3- to C15-linear alkyl, C4- to C12-linear alkyl, C5- to C10-linear alkyl, C6- to C9-linear alkyl or C7- to C8-linear alkyl. In any case, the linear aliphatic molecules do not contain aromatic structures.

[0104] The branched aliphatic polyisocyanate molecules may preferably be selected from C2- to C20-branched alkyl, preferably C3- to C15-branched alkyl, C4- to C12-branched alkyl, C5- to C10-branched alkyl, C6- to C9-branched alkyl, C7- to C8-branched alkyl.

[0105] For the purposes of the present invention, cycloaliphatic polyisocyanates are also to be understood and described as aliphatic polyisocyanates.

[0106] The cyclic aliphatic polyisocyanate molecule may contain at least one, i.e. 1, 2, 3, 4 or more non-aromatic ring structures, which themselves are preferably composed only of C atoms. Of course, the C atoms of the ring structure may carry suitable substituents. The at least one ring structure preferably consists independently of one another of 3, 4, 5, 6, 7 or 8-membered rings. Preferably, the cyclic aliphatic molecule contains 2 to 20 C atoms, for example 3 to 15 C atoms, 4 to 12 C atoms, 5 to 10 C atoms, 6 to 9 C atoms or 7 to 8 C atoms.

[0107] The straight chain, branched or cyclic aliphatic polyisocyanate can exist as a monomer or a polymer. Monomeric polyisocyanates are molecules that are not connected to another molecule, in particular molecules that are not connected to another molecule through one or more crosslinking agents. Polymeric polyisocyanates contain at least two monomers connected to each other through one or more crosslinking agents. The at least two monomers do not necessarily have to be the same monomers, but can also be different. Polymeric polyisocyanates preferably contain at least 2 or more monomers connected together by at least one crosslinking agent, i.e. at least 2, 3, 4, 5, 10, 20, 30, 40, 50, 100 or more monomers.

[0108] The linear, branched or cyclic aliphatic polyisocyanate preferably has a limited size / molecular weight that allows for reactivity with the one or more crosslinking agents. Examples of suitable molecular weights preferably include about 100 g / mol to 5×10 4 g / mol, preferably 120 g / mol to 2×10 4 g / mol, 140 g / mol to 10 4 g / mol, 160 g / mol to 5×10 3 g / mol, 180 g / mol to 2×10 3 g / mol, 200 g / mol to 10 3 g / 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.

[0109] Any number of different linear, branched and / or cyclic aliphatic polyisocyanates may 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 may 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 may also be used. For example, as crosslinking agent, at least one or more, i.e., at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different branched cyclic polyisocyanates may be used.

[0110] Preferably, derivatives of straight chain, branched and / or cyclic aliphatic polyisocyanates are used. As used herein, derivatives are understood to be compounds derived from compounds by chemical reactions in their broadest sense. Examples of derivatives include oligomers and / or adducts of the above-mentioned straight or branched aliphatic polyisocyanates. Preferred oligomers are biuret, isocyanurate, uretdione, iminooxadiazinedione, and preferred adducts are trimethylolpropane adducts. These oligomers / adducts are well known in the prior art and are disclosed, for example, in US 4855490 A or US 4144268 A.

[0111] Preferably, the aliphatic polyisocyanates are present exclusively in monomeric and / or dimeric form (as isocyanates) or in oligomeric form.

[0112] The linear, branched or cyclic polyisocyanate derivatives and / or mixtures thereof can also be obtained by reacting polyisocyanates with polyols (eg glycerol), polyamines, polythiols (eg dimercaptopropanol).

[0113] The isocyanate compound defined above explicitly includes various isomers, if any, either alone or in combination. For example, methylene bis(cyclohexyl isocyanate) (H12MDI) includes 4,4'-methylene bis(cyclohexyl isocyanate), 2,4'-methylene bis(cyclohexyl isocyanate) and / or 2,2'-methylene bis(cyclohexyl isocyanate).

[0114] Exemplary aliphatic polyisocyanates include those that are commercially available, such as BAYHYDUR N304 and BAYHYDUR N3Q5, which are aliphatic water-dispersible polyisocyanates based on hexamethylene diisocyanate, DESMODUR N3400, DESMODUR N3600, DESMODUR N3700, and DESMODUR N3900, which are low viscosity polyfunctional aliphatic polyisocyanates based on hexamethylene diisocyanate, polyfunctional 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.

[0115] According to another preferred variant of the invention, the linear or branched aliphatic and / or alicyclic polyisocyanates are selected from pentamethylene diisocyanate (PDI, for example Stabio D-370N or D-376N from Mitsui Chemicals Inc., Japan), hexamethylene diisocyanate (HDI), ethyl lysine triisocyanate, ethyl lysine diisocyanate and derivatives thereof, preferably wherein each of the derivatives comprises more than one isocyanate group and optionally further comprises one or more groups selected from biuret, isocyanurate, uretdione, iminooxadiazinedione and trimethylolpropane adducts, and / or wherein one or more of the cyclic aliphatic polyisocyanates are selected from isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI, for example Takenate) or selected from Japan 600 from Mitsui Chemicals, Inc.), 1,2-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, methylenebis(cyclohexyl isocyanate) (H12MDI) and derivatives thereof, preferably wherein each of the derivatives comprises more than one isocyanate group and optionally further comprises one or more groups selected from the group consisting of biuret, isocyanurate, uretdione, iminooxadiazinion and trimethylolpropane adducts (e.g. TMP adducts) of H6XDI, in particular Takenate D-120N from Mitsui Chemicals, Inc., Japan).

[0116] Aliphatic polyisocyanates obtained from renewable raw materials such as PDI (Stabio D-370N or D-376N from Mitsui Chemicals, Inc., Japan) are particularly preferred. Such aliphatic polyisocyanates obtained from renewable raw materials were found not to adversely affect the quality / performance of the core-shell capsules.

[0117] In one variant of the process according to the invention, the polyisocyanate used in the preparation of the vegetable protein-based microcapsules according to the invention is used as the sole polyisocyanate component, ie not mixed with another polyisocyanate component different therefrom.

[0118] Examples of monomeric polyisocyanates which can be used according to the invention and contain at least two polyisocyanate groups are:

[0119] 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 a mixture thereof.

[0120] As polymerizable compounds containing at least two polyisocyanate groups, preference is given to industrially produced diisocyanates and polyisocyanates, for example HDI: hexamethylene diisocyanate-(1,6) and / or IPDI: isophorone diisocyanate.

[0121] 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′-diisocyanatodicyclohexylmethane, 2,4- and 2,6-diisocyanatomethylcyclohexane and mixtures thereof.

[0122] 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-cyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate.

[0123] In particular, the use of longer-chain aliphatic diisocyanates having six, seven, eight, nine, ten or even more carbon atoms can lead to the formation of more stable capsule shells or capsule walls.

[0124] In a particularly preferred embodiment, the inner non-aqueous phase comprises a mixture of two or more different polymerizable polyisocyanates, for example polyisocyanates with different chain lengths, which can form mixed polymers.

[0125] The process according to the invention can provide for the use of a combination of at least two different aliphatic polyisocyanates.

[0126] In such a combination, the different reaction rates of the polyisocyanates are utilized. Short chain aliphatic polyisocyanates, ie aliphatic polyisocyanates having one to five carbon atoms, preferably three to five carbon atoms, can achieve higher reaction rates compared to longer chain analogs.

[0127] In another preferred further development of the invention, the different aliphatic polyisocyanates therefore also have different chain lengths. In this case, the longer-chain polyisocyanates preferably have six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, 20, 25 or more carbon atoms, but even more preferably, they have six to twelve carbon atoms, and particularly preferably six to eight carbon atoms. Shorter-chain polyisocyanates are meant to have one to five carbon atoms, and preferably three to five carbon atoms.

[0128] 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 more) may be used.

[0129] For the preparation of the vegetable protein-based microcapsules according to the invention, it is particularly preferred in this case to use a mixture of different aliphatic polyisocyanates having two or more isocyanate groups having a chain length of one to twelve carbon atoms, preferably three to eight carbon atoms, particularly preferably four to seven carbon atoms in the chain.

[0130] In this context, aliphatic polyisocyanates are particularly preferred, especially because of their chemical relationship to bio-based systems. For example, lysine and 1,5-diisocyanatopentane both show the same degradation product, 1,5-diaminopentane, and are therefore particularly suitable for improved biodegradability of microcapsules from an environmental perspective.

[0131] The main embodiment comprises mixtures of longer-chain and shorter-chain diisocyanates in any desired mixing ratio. Preferably, the mixing ratio of longer-chain diisocyanates to shorter-chain diisocyanates is in the range from 4:1 to 1:4, particularly preferably from 2:1 to 1:2.

[0132] Preferably, the process according to the invention can provide that in the abovementioned combination of short-chain aliphatic polyisocyanates and long-chain aliphatic polyisocyanates, the polyisocyanates are present as a mixture in monomeric or oligomeric or polymeric form.

[0133] Preferably, this results in the following use combination in the method according to the invention:

[0134] - short-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and short-chain aliphatic polyisocyanates (monomers or oligomers or polymers);

[0135] - short-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and long-chain aliphatic polyisocyanates (monomers or oligomers or polymers);

[0136] - long-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and short-chain aliphatic polyisocyanates (monomers or oligomers or polymers);

[0137] - long-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and long-chain aliphatic polyisocyanates (monomers or oligomers or polymers);

[0138] It has the above definitions for short chain and long chain.

[0139] The selection of at least two aliphatic polyisocyanates with different chain lengths and different degrees of polymerization can lead to significant gains in stability and performance (fragrance release in the case of fragrances or fragrance capsules) due to the different reaction rates, dissociation bodies and crosslinking structures of the polyisocyanate components.

[0140] The above-mentioned polyisocyanate combinations or polyisocyanate mixtures formed from two different aliphatic polyisocyanates can be used to produce particularly stable and better, ie more densely branched, crosslinks in the capsule shell.

[0141] Thus, the process described herein can be used to prepare high performance (fragrance or odor release) vegetable protein based microcapsules made from a mixture of two different aliphatic polyisocyanates. Such vegetable protein based microcapsules are very stable and are characterized by having excellent fragrance storage properties, which in turn is reflected in better performance (fragrance or odor release) of the capsules, for example in the field of fragrance or odor encapsulation.

[0142] The use of two different aliphatic polyisocyanates can produce microcapsules that even exceed the stability of microcapsules formed from a single polyisocyanate system.

[0143] Compared with microcapsules made from aliphatic-aromatic polyisocyanate mixtures, microcapsules made from aliphatic-aliphatic polyisocyanate mixtures are significantly improved at least in terms of stability, as shown in the following embodiment examples. Therefore, the present invention basically stipulates that aliphatic polyisocyanates are used in the above-mentioned combinations. In any case, the use of any aromatic polyisocyanates is explicitly excluded in the present invention.

[0144] The one or more crosslinking agents, preferably the one or more polyisocyanates, are present in the inner non-aqueous phase in a proportion ranging from 0.1 to 5% by weight, preferably ranging from 0.2 to 4% by weight, based on the total weight of the non-aqueous phase. Most preferably, the amount of the crosslinking agent in the inner non-aqueous phase is in a range of 0.5 to 2% by weight, based on the total weight of the non-aqueous phase. The total weight of the non-aqueous phase is composed of all components of the non-aqueous phase.

[0145] The crosslinking agent is added to the inner non-aqueous phase as such (eg, as a solid) or in the form of an aqueous solution.

[0146] In order to obtain microcapsules based on vegetable proteins which have a very good balance between stability and organoleptic properties (fragrance or odor release) and which also have a biodegradable potential, a particularly advantageous embodiment of the method according to the invention can provide that the total amount of polyisocyanates, based on the amount of wall formers, is 15 to 70% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 35% by weight, or the total amount of polyisocyanates used together as crosslinkers is 0.5 to 4%, preferably 1 to 3%, particularly preferably 1.5 to 2.5%, based on the total amount of hydrophobic active ingredients used (preferably fragrances or odors, in particular in the core of the capsules).

[0147] Wall formers within the meaning of the present invention are all solid components of the inner and outer phase and any optionally added polysaccharides, in particular further crosslinkers and / or polyhydroxyphenols and / or catalysts, and in the context of the present disclosure, all other suitable substances.

[0148] In another advantageous further development of the process according to the invention, provision can be made 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.

[0149] Surprisingly, microcapsules based on vegetable proteins can be prepared in this way which have a particularly good combination of stability properties and very good organoleptic properties (fragrance or odor release). In addition, the total content of polyisocyanates used as crosslinkers can be reduced, which has a positive effect on the environment.

[0150] In another advantageous further development of the process according to the invention, provision can be made for a non-internal, non-aqueous phase to be provided in step (i) 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.

[0151] With regard to the two aliphatic polyisocyanates, reference is made to the detailed explanations throughout the context of the present disclosure, where appropriate also applying to the stated molar ratios thereof.

[0152] Surprisingly, it has been found that the vegetable protein-based microcapsules prepared in this way each exhibit very good stability properties and very good organoleptic properties (fragrance or odor release) when the two aliphatic polyisocyanates are used in a respective molar ratio of 85:15 to 15:85.

[0153] In order to obtain microcapsules based on vegetable proteins which are optimized both with regard to their stability behavior and their organoleptic properties, provision can be made in a particularly preferred aspect of the process according to the invention that an internal non-aqueous phase is provided in step (i), which comprises three crosslinkers, wherein the three crosslinkers are aliphatic or cycloaliphatic polyisocyanates different from one another, wherein preferably at least one cycloaliphatic polyisocyanate and at least one aliphatic polyisocyanate are present, wherein the three polyisocyanates are each used together in an amount of 20 to 60%, based on the total weight of the three polyisocyanates.

[0154] Preferably, three alicyclic polyisocyanates may be used.

[0155] In this case, too, it is particularly advantageous to use a cycloaliphatic polyisocyanate and two aliphatic polyisocyanates that are different from one another.

[0156] With regard to the three polyisocyanates, reference is made to the detailed explanations throughout the context of the present disclosure, where appropriate, the stated ratios thereof also apply likewise.

[0157] In another advantageous further development of the process according to the invention, provision can be made for the three cycloaliphatic polyisocyanates to be used in each case in equal proportions.

[0158] Furthermore, it can be provided that the cycloaliphatic polyisocyanate and the two mutually different aliphatic polyisocyanates are each used in equal proportions.

[0159] In this way, optimized polyisocyanate mixtures can be provided which have a particularly favorable influence on the stability of the microcapsules obtained and on their organoleptic properties (odor or fragrance release), whereby it has surprisingly been found that the total amount of polyisocyanates used can be reduced.

[0160] Furthermore, if appropriate, the advantages or effects of the polyisocyanates described throughout the disclosure also apply additionally and / or supplementarily to the molar ratios and / or quantitative ratios described herein.

[0161] In order to improve the cross-linking of the at least one polysaccharide and / or the at least one vegetable protein, at least one additional cross-linking agent may be added to the inner non-aqueous phase. In one embodiment, the additional cross-linking agent is different from the (first) cross-linking agent. In another embodiment, the at least one additional cross-linking agent may be the same as the cross-linking agent. The cross-linking agent may also comprise the at least one additional cross-linking agent.

[0162] It may be provided that at least one further crosslinker is added in step (i) and / or a further crosslinker is added in step (ii) and / or in step (vii).

[0163] In case of addition in step (i), or in case of addition in step (ii) and / or in step (vii), the at least one further cross-linking agent is selected from transglutaminases, peroxidases, secondary plant substances selected from polyphenols, polyhydroxyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the above cross-linking agents. In this aspect, the at least one further cross-linking agent may be a polyphenol and / or a polyhydroxyphenol.

[0164] Transglutaminase is an enzyme that catalyzes cross-linking via isopeptide bonds between two amino acids (glutamine and lysine). The phenolic groups of the secondary plant matter cross-link the peptides via hydrogen bonds. Aldehydes, cinnamaldehyde and vanillin covalently react with free amino groups of the proteins via reactive aldehyde groups.

[0165] Among the above-mentioned other cross-linking agents, cinnamaldehyde, tannin, ferulic acid and gallic acid are particularly preferred.

[0166] Tannins are particularly preferred. The organoleptic properties of the microcapsules according to the invention can advantageously be significantly improved.

[0167] Very preferably, provision can be made for tannin to be added as the at least one further crosslinking agent in step (i) and / or for tannin to be added as the one further crosslinking agent in step (ii) and / or in step (vii).

[0168] Particularly advantageous combinations of crosslinker and further crosslinker are:

[0169] Polyisocyanates plus transglutaminase;

[0170] Polyisocyanate plus peroxidase;

[0171] Polyisocyanates plus polyphenols;

[0172] Polyisocyanates plus tannins;

[0173] Polyisocyanate plus gallic acid;

[0174] Polyisocyanate plus ferulic acid;

[0175] Polyisocyanates plus hesperidin;

[0176] Polyisocyanate plus cinnamaldehyde;

[0177] Polyisocyanate plus vanillin;

[0178] Polyisocyanates plus carvacrol; or

[0179] A mixture of a polyisocyanate plus two or more of the above other crosslinking agents.

[0180] The additional cross-linking agent may be added to the inner non-aqueous phase as such (eg, as a solid) or in the form of a solution.

[0181] The combined use of at least one crosslinker and at least one further crosslinker which are different from one another leads to microcapsules having a significantly improved stability and thus to a lower proportion of leakage of the hydrophobic active ingredient.

[0182] In step (i) of the process according to the invention, if appropriate, the at least one crosslinking agent is first substantially dissolved in an inert non-aqueous solvent or in a solvent mixture of inert non-aqueous solvents together with the at least one or more active ingredients to be encapsulated. 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 the above-mentioned components are dissolved in the solvent or in the solvent mixture, so that they can be used in the process according to the invention. Preferably, the at least one polyisocyanate and the at least one active ingredient to be encapsulated are completely dissolved in the solvent or in the solvent mixture. If the solvent does not ensure sufficient solubility of the isocyanate, this disadvantage can be overcome by using suitable solubility promoters.

[0183] Preferred solvents for the inner non-aqueous phase are immiscible with water and do not react with the isocyanate component(s) or the reactive ingredient component(s) and have little or no odor in the amounts used.

[0184] The term "solvent" in the context of the present invention includes all types of oil bodies or oil components, in particular vegetable oils, for example rapeseed oil, sunflower oil, soybean oil, olive oil and the like, 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 methyl or ethyl esters of vegetable oils ( ME 18RD-F, ME18SD-F, ME 12C-F, 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 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, for example 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, myristyl Stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl stearate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, oleyl myristate, oleyl palmitate, oleyl stearate, isostearyl Oleyl fatty acid, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, sinacyl myristate, sinacyl palmitate, sinacyl stearate, sinacyl isostearate, sinacyl oleate, sinacyl behenate and sinacyl erucate.

[0185] Also suitable are: esters of linear C6 to C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18 to C38 alkylhydroxycarboxylic acids with linear or branched C6 to C22 fatty acids, in particular Dioctylalat, esters of linear or branched fatty acids with polyols, for example propylene glycol, dimer diol or trimer triol, and / or Guerbet alcohols, triglycerides based on C6 to C10 fatty acids, liquid mono- / di- / triglyceride mixtures of C6 to C18 fatty acids, esters of C6 to C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2 to C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear or branched C6 to C22 fatty alcohol carbonates, for example dicaprylyl carbonate ( CC); Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, benzoates 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, for example dicaprylyl ether, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, polysiloxane polymethicone grade etc.), aliphatic hydrocarbons or cycloalkanes, for example squalane, squalene or dialkylcyclohexanes and / or mineral oil.

[0186] Preferred solvents are also, in particular, esters of linear C6 to C22 fatty acids with branched alcohols, esters of C18 to C38 alkylhydroxycarboxylic acids with one or more linear or branched C6 to C22 fatty alcohols, in particular dioctyl malate, esters of linear or branched fatty acids with polyols (e.g. propylene glycol, dimer diol or trimer triol, and / or Guerbet alcohols), triglycerides based on C6 to C10 fatty acids, liquids based on C6 to C18 fatty acids Mono- / di- / triglyceride mixtures, esters of 6- to C22-fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2- to C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6- to C22-fatty alcohol carbonates, for example dicaprylyl carbonate (Cetiol TM 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 radical, for example dicaprylyl ether (Cetiol TM OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclopolydimethylsiloxane, silicone methicon type, etc.), and / or aliphatic hydrocarbons or cycloalkanes, for example squalane, squalene or dialkylcyclohexanes.

[0187] In addition, in the context of the present invention, liquid straight and / or branched and / or saturated or undersaturated hydrocarbons or any desired mixtures thereof can be used as solvents. These can be, for example, alkanes having 4 to 22, preferably 6 to 18 carbon atoms, or any desired mixtures thereof.

[0188] Particularly suitable inert solvents for the internal non-aqueous phase are alkylaromatic hydrocarbons, for example diisopropylnaphthalene or substituted biphenyls, chlorinated biphenyls, paraffins, chlorinated paraffins, natural vegetable oils, for example cottonseed oil, peanut oil, palm oil, tricresyl phosphate, 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 and any mixtures of these hydrophobic solvents and mixtures of one or more of these hydrophobic solvents with kerosene, paraffins and / or isoparaffins.

[0189] In order to provide the internal non-aqueous phase, preferably vegetable oil triglycerides, benzyl benzoate or isopropyl myristate are used as solvents. Most preferably, vegetable oils are selected from 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.

[0190] In the process according to the invention, the abovementioned solvents are used either alone or as a mixture of two or more solvents.

[0191] In an alternative and preferred variant of the process according to the invention, the at least one polyisocyanate is dissolved directly in a solution of the at least one active ingredient, preferably one or more fragrances or flavorings or fragrance oils, so that essentially no solvent as described above is present in the core of the vegetable protein-based microcapsules according to the invention. The absence of solvent in the microcapsule core has the advantage that it reduces manufacturing costs and takes environmental factors into account.

[0192] The fragrance or flavoring is especially dissolved in a solvent commonly used in the fragrance or flavoring industry. The solvent is preferably not an alcohol, since alcohol reacts with the isocyanate. Examples of suitable solvents are diethyl phthalate, isopropyl myristate, (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% and even more preferably less than 10% solvent, all of which percentages are 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.

[0193] If the at least one hydrophobic active ingredient is already present in a mixture with a solvent or solvent mixture, then there is no need to use an inert solvent or solvent mixture. In this case, the at least one crosslinking agent can be mixed directly with the hydrophobic active ingredient to obtain an inner non-aqueous phase.

[0194] In principle, any material suitable for inclusion in microcapsules can be used as active ingredient to be encapsulated or as core material for preparing microcapsules according to the invention. The active substances to be encapsulated are preferably hydrophobic, i.e. water-insoluble or water-immiscible liquids or solids and suspensions. These are mainly non-polar substances. Such hydrophobic substances are almost always lipophilic, i.e. they dissolve well in fats and oils.

[0195] In the context of the present specification, the core material is a hydrophobic active ingredient, ie a substance which has a specific action or causes a specific reaction, such as a medicinal substance, a plant protection agent, a cosmetic active ingredient, a food active ingredient or the like.

[0196] The 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 during the preparation of the microcapsules according to the invention, the active ingredient to be encapsulated is in the inner non-aqueous phase and does not mix with the outer aqueous phase, because otherwise no emulsion can be formed and the capsule wall material cannot be deposited on the droplet surface. As a result, the lipophilic active ingredient is completely trapped inside the microcapsule as core material during the subsequent emulsification and crosslinking of the capsule wall components. The inner non-aqueous phase formed in this way is characterized in that it has an organic hydrophobic, oily character.

[0197] As mentioned above, it may be provided that in step (ii) a further crosslinking agent is added. This may be a crosslinking agent selected from the group consisting of transglutaminases, peroxidases, secondary plant substances selected from the group consisting of polyphenols, polyhydroxyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the above crosslinking agents.

[0198] The amount of the further crosslinking agent optionally added in step (ii) may be 0.1% to 1.0%, preferably 0.15% to 0.5%, particularly preferably 0.17% to 0.23%, relative to the total amount of the external aqueous phase.

[0199] 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 flavor oil or flavoring (fragrance or flavoring mixture), a cooling agent, a TRPV1 or TRPV3 modulator, a substance that produces a pungent taste or a warm or hot sensation on the skin or mucous membranes, or a substance that produces a tingling or stinging sensation in the mouth or throat, or an active ingredient with an astringent effect, a pesticide, a biocide, an insecticide, a substance from the group of insect repellents, a food additive, a cosmetic active ingredient, a pharmaceutical active ingredient, a dye, a dye precursor, an agrochemical, a dye, a luminescent coating, an optical brightener, a solvent, a wax, a silicone oil, a lubricant, a paper printing coating, or a mixture of two or more of the above active ingredients.

[0200] In a preferred embodiment 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 flavoring substance or a flavoring substance mixture of two or more flavoring substances (flavorings), or else a biogenin.

[0201] In a preferred embodiment according to the first and / or second aspects of the present invention, the microcapsules contain a core material in the form of a hydrophobic single fragrance or single odorant, wherein the core material contains at least one single fragrance or single odorant or a mixture thereof, which is selected from one or more of the following groups: extracts of natural raw materials and fractions thereof or components separated therefrom; single fragrances from the group of 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, valerates, caproates, crotonates, tiglates and 3-methyl-2-butenoates of acyclic terpene alcohols; Cyclic terpene aldehydes and ketones and their dimethyl and diethyl acetals; formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglates and 3-methyl-2-butenoates of cyclic terpene alcohols; cyclic terpene aldehydes and ketones; cyclic alcohols; cyclic and alicyclic ethers; cyclic ketones and macrocyclic ketones; alicyclic aldehydes; alicyclic ketones; esters of cyclic alcohols; esters of alicyclic alcohols; esters of alicyclic carboxylic acids; aromatic hydrocarbons; aromatic aliphatic alcohols; esters formed from aromatic aliphatic alcohols and aliphatic carboxylic acids; aromatic aliphatic ethers; aromatic and aromatic aliphatic aldehydes; aromatic and aromatic aliphatic ketones; aromatic and aromatic aliphatic carboxylic acids and their esters; nitrogen-containing aromatic compounds; phenyl ethers and phenyl esters; heterocyclic compounds; lactones; and mixtures of the above active ingredients.

[0202] Suitable fragrances and flavorings for preparing capsules according to the invention are described, for example, in the following literature: "Riechstoffe (fragrances)", Steffen Arctander, "Perfume and Flavor Chemicals (fragrance and flavoring chemicals)", self-published, Montclair, NJ, 1969; H. Surburg, J. Panten, "Common Fragrance and Flavor Materials (common fragrance and flavoring materials), 5th edition, Wiley-VCH, Weinheim, 2006.

[0203] Preferably, the vegetable protein-based microcapsules according to the present invention comprise a core material in the form of a hydrophobic single fragrance or single flavoring, wherein the core material comprises at least one single fragrance or single flavoring selected from one or more of the following groups:

[0204] - hydrocarbons, for example 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valenciaene; (E,Z)-1,3,5-undecatriene;

[0205] aliphatic alcohols, for example hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 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-undecanol; 4-methyl-3-decen-5-ol;

[0206] - aliphatic aldehydes and their acetals, 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-undecadienal; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde;

[0207] - aliphatic ketones and their oximes, for example 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one;

[0208] - aliphatic sulfur-containing compounds, such as 3-methylmercaptohexanol; 3-methylmercaptohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylmercaptohexyl acetate; 1-menthene-8-thiol;

[0209] - aliphatic nitriles, for example 2-nonenenitrile; 2-tridecenenitrile; 2,12-tridecenenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0210] - aliphatic carboxylic acids and their esters, 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-octen-3-yl acetate; ethyl butyrate; butyl butyrate; butyl isopentyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynoate; methyl 2-nonynoate; allyl 2-isopentyloxyacetate; methyl 3,7-dimethyl-2,6-octadienoate;

[0211] acyclic terpene alcohols, 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; 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 formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters, 3-methyl-2-butenoates;

[0212] - acyclic terpene aldehydes and ketones, for example geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral and 7-hydroxy-3,7-dimethyloctanal;

[0213] - Cyclic terpene alcohols, for example: menthol; isopulegol; α-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambroxanol; vetiverol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters, 3-methyl-2-butenoate;

[0214] - cyclic terpene aldehydes and ketones, 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; γ-damascenone; δ-damascenone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-endomethylnaphthalen-8(5H)-one; nootkatone; dihydronootkatone; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedar oil (methyl cedar ketone);

[0215] - cyclic alcohols, for example 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-(Z2,Z5,E9)-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; from the group of alicyclic alcohols, for example 3,3,3-trimethylcyclohexylmethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 2-ethyl 3-Methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-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;

[0216] - cyclic and alicyclic ethers, for example eucalyptol; cedryl methyl ether; cyclododecyl methyl ether; (ethoxymethoxy)-cyclododecane; α-cedryne epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[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;

[0217] - cyclic ketones, 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-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0218] - cycloaliphatic aldehydes, for example 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0219] - cycloaliphatic ketones, for example 1-(3,3-dimethyl-cyclohexyl)-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-naphthylmethyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone;

[0220] - esters of cyclic alcohols, for example 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl 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;

[0221] - esters of cycloaliphatic carboxylic acids, for example allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmonate; methyl jasmonate; 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;

[0222] - aromatic hydrocarbons, such as styrene and diphenylmethane;

[0223] - aromatic aliphatic alcohols, for example benzyl alcohol; 1-phenylethanol; 2-phenylethanol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 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;

[0224] - esters formed from aromatic aliphatic alcohols and aliphatic carboxylic acids, 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-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0225] - aromatic aliphatic ethers, for example 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated atroaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

[0226] - aromatic and aromatic aliphatic aldehydes, for example benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroataldehyde; 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; a-butylcinnamaldehyde; a-amylcinnamaldehyde; a-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;

[0227] - aromatic and araliphatic ketones, for example acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanylmethyl 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-naphthylacetophenone;

[0228] - aromatic and araliphatic carboxylic acids and their esters, for example benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl 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;

[0229] - Nitrogen-containing aromatic compounds, such as 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-methyl-2-pentenoic acid nitrile; 5-phenyl-3-methylvaleric acid nitrile; methyl anthranilate; methyl N-methyl anthranilate; methyl anthranilate and 7-hydroxy-3,7- Schiff bases formed from dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 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;

[0230] -phenols, phenyl ethers and phenyl esters, for example: estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-tolylphenyl acetate; from the group of the heterocyclic compounds, for example 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0231] -lactones, such as 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecalactone; 1,4-dodecalactone; 1,5-decanolactone; 1,5-dodecalactone; 1,15-pentadecalactone; cis- and trans-11-pentadeca-1,15-lactone; cis- and trans-12-decene-1,15-lactone Pentaene-1,15-lactone; 1,16-hexadecene-1,16-lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecene-lactone; 11-oxa-1,16-hexadecene-lactone; 12-oxa-1,16-hexadecene-lactone; 1,12-dodecanediol glycol ester; 1,13-tridecanediol glycol ester; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin;

[0232] and stereoisomers, enantiomers, positional isomers, diastereomers, cis / trans isomers or epimers of the above substances.

[0233] Among the abovementioned individual fragrances or individual odorants which can be encapsulated within the meaning of the present invention, particular preference is given to using fragrances or odorants which have aldehyde, carboxylic acid or ester functions.

[0234] Aldehyde fragrances or odorants, which also include the corresponding acetals as well as esters and lactones, can be divided into the following categories, namely,

[0235] (i) aliphatic aldehydes and their acetals;

[0236] (ii) alicyclic aldehydes;

[0237] (iii) aromatic or araliphatic aldehydes;

[0238] (iv) aliphatic, aromatic or araliphatic esters; and

[0239] (v) lactones;

[0240] and mixtures thereof.

[0241] The above-mentioned fragrance or odorant having aldehyde, carboxylic acid or ester functional group and their mixture are selected from one or more of the following groups:

[0242] - aliphatic aldehydes and their acetals, 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; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde;

[0243] - cycloaliphatic aldehydes, for example 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0244] - aromatic and aromatic aliphatic aldehydes, for example: benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroataldehyde; 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-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;

[0245] - aliphatic carboxylic acid esters, 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 amyl ester; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynoate; methyl 2-nonynoate; allyl 2-isopentyloxyacetate; methyl 3,7-dimethyl 2,6-octadienoate;

[0246] - esters of cyclic alcohols, for example 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl 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;

[0247] - esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, 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-dimethylphenethyl acetate; α,α-dimethylphenethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0248] - esters of cycloaliphatic carboxylic acids, for example allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmonate; methyl jasmonate; 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;

[0249] - Esters of aromatic and araliphatic carboxylic acids, for example: methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl 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.

[0250] Listed below are aldehydes, acetals, esters and lactones and their commercial names which are particularly preferred as representatives of groups (i) to (v) for the purposes of the process according to the invention:

[0251] ALDEHYDE: 2-METHYLVALDEALDE; ALDEHYDE C12 MNA HM; ALDEHYDE C4; ALDEHYDE C5; ALDEHYDE C6; ALDEHYDE C7; ALDEHYDE C8; ALDEHYDE C9; ALDEHYDE C10; ALDEHYDE C11ISO; ALDEHYDE C11MOA PURE; ALDEHYDE C11UNDECANAL; ALDEHYDE C11UNDEYLENIC; ALDEHYDE C12; ALDEHYDE C12MNA; ALDEHYDE C13; ALDEHYDE MADARINE; AMYL CINNAMIC ALDEHYDE ALPHA; ANISALALDEHYDE-O; ANISYLALDEHYDE; BENZALDEHYDE NAT.; BERGAMAL; BORONAL; BOURGENOAL; CAMPHONELIC ALDEHYDE; CITRAL; CITRONELLAL HM; CITRONELLYL OXYACET ALDEHYDE; CITRYLAL; CITROYLAL E HM; CORTEX ALDEHYDE; CORTEX ALDEHYDE 50PCT PEMOSA;CROTONIC ALDEHYDE;CUMINALALDEHYDE;CYCLAMEN ALDEHYDE;DECADIENAL TRANS,TRANS-2,4,DECANAL CIS-4;DECANALTRANS-2;DECANAL TRANS-2NAT;DECANAL TRANS-4;DECANAL-9,1;DODECANIENAL 2,6;DODECANAL TRANS-2;DUPICAL;EPOXYDECENAL-4,5-2 10% TRI;ETHYL HEXANAL; FLORHYDRAL;GERALDEHYDE;HELIONAL;HELIOPAN;HELIOTROPIN;HEPTADIENALTRANS,TRANS,2-4;HEPTENAL CIS-4;HEPTENAL TRANS-2;HEXENAL TRANS-2;HEXYLCINNAMIC ALDEHYDE ALPHA;HYDRATROPIC ALDEHYDE;HYDROXY CITRONELLAL;INTRELEVENALDEHYDE SPEC.;ISONONYL ALDEHYDE;ISOVALERIC ALDEHYDE;LEMON ALDEHYDE H&R JS I;LILIAL;LINOLAL;LYRAL;MAJANTAL;MANDRINAL;MANDRAINE ALDEHYDE 10% IN TEC BHT;MEFRANAL; METHODY CITRONELLAL;METHYL BUTYRALDEHYDE;METHYLCINNAMIC 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 50DPG;NEOCYCLO CITRAL;NONADIENAL;TRANS,CIS-2,6;NONENAL CIS-6;NONENAL TRANS-2; 3 / 060251; PENTENAL TRANS-2; PERILLA ALDEHYDE; PHENYLACET ALDEHYDE; PHENYLBUTENAL TRANS-2,2; ALDEHYDE; PS-IRALDEIN X NEU; SAFRANAL; SALICYLIC ALDEHYDE FG; SILVIAL; TETRAHYDRO CITRAL; TRANS-2;VERNALALDEHYDE;VERTOCITRAL;VERTOMUGAL;VERTIPRENAL;VETRAL ROH; ZIMTALDEHYD NAT.HM; Acetal: FLOROPAL; HEPTANAL DIETHYLACETAL; NONANDIENAL DIETHYL ACETAL; OKOUMAL; PHENYLACET ALD.GLYCERIN ACETAL;

[0252] In a further variant of the method according to the invention, the flavouring substances can also be encapsulated in the form of individual flavourings as core material, wherein the core material comprises at least one individual flavouring substance or a mixture thereof as the active ingredient.

[0253] Typical examples of flavoring substances or flavorings which can be encapsulated within the meaning of the present invention are selected from the group consisting of: acetophenone; allyl hexanoate; α-ionone; β-ionone; anisaldehyde; anisyl acetate; anisyl formate; benzaldehyde; benzothiazole; benzyl acetate; benzyl alcohol; benzyl benzoate; β-ionone; butyl butyrate; butyl hexanoate; butylidenephthalide; carvone; camphene; caryophyllene; eucalyptol; cinnamyl acetate; citral; citronellol; citronellal; citronellyl acetate; cyclohexyl acetate; cymene; damascenone; decalactone; dihydrocoumarin; dimethyl anthranilate; dimethyl anthranilate; dodecalactone; ethoxyethyl acetate; ethyl butyric acid; ethyl butyrate; ethyl decanoate; ethyl hexanoate; ethyl crotonate; ethyl furanone; ethyl guaiacol; ethyl isobutyrate; ethyl isovalerate; ethyl lactate; ethyl methylbutyrate; ethyl propionate; eucalyptol; eugenol; ethyl heptanoate; 4-(p-hydroxyphenyl)-2-butanone; gamma-decanoic acid; geraniol; geranyl acetate; geranyl acetate; viniferal; methyl dihydrojasmonate (e.g. ); 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 hexanoate; trans-2-hexenyl hexanoate; cis-3-hexenyl formate; cis-2-hexyl acetate; cis-3-hexyl acetate; trans-2-hexyl acetate; cis-3-hexyl formate; p-hydroxybenzyl acetone; isopentanol; isopentanyl isovalerate; isobutyl butyrate; isobutyraldehyde; isoeugenol methyl ether; isopropyl methylthiazole; lauric acid; levulinic acid; linalool; linalool oxide; Linalyl acetate; menthol; menthofuran; methyl anthranilate; methyl butanol; methyl butyric acid; 2-methylbutyl acetate; methyl caproate; methyl cinnamate; 5-methylfurfural; 3,2,2-methylcyclopentenolone; 6,5,2-methylheptenone; methyl dihydrojasmonate; methyl jasmonate; 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-nonadienol; 2,6-nonadienol; 2,4-nonadienol; nootkatone; δ-octalactone ; γ-octalactone; 2-octanol; 3-octanol; 1,3-octenol; 1-octyl acetate; 3-octyl acetate; palmitic acid; trimeraldehyde; phellandrene; pentanedione; phenylethyl acetate; phenylethyl alcohol; phenylethyl isovalerate; piperonal; propionaldehyde; propyl butyrate; longifolia menthol; longifolia menthol; sweet orange aldehyde; sulfurol; terpinene; terpineol; terpinolene; 8,3-thiomenthone; 4,4,2-thiomethylpentyl ketone; thymol; δ-undecalactone; γ-undecalactone; valencia orangene; 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 soy sauce ketone (2-ethyl-4-hydroxy-5-methyl-3(2H)-furanone), chicoryone (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-lactone (preferably γ-undecalactone, γ-nonalactone, γ-decanolactone); δ-lactone (preferably 4-methyl δ-decanolactone, Massoilacton, δ-decanolactone, Tuberolacton); 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; ethyl 3-methylbutyrate; ethyl hexanoate; allyl hexanoate; n-butyl hexanoate; ethyl octanoate; ethyl 3-methyl-3-phenylglycidate; ethyl 2-trans-4-cis-decadienoate; 4-(p-hydroxyphenyl)- 2-Butanone; 1,1-dimethoxy-2,2,5-trimethyl-4-hexane; 2,6-dimethyl-5-heptene-1-al; phenylacetaldehyde; 2-methyl-3-(methylthio)furan; 2-methyl-3-furanthiol; bis(2-methyl-3-furanyl) disulfide; furfurylthiol; methylthiopropanal; 2-acetyl-2-thiazoline; 3-mercapto-2-pentanone; 2,5-dimethyl-3-furanthiol; 2,4,5-trimethylthiazole; 2-acetylthiazole; 2,4-dimethyl-5-ethyl Thiazole; 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 -methyl tridecaldehyde; 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 stereoisomers, enantiomers, positional isomers, diastereomers, cis / trans isomers or epimers of these substances not explicitly mentioned herein; and mixtures of the above substances. ;

[0254] In an alternative embodiment according to the invention, in the vegetable protein-based microcapsules according to the invention, a fragrance or odorant mixture or a fragrance oil or a fragrance mixture or fragrance is used as the active ingredient to be encapsulated or as the core material. These are compositions containing at least one fragrance or odorant or flavoring substance. Such compositions, in particular fragrance or odorant mixtures or fragrance oils, preferably contain two, three, four, five, six, seven, eight, nine, ten or more fragrance or odorant substances. The fragrance or odorant mixture or fragrance oil is preferably selected from: extracts of natural raw materials, such as essential oils, extracts, absolute oils, resins, fragrant resins, balms, tinctures, such as amber tincture; fragrant tree oil; angelica seed oil; angelica root oil; fennel oil; valerian oil; basil oil; tree moss absolute oil; laurel oil; artemisia oil; benzoin resin Bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; buco leaf oil; cabrera wood oil; juniper oil; sweet calendula oil; camphor oil; cananga oil; cardamom oil; quinoa oil; cinnamon oil; acacia absolute; castoreum absolute; cedar leaf oil; cedar oil; labdanum oil; citronella oil; lemon oil; copaiba balm; copaiba balm oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill oil; dill seed oil; Eau de brouts absolute; oakmoss absolute; elemi oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; fennel oil; spruce needle oil; geranium oil; geranium resin; geranium oil; grapefruit oil; guaiac wood oil; guyun incense balm; guyun incense balm oil; helichrysum absolute; helichrysum oil; ginger oil; orris root absolute; orris root oil; jasmine absolute; calamus oil; blue chamomile oil; Roman chamomile oil; carrot seed oil; quinoa oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavender absolute; lavender oil; lavender absolute; lavender oil; lemongrass oil; angelica oil; distilled lime oil; pressed lime oil; agarwood oil; litsea cubeba oil; bay leaf oil; nutmeg oil Marjoram oil; mandarin oil; cassia bark oil; mimosa absolute; musk seed oil Musk tincture; muscadine sage oil; nutmeg oil Myrrh Absolute; Myrrh Oil; Myrtle Oil; Clove Leaf Oil; Clove Flower Oil; Neroli Oil; Frankincense Absolute; Frankincense Oil; Red Myrrh Oil; Neroli Absolute; Orange Oil; Oregano Oil; Palmarosa Oil; Patchouli Oil; Perilla Seed Oil; Peruvian Balm Oil; Parsley Leaf Oil; Parsley Seed Oil; Orange Leaf Oil; Peppermint Oil; Allspice Oil; Pine Oil; Polly Oil Rose absolute; rosewood oil; rose oil; rosemary oil; dalmatine sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; marigold oil; fir oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla essence; violet absolute; verbena oil; vetiver oil; juniper berry oil; wine yeast oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; civet absolute; laurel leaf oil; cassia bark oil, and fractions thereof or components isolated therefrom.

[0255] Most preferably, in the method according to the invention, an aroma or odorant or flavoring is used which is chosen from: AGRUMEX LC; AGRUNITRIL; ALDEHYD C11 UNDECYLENIC; ALDEHYD C12 LAURIN; ALDEHYD C12MNA; ALDEHYD C14 SOG; ALDEHYD C16 SOG.; ALLYLAMYLGLYCOLAT; ALLYLCAPRONAT; ALLYLCYCLOHEXYLPROPIONAT; ALLYLHEPTYLAT; 10TEC; Krist.10% IPM; AMBROXIDE; ANETHOL NAT.EX STERNANIS; ANISALDEHYD REIN; BENZYLACETON; BENZYLSALICYLAT; BORNEOL L / ISOBORNEOL 65 / 35; BUCCOBLAETTEROEL; CITRONELLOL 950; CLONAL; CYCLOHEXYLSALICYLAT; CYMOL PARA SUPRA; DAMASCONE DELTA; DIHYDROMYRCENOL; DIMETHYLBENZYLCARBINYLBUTYRAT; DYNASCONE; ETHYLENBRASSYLAT; ETHYLMETHYLBUTYRAT-2; ETHYLSAFRANAT; EUCALYPTOL NAT.; FENCHELOEL AROMA TYP SUESS NAT.; FILBERTONE 10% IPM; FILBERTONE; FLOROPAL; GALBASCONE; GERANIOL 60; 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<10PPM); LEMONILE; LIGUSTRAL; LILIAL; LINALOOL; MANZANATE; MELONAL; METHYLHEPTINCARBONAT; METHYLOCTINCARBONAT; MUSCENONE; NEOCYCLOCITRAL; NEROLIN BROMELIA; NEROLIN YARA YARA KRIST.; NEROLIONE; NORLIMBANOL; ORANGENOEL; ORIVONE; OZONIL; PATCHOULIOEL ENTF.; PFLANZENOEL TRIGLYCERID; PHELLANDRENFRAKTION EX EUKALYPTUSOEL; PHENYLETHYLACETAT; ROSENOXID HIGHCIS; STYROLYLACETAT; TERPINEN GAMMA; TETRAHYDROLINALOOL; TIMBERSILK; TRIETHYLCITRAT; UNDECAVERTOL; VERTTOCITRAL; VERTOFIX; K and mixtures of the above active ingredients.

[0256] Exemplary cooling agents used as hydrophobic active ingredients in the preparation of microcapsules according to the present invention include one or more menthol and menthol derivatives (e.g., L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), menthyl ethers (e.g., (1-menthoxy)-2-propanediol, (1-menthoxy)-2-methyl-1,2-propanediol, 1-menthyl methyl ether), menthyl esters (e.g., menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl lactate, L-menthyl lactate, menthyl acetate, menthyl isobutyrate, menthyl lactate, menthyl lactate, menthyl acetate ... Menthyl esters, D-lactate L-menthyl, (2-methoxy)-menthyl acetate, (2-methoxyethoxy)menthyl acetate, pyroglutamic acid menthyl), menthyl carbonates (e.g. propylene glycol menthyl carbonate, ethylene glycol menthyl carbonate, glycerol menthyl carbonate or mixtures thereof), half esters of menthol and dicarboxylic acids or derivatives thereof (e.g. monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinic acid-N,N-(dimethyl)amide (O-Menthylsuccinat-N,N-(dimethyl)amide) -(dimethyl)amid), O-menthylsuccinamide, menthanecarboxylic acid amides (e.g., menthanecarboxylic acid-N-ethylamide [WS3], N-α-(methanecarbonyl)glycine ethyl ester [WS5], menthanecarboxylic acid-N-(4-cyanophenyl)-amide, menthanecarboxylic acid N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)butyric acid derivatives Bioagents (e.g. 2,3-dimethyl-2-(2-propyl)-butyric acid-N-methylamide [WS23]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g. p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g. 3-methyl)-2-(1-pyrrolidinyl)-2-cyclopenten-1-one) or tetrahydropyrimidin-2-one (e.g. Icilin or related compounds as described in WO 2004 / 026840). Other cooling agents are menthol (L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), L-menthyl methyl ether, menthyl formate, menthyl acetate), menthone, isopulegol, acetate L-(-)-isopulegol ester) and cubeb, which have a cooling seasoning 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).

[0257] In an alternative variant, a TRPV1 or TRPV3 modulator is used as the active ingredient to be encapsulated or as the core material in the plant protein-based microcapsules according to the invention. TRPV1 and TRPV3 modulators are known in the prior art and refer to TRP channels (transient receptor potential channels) of the vanilloid (TRPV) subfamily. TRPV1 modulators impart a spicy taste and the sensation of heat associated with capsaicin and piperine. TRPV3 proteins belong to a family of non-selective cation channels that play a role in various processes including temperature sensation and vascular regulation. TRPV3 channels are directly activated by a variety of natural compounds such as carvacrol, thymol and eugenol. Some other monoterpenoids that either cause a warm sensation or are skin sensitizers can also open the channel. Monoterpenoids can also induce agonist-specific desensitization of TRPV3 channels in a calcium-independent manner.

[0258] In a further variant, active substances are used as the active substances to be encapsulated or as the core material in the vegetable protein-based microcapsules according to the invention, which are selected from substances that cause a pungent taste or a warm or hot sensation on the skin or mucous membranes, or substances that cause a tingling or tingling sensation in the mouth or throat, or substances with a pungent or irritating or astringent effect.

[0259] The heat-inducing or pungent active ingredients are preferably selected from the group consisting of red pepper powder, chili pepper powder, red pepper extract, pepper extract, chili pepper extract, ginger root extract, extract of Aframomummelegueta, extract of bahia grass (Jambu-Oleoresin; Spilanthes acmella or Spilanthes oleracea), extract of Zanthoxylum piperitum, extract of Kaempferia galanga, extract of Polygonium extracts of capsaicinoids, in particular capsaicin, dihydrocapsaicin or synthetic capsaicin; gingerols, in particular gingerol-[6], gingerol-[8] or gingerol-

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

[10] ; gingerdiones, in particular gingerdione-[6], gingerdione-[8] or gingerdione-

[10] ; paradols, in particular gingerdione-[6], gingerdione-[8] or gingerdione-

[10] ; dehydrogingerdiones, in particular dehydrogingerdione-[6], dehydrogingerdione-[8] or dehydrogingerdione-

[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.

[0260] The active ingredients perceived as pungent or irritating are preferably selected from the group consisting of aromatic isothiocyanates, in particular phenethyl isothiocyanate, allyl isothiocyanate, cyclopropyl isothiocyanate, butyl isothiocyanate, 3-methylthiopropyl isothiocyanate, 4-hydroxybenzyl isothiocyanate, 4-methoxybenzyl isothiocyanate and mixtures thereof.

[0261] The stinging agent is preferably selected from: 2E,4E-decadienoic acid-N-isobutylamide (trans-serrulate chrysanthemum lysine), in particular as described in WO 2004 / 043906; 2E,4Z-decadienoic acid-N-isobutylamide (cis-serrulate chrysanthemum lysine), in particular as described in WO Those described in 2004 / 000787; 2Z,4Z-decadienoic acid-N-isobutylamide; 2Z,4E-decadienoic acid-N-isobutylamide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic 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 (Achilleamid); 2E,4E-decadienoic acid-N-piperid (Achilleamid); Sarmentin); 2E-decenoic acid-N-isobutylamide; 3E-decenoic acid-N-isobutylamide; 3E-nonenoic acid-N-isobutylamide; 2E,6Z,8E-decatrienoic acid-N-isobutylamide (Spilanthol); 2E,6Z,8E-decatrienoic acid-N-([2S]-2-methylbutyl)amide (Homospilanthol); 2E,6Z,8E-decatrienoic acid-N-([2R]-2-methylbutyl)amide; 2E-decene-4-ynoic acid-N-isobutylamide; 2Z-decene-4-ynoic acid-N-isobutylamide; 2E,6Z,8E,10E-docotetraenoic acid-N-(2-methylpropyl)amide (α-Sanshool); 2E,6Z,8E,10E-docotetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (α-hydroxysanshool); 2E,6E,8E,10E-docotetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (γ-hydroxysanshool); 2E,4E,8Z,10E,12E-tetradecotetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (γ-hydroxysanshool); 2E,4E,8E,10E,12E-tetradecotetraenoic acid- N-(2-Hydroxy-2-methylpropyl)amide (γ-hydroxyiso-zanthoxycin); 2E,4E,8Z,10E,12E-tetradecanoic acid-N-(2-methyl-2-propenyl)amide (γ-dehydrozanthoxycin); 2E,4E,8Z,10E,12E-tetradecanoic acid-N-(2-methylpropyl)amide (γ-zanthoxycin); 2E,4E,8Z,11Z-tetradecanoic acid-N-(2-hydroxy-2-methylpropyl)amide (bungeanool); 2E,4E,8Z,11E-tetradecanoic acid-N-(2-hydroxy-2-methylpropyl)amide (iso-zanthoxycin);2E,4E,8Z-tetradecadienoic acid-N-(2-hydroxy-2-methylpropyl)amide (dihydrozanthoxylum bungeanum) and 2E,4E-tetradecadienoic acid-N-(2-hydroxy-2-methylpropyl)amide (tetrahydrozanthoxylum bungeanum) and mixtures thereof. ;

[0262] The active ingredient with astringent action is preferably selected from the group consisting of: catechins, in particular epicatechin, gallocatechin, epigallocatechin and their respective gallic acid esters, in particular epigallocatechin gallate or epicatechin gallate, their oligomers (proanthocyanidins, proanthocyanidins, proanthocyanidins, procyanidins, thearubigenine, thearubigenin) and 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 quercetin, rutin, carbohydrate gallic acid esters, for example tannins, pentagalloyl glucose or their reaction products, for example elligatannin, aluminum salts, for example alum and mixtures thereof.

[0263] In a further variant of the first and / or second aspect of the invention, the biogenin may also be encapsulated as a core material, wherein the core material comprises at least one biogenin or a mixture thereof.

[0264] Biogenins are biologically active ingredients such as tocopherol, tocopheryl acetate, tocopheryl palmitate, ascorbic acid, carnotin, carnosine, caffeine, (deoxy)ribonucleic acid and its cleavage products, beta-glucan, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

[0265] In a further variant of the method according to the invention, substances used for paper printing coatings are also used as the active ingredient to be encapsulated or as the core material, as described in US Pat. No. 2,800,457 A, the relevant disclosure of which is incorporated by reference in its entirety into the present specification.

[0266] The inner 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 hydrophobic 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 additionally up to 100% by weight of a hydrophobic solvent, based on the total weight of the inner non-aqueous phase.

[0267] Thus, a high loading of the vegetable protein-based microcapsules according to the invention with active ingredients can be achieved using the method according to the invention.

[0268] In a further step (ii) of the process according to the invention, an external aqueous phase is provided which comprises at least one vegetable protein,

[0269] and optionally at least one first polysaccharide and / or at least one additional cross-linking agent and / or at least one polyhydroxyphenol and / or at least one protective colloid, and further optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the vegetable protein.

[0270] The polyhydroxyphenol optionally added in step (ii) may also be a further crosslinking agent. The polyhydroxyphenol may also be a crosslinking agent itself. Optionally, the polyhydroxyphenol may be added alternatively or additionally in step (i). The polyhydroxyphenol is also preferably a tannin.

[0271] In a preferred embodiment of the present invention, an external aqueous phase may be provided in step (ii), which comprises at least one vegetable protein and at least one first polysaccharide.

[0272] In case an external aqueous phase comprising at least one vegetable protein and at least one first polysaccharide is provided in step (ii), the vegetable protein is particularly preferred, wherein the vegetable protein is preferably selected from pea protein, sunflower protein, pumpkin protein or soy protein.

[0273] In case an external aqueous phase comprising at least one vegetable protein and at least one first polysaccharide is provided in step (ii), the at least one first polysaccharide is particularly preferably carboxymethylcellulose (CMC) and / or pectin.

[0274] The pectin is preferably a highly esterified pectin, which preferably has a degree of esterification of at least 50%, particularly preferably >68%.

[0275] Suitable solvents for preparing the external aqueous phase are water or a mixture of water and at least one water-miscible organic solvent. Suitable organic solvents are, for example, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol and other analogs. However, the solvent is preferably water.

[0276] According to the invention, the at least one vegetable protein or the at least one additional vegetable protein is chosen from protein isolates, vegetable proteins in fraction form, partial or complete hydrolysates or intermediates produced by physicochemical processes or fermentation or enzymatic treatment of proteins, in particular vegetable proteins from the group consisting of cereals, in particular wheat, barley, rye, spelt, gluten, in particular wheat gluten, rapeseed, rice, potato, corn, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, bean, pea, pumpkin and sunflower, other proteins from edible plants, chitosan and mixtures thereof.

[0277] The at least one vegetable protein is particularly preferably selected from pumpkin protein, soy protein, sunflower protein and pea protein. The at least one vegetable protein is particularly preferably pumpkin protein. These have particularly good stability. Alternatively, soy protein and pumpkin protein are also preferred due to their organoleptic properties.

[0278] Among the abovementioned proteins, pea, pumpkin, soybean and sunflower are particularly preferred. In combination with aliphatic polyisocyanates as crosslinkers, they are particularly suitable for obtaining vegan microcapsules which are characterized by particularly high stability and good organoleptic properties.

[0279] The amino acid may be a proteinogenic L-amino acid. These may be selected from 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.

[0280] The above-mentioned proteins also have the advantageous effect that they have an emulsifying effect. Due to their emulsifying effect, they contribute to stabilizing the emulsion. Due to their more or less flexible structure and the fact that they have regions with different charges within the molecule, proteins are amphipathic and therefore surface-active. By modifying the proteins, for example by physical or chemical modification, the secondary and / or tertiary structure of the molecule can be altered. This can affect the emulsifying properties by changing the spatial availability of the charged regions of the molecule or by exposing the amino acid side chains. Due to these advantageous properties, additional emulsifiers or protective colloids can be omitted in the method according to the invention.

[0281] The proportion of the at least one protein, preferably pea protein, pumpkin 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.

[0282] According to a further aspect of the present invention, the at least one first polysaccharide and / or the at least one further polysaccharide may be selected from

[0283] - indigestible fibres and dietary fibres, in particular insoluble dietary fibres, in particular cellulose, cellulose derivatives, such as hydroxyethylcellulose, in particular quaternized hydroxyethylcellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), hemicelluloses, lichenin, chitin, chitosan, lignin, xanthan gum, vegetable fibres, in particular cereal fibres, potato fibre, apple fibre, citrus fibre, bamboo fibre, extracted beet fibre; oat fibre and soluble dietary fibres, in particular inulin, in particular natural inulin, highly soluble inulin, granulated inulin, high-performance inulin, pectin, alginates, agar, carrageenan, tragacanth, gum arabic, konjac gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, dextran and lactulose;

[0284] - 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 fructo-oligosaccharides; and

[0285] - sugar alcohols, in particular sorbitol, mannitol, isomalt, maltitol, maltitol syrup, lactitol, xylitol, erythritol;

[0286] - Gellan gum; glucose,

[0287] - Glycosaminoglycans, especially hyaluronic acid

[0288] and mixtures of the above polysaccharides.

[0289] Among the above polysaccharides, gum arabic and maltodextrin are particularly preferred. The most preferred are maltodextrin DE8-10 potato; DE17-20 corn; DE8-10 corn; DE17-20 potato and DE18-20 wheat.

[0290] In a particularly advantageous further development of the invention, it can be provided that the at least one first polysaccharide and / or the at least one further polysaccharide are selected from hyaluronic acid, carrageenan, gellan gum, agar, alginates, xanthan gum. In this way, microcapsules based on vegetable proteins are obtained with very good organoleptic properties.

[0291] In particular, it can 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.

[0292] The proportion of the at least one polysaccharide in the external aqueous phase is in the range of 0.1 to 3.0 wt.-%, preferably in the range of 0.2 to 1.0 wt.-%, based on the total weight of the external aqueous phase. Most preferably, the at least one polysaccharide is in the range of 0.25 to 0.75 wt.-%, based on the total weight of the external aqueous phase.

[0293] Preferably, the outer aqueous phase is provided with the two main components of the capsule shell, namely at least one protein and at least one polysaccharide. The combined use of protein and polysaccharide leads to the formation of soluble or insoluble protein-polysaccharide complexes. The emulsion formed in this way has a lower tendency to form aggregates, so that in the method according to the invention, no protective colloid or additional emulsifier needs to be added.

[0294] The following combinations of proteins and polysaccharides are particularly preferred for constructing the capsule wall or capsule shell: pea protein and maltodextrin; pumpkin protein and maltodextrin; sunflower protein and maltodextrin; soy protein and maltodextrin.

[0295] The components, proteins and polysaccharides, described above and exemplified for the capsule wall structure can be readily obtained from biological sources. In addition, they themselves are also readily biodegradable.

[0296] In an alternative variant of the process according to the invention, the external aqueous phase is provided with only one of the main components of the capsule shell, a protein or a polysaccharide. In this variant, the other main component, a polysaccharide or a protein, is optionally added in process step (iv) and / or step (vi) after emulsification / dispersion and before or simultaneously with the addition of the catalyst, the addition of the catalyst being optionally carried out in process step (v).

[0297] 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 polyisocyanate content.

[0298] Surprisingly, however, this lower degree of crosslinking leads on the one hand to stable microcapsules and on the other hand to microcapsules with improved biodegradability, as is illustrated in the following exemplary embodiments.

[0299] Protective colloids may optionally be added to the external aqueous phase.

[0300] A protective colloid is a polymer system which prevents the aggregation (agglomeration, coagulation, flocculation) of the emulsified, suspended or dispersed components in a suspension or dispersion. During solvation, the protective colloid binds large amounts of water and produces high viscosities in aqueous solutions, depending on the concentration. During the preparation of an oil-in-water emulsion, the hydrophobic part of the protective colloid attaches itself to the primary particles and diverts the polar (i.e. hydrophilic) part of its molecules towards the aqueous phase. By attaching to the interface in this way, it reduces the interfacial tension and prevents the agglomeration of the primary particles. It also stabilizes the emulsion and promotes the formation of relatively small droplets and thus the formation of corresponding microcapsules.

[0301] In the process according to the invention, the protective colloid has, in addition to the above-mentioned properties, emulsifying properties. If the protective colloid, for example carboxymethylcellulose (CMC), acid-modified starch, polyvinyl alcohol, ammonium derivatives of polyvinyl alcohol, polystyrene sulfonates, polyvinyl pyrrolidone, polyvinyl acrylate, has sufficient emulsifying properties, in the process according to the invention it is even advantageously possible to dispense with the use of emulsifiers in the downstream emulsification / dispersion step (iii).

[0302] The protective colloid used in the process according to the invention is selected from the group consisting of

[0303] - diols, in particular ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, isobutylene glycols, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and

[0304] polyols, preferably triols, in particular glycerol and ethoxylation products thereof, trimethylolpropane and ethoxylation products thereof, polyvinyl alcohol (PVOH) and derivatives thereof, in particular ammonium-functionalized or sulfonate-functionalized polyvinyl alcohol, polyphenols, preferably 1,3,5-trihydroxybenzene, polysaccharides, in particular glucose, starch or chemically, mechanically and / or enzymatically modified starch, cellulose derivatives, for example hydroxyethylcellulose, in particular quaternized hydroxyethylcellulose, and carboxymethylcellulose,

[0305] - polyvinyl pyrrolidone, maleic acid vinyl copolymer, sodium lignin sulfonate, maleic anhydride / styrene copolymer, ethylene / maleic anhydride copolymer, copolymers of ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitan, sodium lauryl sulfate,

[0306] - vegetable polymers, in particular gum arabic (Senegal and Seyal types), mastic, shellac, lignin, chitosan, saponins

[0307] and mixtures of the above compounds.

[0308] Starch, in particular modified starch or plant polymers, is a biodegradable naturally occurring substance. In combination with the polyisocyanates described herein, the present method can therefore provide a bio-based and biodegradable capsule shell. Therefore, in the method according to the invention, the starch and the plant polymer also act as a so-called biocrosslinker.

[0309] 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.

[0310] The chemically modified starch is preferably acid-modified starch, alkali-modified starch, oxidized starch, acetylated starch, succinate-esterified starch or octenylsuccinate-esterified starch.

[0311] Preferably, the external aqueous phase comprises at least one protective colloid chosen from polyvinyl pyrrolidone, polyvinyl alcohol, polyols, polyphenols or starch and mixtures thereof.

[0312] Even more preferably, polyols, polyphenols or starch, in particular modified starch, are used as protective colloid. For the preparation of the microcapsules according to the invention, particular preference is given to using polyvinyl alcohol or its ammonium derivatives, 1,3,5-trihydroxybenzene, modified starch or carboxymethylcellulose as protective colloid.

[0313] According to the invention, combinations of two or more different protective colloids can also be used for the preparation of the microcapsules according to the invention.

[0314] It has proven to be particularly advantageous to use, in the process according to the invention, one of the above-mentioned protective colloids in combination with starch as a further protective colloid in the external aqueous phase. Due to the large number of functional hydroxyl groups, this combination stabilizes the emulsion and, on the other hand, promotes the reaction between the protective colloid and the one or more polyisocyanates, thereby shifting the reaction equilibrium in the reaction of the protective colloid with the one or more polyisocyanates towards the product, i.e. the polyurethane. In addition, the large number of functional hydroxyl groups in starch also allows the formation of particularly pronounced steric crosslinks.

[0315] Depending on the number of functional groups and / or the size of the protective colloid, the protective colloids described above have different reaction rates with the isocyanate groups of the at least one polyisocyanate. For example, glycerol, due to its size, reacts faster with the isocyanate groups than starch. Thus, the crosslinking of the protective colloid with the isocyanate groups of the polyisocyanate can be controlled by selecting the protective colloid.

[0316] The combination of glycerol with starch or with modified starch or glycerol with quaternized hydroxyethylcellulose or gum arabic of the Seychelles type has proven to be a particularly advantageous combination; this combination exploits the above-mentioned properties of the two protective colloids: on the one hand, the high reaction rate of glycerol and on the other hand, the number of polymerizable functional groups of the other protective colloid.

[0317] The protective colloids used in the process according to the invention have a dual function, i.e. on the one hand they act as protective colloids and thus prevent agglomeration of the emulsified, suspended or dispersed components, stabilize the subsequently formed emulsion, promote the formation of small droplets and stabilize the microcapsule dispersion finally formed.

[0318] The external aqueous phase is preferably prepared by adding the polysaccharide and / or the protein and optionally the protective colloid successively (or vice versa) to the external aqueous phase, or by adding the components simultaneously to the external aqueous phase, under stirring.

[0319] To improve the solubility of the protein, the pH of the external aqueous phase is optionally adjusted to a pH below the isoelectric point of the protein, ie to a pH below the isoelectric point of the protein used.

[0320] The isoelectric point is the pH value at which the isoelectric state is reached, i.e., the pH value at which the positive and negative charges of amphoteric electrolytes or zwitterions (e.g., amino acids and proteins) are in equilibrium. This value is a characteristic constant for each amino acid and depends on the pK of the functional group. a In addition to amino acids, peptides and proteins also have an isoelectric point. At the isoelectric point, amino acids and therefore also proteins have the lowest water solubility.

[0321] Preferably, the pH of the aqueous phase is adjusted to a 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, and most preferably to a weakly acidic 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 at such a pH value, the emulsifying properties and solubility of the protein are maximal.

[0322] The pH 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 prior to the emulsification step and the pH is set within the above range.

[0323] The inner non-aqueous phase comprising at least one crosslinker and at least one hydrophobic active ingredient is emulsified or dispersed in the outer aqueous phase in a further process step (iii) to form an oil-in-water emulsion / dispersion.

[0324] The oil-in-water emulsion is prepared by mixing the inner non-aqueous phase and the outer aqueous phase. The weight ratio of the inner non-aqueous phase to the outer aqueous phase is preferably in the range of 70:30 to 60:40, preferably in the range of 30:70 to 60:40.

[0325] In order to promote the formation of an emulsion or dispersion by an internal non-aqueous phase and an external aqueous phase, to stabilize the formed emulsion or dispersion and to prevent separation of the internal non-aqueous (oily / organic / hydrophobic) phase and the external aqueous (hydrophilic) phase, in the method according to the invention, a stabilizer and / or an emulsifier or an emulsification aid is optionally added to the emulsion or dispersion.

[0326] In order to prevent separation of the inner non-aqueous (oil) phase and the outer aqueous phase, a stabilizer is preferably added to the outer aqueous phase to stabilize the emulsion / dispersion.

[0327] Preferred stabilizers for the preparation of polysaccharide and protein-based microcapsules according to the invention are in particular acrylic copolymers having sulfonate groups. Also suitable are copolymers of acrylamide and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, for example K15, K30 or K90 (BASF), sodium polycarboxylate, sodium polystyrene sulfonate, vinyl and methyl vinyl ether maleic anhydride copolymers and ethylene, isobutylene or styrene maleic anhydride copolymers, microcrystalline cellulose (e.g. sold under the name of ), Diutan Gum, xanthan gum or carboxymethyl cellulose.

[0328] Stabilizers can be used in amounts in the range from 0.01 to 10% by weight and preferably in the range from 0.1 to 3% by weight, based in each case on the external aqueous phase.

[0329] Optionally, an emulsifier is used in the process according to the invention, preferably an O / W emulsifier, which enables a homogeneous distribution of the oil droplets of the inner non-aqueous phase in the outer aqueous phase and stabilizes the emulsion. The same applies in the case of mixing solid, insoluble active ingredients in the outer aqueous phase in order to stabilize the dispersion obtained.

[0330] The addition of emulsifiers is optional, in particular if the protein or the protective colloid has no or only low, ie insufficient, emulsifying properties. If emulsifying proteins and / or protective colloids are used, the use of emulsifiers can advantageously be omitted in the process according to the invention.

[0331] Suitable emulsifiers include nonionic surfactants from at least one of the following groups:

[0332] - addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide onto linear fatty alcohols having 8 to 22 C atoms, onto fatty acids having 12 to 22 C atoms, onto alkylphenols having 8 to 15 C atoms in the alkyl radical and onto alkylamines having 8 to 22 carbon atoms in the alkyl radical;

[0333] - alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alkyl(alkenyl) group and their ethoxylated analogs;

[0334] - addition products of 1 to 15 mol of ethylene oxide onto castor oil and / or hardened castor oil;

[0335] - addition products of 15 to 60 mol of ethylene oxide onto castor oil and / or hardened castor oil;

[0336] - 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 adducts thereof with 1 to 30 mol of ethylene oxide;

[0337] - partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 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 and adducts thereof with 1 to 30 mol of ethylene oxide, preferably

[0338] - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol;

[0339] - mono-, di- and tri-alkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

[0340] - lanolin alcohol;

[0341] - polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

[0342] Block copolymers, such as polyethylene glycol-30 dipolyhydroxystearate;

[0343] Polymeric emulsifiers, such as the Pemulen types (TR-1, TR-2) from Goodrich or SP;

[0344] - Polyalkylene glycols and glycerol carbonate.

[0345] Typical anionic emulsifiers which can be used in the process according to the invention for preparing isocyanate-based microcapsules are aliphatic fatty acids having 12 to 22 carbon atoms, for example palmitic acid, stearic acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, for example azelaic acid or sebacic acid.

[0346] In addition, zwitterionic surfactants can be used as emulsifiers for preparing the polysaccharide and protein-based microcapsules in the method according to the invention. Zwitterionic surfactants are surface-active compounds with at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are so-called betaines, such as N-alkyl-N, N-dimethyl ammonium glycinates, such as coconut oil alkyl dimethyl ammonium glycinates, N-acylaminopropyl-N, N-dimethyl ammonium glycinates, such as coconut oil acyl aminopropyl dimethyl ammonium glycinates, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazoline, each of which has 8 to 18 C atoms in the alkyl or acyl group, and coconut oil acyl aminoethyl hydroxyethyl carboxymethyl glycinate (Kokosacylaminoethylhydroxyethylcarboxymethylglycinate). Particularly preferred are fatty acid amide derivatives known by the CTFA name cocoamidopropyl betaine.

[0347] Amphoteric surfactants are also suitable emulsifiers. Amphoteric surfactants are understood to be those surface-active compounds that contain at least one free amino group and at least one-COOH or-SO3H group and can form inner salts in addition to the C8 / 18 alkyl or acyl group in the molecule. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each of which has about 8 to 18 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, cocoacylaminoethylaminopropionate and C12 / 18-acylsarcosine.

[0348] Finally, cationic surfactants may also be used as emulsifiers, of which those of the esterquat type are particularly preferred, 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, cetyldimethylbenzyl ammonium chloride, cetylpyridinium chloride, cetyltrimethylammonium bromide (cetrimonium bromide), dequalinium chloride is particularly preferred.

[0349] The emulsifiers can be added to the external aqueous phase in an amount of about 0.1 to about 10% by weight and preferably about 1 to about 5% by weight, based in each case on the total weight of the external aqueous phase.

[0350] The emulsion formation (for liquid active ingredients) or dispersion formation (for solid active ingredients), i.e. the emulsification or dispersion of the inner non-aqueous or oil phase with the outer aqueous or hydrophilic phase, is carried out under high turbulence or high shear, whereby the intensity of the turbulence or shear determines the diameter of the microcapsules obtained. The preparation of the microcapsules can be carried out continuously or discontinuously. With increasing viscosity of the aqueous phase or decreasing viscosity of the oil phase, the size of the capsules generally decreases.

[0351] The method according to the invention for preparing microcapsules based on polysaccharides and proteins can be carried out, for example, using the "inline" technology. In this process, the inner non-aqueous phase and the outer aqueous phase are first fed separately into an emulsification turbine by means of a forced metering pump and are combined shortly before entering the emulsification turbine or in the emulsification turbine, with a flow volume of 1200 to 1500 l / h. In addition, the method according to the invention for preparing microcapsules based on polysaccharides and proteins can also be carried out in conventional dispersing devices or emulsification devices.

[0352] To prepare the microcapsules according to the invention, the emulsification or dispersion of the external aqueous phase and the internal non-aqueous phase is carried out, for example, with the aid of an emulsifying turbine (IKA Eurostar 20 high-speed stirrer).

[0353] The process of emulsification or dispersion in the method according to the invention is advantageously carried out at a stirring speed of 1000 to 5000 rpm, preferably at 2000 to 4000 rpm, for a period of 30 seconds to 20 minutes, preferably 1 to 7 minutes, and most preferably 1 to 5 minutes, until a capsule size of 10 to 75 μm ± 5 μm (D50) or 75-155 ± 10 μm (D90) has been achieved.

[0354] After the emulsification or dispersion step (iii) is completed, there is an oil-in-water emulsion or dispersion in which the inner oil phase having the active ingredient to be encapsulated is finely emulsified or dispersed in the outer water phase in the form of droplets.

[0355] In an alternative variant of the method according to the invention, as described above, at least one polysaccharide or at least one protein is optionally added in method step (iv) after the emulsification or dispersion step (iii). If in method step (ii), the external aqueous phase is provided with only at least one main protein component, at least one polysaccharide is added in method step (iv). On the other hand, if in method step (ii), the external aqueous phase is provided with only at least one polysaccharide main component, at least one protein is added in method step (iv). The separate addition leads to the formation of multiple layers ("layer by layer"), the individual layers of which are cross-linked to each other in the subsequent method step (v). This makes it possible, for example, to control the charge of the emulsion and thus the aggregation stability.

[0356] Alternatively, a further protein and / or polysaccharide can optionally be added in process step (iv), which is identical or different from the at least one protein and / or at least one polysaccharide from process step (ii) or has a different charge or changes its charge when the pH value changes. By adding a further protein and / or polysaccharide, further layers are built up ("layer by layer"), the individual layers of which are cross-linked with one another in the subsequent process step (v). This leads to a denser and more stable network of the capsule wall components and thus to the formation of a more stable capsule shell, which increases the stability of the microcapsules.

[0357] In a further preferred embodiment of the present invention, it can therefore be provided that at least one polysaccharide and / or at least one protein is added in process step (iv).

[0358] The additional proteins and / or additional polysaccharides are selected from the vegetable proteins and / or polysaccharides as already defined in detail above for process step (ii). The same applies to the preferred variants or preferred combinations of the vegetable proteins and / or polysaccharides described therein.

[0359] In a further preferred embodiment of the present invention, an external aqueous phase comprising at least one vegetable protein and at least one first polysaccharide can be provided in step (ii), and at least one polysaccharide and / or at least one protein can additionally be added in step (iv).

[0360] Particularly preferably, it can be provided that in step (ii) an external aqueous phase comprising at least one vegetable protein and at least one first polysaccharide is provided, and in process step (iv) at least one polysaccharide and / or at least one protein is additionally added, wherein the at least one vegetable protein in step (ii) and in step (iv) is preferably selected from pea protein, pumpkin protein, soy protein or sunflower protein, and wherein the at least one polysaccharide in step (ii) and in step (iv) is pectin and / or carboxymethylcellulose (CMC).

[0361] The pectin is preferably a highly esterified pectin, preferably having a degree of esterification of at least 50%, particularly preferably a degree of esterification of >68%.

[0362] In the subsequent process step (v) of the process according to the invention, a first crosslinking of the material of the capsule shell or capsule wall is also carried out under stirring.

[0363] The first crosslinking takes place after emulsification or dispersion, optionally by addition of a catalyst, to crosslink the above-mentioned layers of capsule wall components ("layer by layer") and stabilize the resulting capsule shell. At the interface between the external aqueous phase and the dispersed internal phase, i.e. at the interface of the emulsified or dispersed oil droplets surrounding the active ingredient to be encapsulated, a catalytic polymerization reaction is formed by interfacial polymerization between the carboxyl and / or sulfonyl and / or hydroxyl groups of the polysaccharide on the one hand and the amino groups of the protein on the other hand and the isocyanate groups of the crosslinking agent.

[0364] Therefore, in a further embodiment of the present invention, it can be provided that in step (v) the first crosslinking is carried out by adding at least one catalyst to obtain a microcapsule slurry; wherein the at least one catalyst is selected from diazabicyclo[2.2.2]octane (DABCO), bismuth catalysts and tin catalysts and mixtures of two or more of the above catalysts.

[0365] Due to the catalytic crosslinking between the functional groups of the at least one polysaccharide and / or at least one vegetable protein of the above layer and the functional groups of the crosslinking agent, a first crosslinking unit or a first crosslinking matrix is ​​formed for constructing the capsule shell or capsule wall.

[0366] In the method according to the invention, the first crosslinking unit is formed based on a polyaddition reaction between a polysaccharide and a crosslinking agent and / or a vegetable protein and a crosslinking agent. In this method, 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 vegetable proteins and polysaccharides are formed during the first crosslinking step (v) to form the capsule wall matrix or capsule shell.

[0367] The greater the number of crosslinking functional groups of the capsule wall building blocks, the greater the spatial crosslinking, and the denser and more stable the capsule shell or capsule wall of the resulting microcapsule. In addition to the number of functional groups, the chain length of the individual capsule wall building blocks also significantly affects the mechanical properties of the microcapsules, i.e., the stability: for example, the large number of hydroxyl groups in starch enables the formation of particularly pronounced spatial crosslinks; longer chain capsule wall building blocks, such as polyisocyanates, lead to the formation of more stable capsule walls.

[0368] By forming the first cross-linked matrix or the first cross-linked unit, the emulsified or dispersed oil droplets having the core material (i.e., the encapsulated active ingredient) are surrounded by the cross-linked matrix or the cross-linked unit on the outside located at the interface, thereby generating a capsule wall, which makes diffusion of the encapsulated active ingredient more difficult.

[0369] Adding the at least one catalyst to the emulsion or dispersion accelerates the cross-linking reaction between the polysaccharide and / or vegetable protein and the cross-linking agent and catalyzes the reaction in a manner that favors the formation of a first cross-linking matrix or first cross-linking unit.

[0370] The catalyst that can be added in the method according to the present invention can preferably be diazabicyclo [2.2.2] octane (DABCO), which is also known as triethylenediamine (TEDA), a bicyclic tertiary amine. DABCO is generally used as a catalyst for preparing polyurethane plastics. Tertiary amines with free electron pairs are beneficial to the reaction between the isocyanate groups of the crosslinking agent and the hydroxyl groups of the polysaccharide.

[0371] In addition to DABCO, catalysts based on bismuth or tin, for example catalysts based on bismuth(II) salts or bismuth(III) salts, as described in KC Frisch & L.P. Rumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5:1, pp. 103-149, DOI: 10.1080 / 15583727008085365, the disclosure of which in this respect is incorporated in its entirety into the present description.

[0372] Preferably, a combination of DABCO and one of the above catalysts can be used. Such a mixture leads to a multiplication of reactivity, as described in the following document: KC Frisch & L.P. Rumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5: 1, pp. 103-149, DOI: 10.1080 / 15583727008085365, the disclosure of which is incorporated into this specification in its entirety.

[0373] In the process according to the invention, DABCO and the above-mentioned catalyst preferably catalyze the polyurethane reaction between the at least one polymerizable aliphatic polyisocyanate having two or more isocyanate groups and the diol or polyol.

[0374] In one embodiment of the process according to the invention, the catalyst can be added to the external aqueous phase. It can be provided that the amount of catalyst added to the external aqueous phase is in the range of 0.001 to 2% by weight, preferably in the range of 0.02 to 1.0% by weight, and particularly preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the external aqueous phase.

[0375] However, larger amounts of catalyst may be added if desired.

[0376] Preferably, the catalyst itself (for example as a solid) or in the form of an aqueous solution (preferably in water) is added to the emulsion or dispersion under stirring. It can be provided that the amount of the catalyst is in the range of 0.001 to 2% by weight, preferably in the range of 0.02 to 1.0% by weight, and particularly preferably in the range of 0.05 to 0.8% by weight, based on the total weight of the external aqueous phase.

[0377] Preferably, it can be provided that the catalyst is present in the aqueous solution in a concentration of 0.5 to 2 mol / l, preferably 1 mol / l.

[0378] The catalyst is added at a stirring speed of 500 to 2000 rpm, preferably at 1000 to 1500 rpm and at a temperature in the range of 20 to 30°C, preferably at a temperature of 22 to 26°C.

[0379] Even more preferably, the first crosslinking of step (v) of the process is carried out by gradually heating the emulsion or dispersion to a temperature in the range of 60 to 90° C., preferably to a temperature in the range of 65 to 85° C., most preferably to a temperature in the range of 70 to 80° C. The first crosslinking in the process according to the invention is carried out for a time of about 30 to 90 minutes, preferably for a time of 40 to 70 minutes, and most preferably for a time of 60 minutes.

[0380] In a further embodiment of the present method, the first crosslinking may be carried out at a temperature of 20°C to 40°C, preferably 20°C to 30°C, in particular at room temperature.

[0381] After initial crosslinking and formation of the capsule shell or capsule wall, the capsules prepared according to the process of the invention are present as coarse microcapsules in the form of an aqueous dispersion or slurry.

[0382] After crosslinking, the microcapsules in the slurry still have a flexible shell which is not particularly stable and can therefore break easily. For this purpose, the shell is hardened. The hardening in process step (vi) is preferably carried out by gradually heating the microcapsule slurry to a temperature of at least 60° C., preferably a temperature in the range of 60° C. to 90° C., preferably a temperature in the range of 65° C. to 80° C., up to a maximum of the boiling point of the microcapsule slurry. The curing is generally carried out for a period of at least 1.5 hours, preferably for a period of 2 to 5 hours, most preferably for a period of 3 hours.

[0383] It is also advantageous to add a hardening substance to the microcapsule slurry. For this purpose, natural vegetable tannins of the tannin type are used, which, from a chemical point of view, are proanthocyanidins, which are found in dicotyledonous perennials, shrubs and leaves, especially in tropical and subtropical areas. Terpenes generally have a molecular weight in the range of 500 to 3000 KDa. A preferred example of a suitable tannin is Corigallin. For hardening, an aqueous preparation of the tannin is added to an aqueous dispersion containing the crude microcapsules. The amount of tannin added is generally about 0.1 to about 2% by weight, based on the microcapsules, and preferably about 0.5 to about 1.5% by weight.

[0384] In order to optimize the crosslinking of the capsule wall matrix, in an alternative variant of the process according to the invention, further vegetable proteins and / or further polysaccharides can optionally be added to the microcapsule slurry in process step (vi).

[0385] The additional vegetable proteins and / or additional polysaccharides are selected from the group consisting 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 vegetable proteins and / or polysaccharides are also fully valid for the additional vegetable proteins and / or polysaccharides.

[0386] The additional vegetable protein and / or the additional polysaccharide may be the same as or different from the vegetable protein and / or polysaccharide of process step (ii).

[0387] The addition of further vegetable proteins and / or further polysaccharides leads to further crosslinking with the crosslinking agent and contributes to the formation of a particularly dense and stable network of the capsule wall building blocks.

[0388] The curing step (vi) of the process according to the invention is followed by a step of cooling the microcapsule slurry to room temperature and a second crosslinking step of the capsule wall building units, optionally by adding a further crosslinking agent.

[0389] As additional crosslinking agent for further crosslinking in the method according to the invention, at least one additional crosslinking agent is used, which is selected from transglutaminases, peroxidases, secondary plant substances, which are selected from polyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the above crosslinking agents, as already described above for the first and additional crosslinking agents. The same definitions and preferred embodiments for the first crosslinking agent and the additional crosslinking agent are also fully valid for the additional crosslinking agent.

[0390] Among the above-mentioned other cross-linking agents, cinnamaldehyde, tannin, ferulic acid and gallic acid are particularly preferred.

[0391] The at least one further cross-linking agent may be added in the non-aqueous phase. Alternatively or additionally, the at least one further cross-linking agent may be added in the aqueous phase.

[0392] The additional crosslinking agent is present in an amount ranging from 0.1 to 5 wt %, preferably 0.15 to 2.5 wt %, based on the total weight of the non-aqueous phase. Most preferably, the crosslinking agent is present in an amount ranging from 0.1 to 1 wt %, based on the total weight of the non-aqueous phase, in the inner non-aqueous phase.

[0393] The additional crosslinking agent can be added to the emulsion or dispersion as such (eg as a solid) or in the form of an aqueous solution.

[0394] Even more preferably, the further crosslinking in process step (vii) is carried out by gradually heating the emulsion or dispersion to a temperature in the range of 20° C. to 50° C., preferably to a temperature in the range of 30° C. to 40° C. The further crosslinking in the process according to the invention is carried out for a time of about 20 minutes to 10 hours, preferably for a time of 30 minutes to 8 hours.

[0395] In order to optimize the first crosslinking in method step (v) and / or the further crosslinking in method step (vii) of the method according to the invention, the pH of the emulsion or dispersion is optionally adjusted to a pH value above or below the isoelectric point of the protein used. When the pH value is below the isoelectric point, the net electrostatic charge on the protein is positive; above the isoelectric point, the net charge on the protein is negative.

[0396] Preferably, the pH is adjusted to a pH in the range of pH 2.0 to pH 4.0, even more preferably to a pH in the range of pH 2.5 to pH 3.5, and most preferably to a pH in the range of pH 2.9 to pH 3.3, to obtain a positive charge of the protein. To obtain a negative charge of the protein, the pH is preferably adjusted to a pH in the range of pH 8.0 to pH 12.0, even more preferably to a pH in the range of pH 9.0 to pH 10.0, and most preferably to a pH in the range of 9.3 to 9.6.

[0397] For this purpose, an organic acid (eg formic acid or acetic acid) or a base (eg sodium hydroxide) is added to the emulsion or dispersion and the pH is set within the abovementioned range.

[0398] Carrying out the first crosslinking and / or further crosslinking at a pH value above or below the isoelectric point has the advantage that the charge of the proteins is changed and electrostatic interactions can thus positively influence capsule formation. Furthermore, such modification of the proteins has a positive influence on their emulsifying capacity.

[0399] During the first crosslinking step and any further crosslinking steps, the stirring power is reduced, for example to a stirring speed of about 800 to 1400 rpm, in order to prevent the microcapsules from immediately breaking up again.

[0400] An important criterion for the usability of microcapsules is the weight ratio of core material to capsule wall material. Although on the one hand the aim is to achieve the highest possible core material ratio in order to maximize the usefulness of the capsules, on the other hand the capsules must still have a sufficient proportion of capsule wall material to ensure the stability of the capsules.

[0401] According to the invention, it has proven particularly advantageous to design the microcapsules in such a way that the weight ratio of core material to capsule wall material is from 50:50 to 98:2, preferably from 80:20 to 97.5:2.5.

[0402] After complete curing, the microcapsules produced by the process according to the invention are available as a dispersion in water, which is also referred to as microcapsule dispersion or microcapsule slurry. Basically, the microcapsules can already be sold in this form.

[0403] In order to prevent separation or emulsification of such suspensions and thus achieve high storage stability, it has proven to be advantageous if the suspension has a viscosity of 12 to 2000 mPas. In order to achieve the desired viscosity of the suspension, thickeners are preferably used.

[0404] Preferably, xanthan gum, Diuthan Gum, carboxymethylcellulose (CMC), microcrystalline cellulose (MCC) or guar gum is used as the thickener.

[0405] To improve shelf life, one or more preservatives may optionally be added to the microcapsule slurry, or the microcapsule slurry may be dried.

[0406] Preservatives preferably used are 1,2-hexanediol, 1,2-octanediol, products based on phenoxyethanol, products formed from a mixture of 1,2-benzisothiazolin-3-one (2.5%) and 2-methyl-4-isothiazolin-3-one (2.5%), sodium benzoate and the like.

[0407] Alternatively, and for preservation purposes, the microcapsule slurry is preferably dried.

[0408] Methods such as freeze drying can be used to dry the microcapsule slurry, but spray drying, for example in a fluidized bed, is preferred. It has proven to be advantageous to add additional polysaccharides, preferably dextrins, and in particular maltodextrins, to the suspension at a temperature of about 20 to about 50° C., and preferably about 40° C., which supports the drying process and protects the capsules during this process. The amount of polysaccharide used may be about 50 to about 150% by weight, and preferably about 80 to about 120% by weight, relative to the mass of capsules in the dispersion.

[0409] The spray drying itself can be carried out continuously or batchwise in a conventional spray system with an inlet temperature of about 170 to about 200°C, and preferably about 180 to 185°C, and an outlet temperature of about 70 to about 80°C, and preferably about 72 to 78°C.

[0410] The catalytic crosslinking of polysaccharides and / or proteins with the crosslinking agent and optionally additional crosslinking agents introduces macromolecules into the network of the capsule shell, which increases the proportion of natural components in the capsule shell or in the microcapsule slurry, and which therefore increases the biodegradability of the capsule shell, as exemplified in the examples of the following embodiments.

[0411] The method according to the invention is also characterized in that vegetable proteins, polysaccharides and one or more aliphatic polyisocyanates are polymerized and / or crosslinked as main components, thereby enabling the preparation of very stable vegan microcapsules based on biocompatible polymers with excellent organoleptic properties. Another particularly advantageous feature of the method according to the invention is that the polyisocyanate no longer serves as the main material in the vegetable protein-based microcapsules according to the invention, but is mainly used as a crosslinker for the amino acids and the above-mentioned other components. This reduction in the amount of polyisocyanate used is characterized as a further advantage of the method according to the invention.

[0412] The process according to the invention thus makes it possible to replace part of the polyisocyanate with a biodegradable wall material, such as a protein and / or a polysaccharide, thereby reducing the polyisocyanate content without any loss or reduction in the functionality of the microcapsules, such as the olfactory properties and positive secondary properties, such as high stability, i.e. the ability to retain the active ingredient. The process according to the invention can thus be used to prepare microcapsules which, on the one hand, have excellent functionality and which, at the same time, are rapidly biodegradable.

[0413] In order to obtain vegetable protein-based microcapsules having outstanding stability properties and also excellent organoleptic properties and also with a reduced amount of aliphatic polyisocyanates used, it can be provided 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 tannin.

[0414] Here, the polysaccharide may be the first polysaccharide according to step (ii). Alternatively or additionally, the polysaccharide may be the further polysaccharide according to step (iv) and / or step (vi).

[0415] Surprisingly, it has been found that an amount of hyaluronic acid of 1 to 15% by weight, preferably 2 to 13% by weight, particularly preferably 2.5 to 6% by weight, relative to the amount of wall-forming agent can be particularly advantageous.

[0416] It is particularly preferred to add the hyaluronic acid after the emulsion has been formed.

[0417] In particular, it can also be provided that the content of hyaluronic acid is in the range of 0.1 to 5% by weight, preferably in the range of 0.15 to 2.5% by weight, particularly preferably in the range of 0.2 to 1.0% by weight, based on the total weight of the non-aqueous inner phase, and / or in the range of 0.1 to 5% by weight, preferably in the range of 0.15 to 2.5% by weight, particularly preferably in the range of 0.25 to 1.0% by weight, based on the total weight of the aqueous outer phase.

[0418] On the one hand, this can reduce the amount of aliphatic polyisocyanates used for crosslinking, which may have a positive impact on the environment. On the other hand, reducing the amount of polyisocyanates may have a positive impact on the biodegradability of the vegetable protein-based microcapsules. Another advantage is that neither the stability nor the organoleptic properties of the microcapsules are adversely affected.

[0419] In a further preferred embodiment of the method according to the invention, provision can be made that, in addition to the addition of hyaluronic acid, at least one catalyst is added after the emulsion has been formed.

[0420] This makes it possible to obtain particularly stable vegetable protein-based microcapsules with very good organoleptic properties (odor or fragrance release) within a total reaction time of less than 7 hours.

[0421] In a second aspect, the present invention relates to vegetable protein-based microcapsules or corresponding microcapsule slurries prepared according to the method of the present invention.

[0422] The vegetable protein-based microcapsules according to the invention are characterized in that they consist of or contain the following substances:

[0423] (a) a core comprising or consisting of at least one hydrophobic active ingredient;

[0424] (b) a capsule shell comprising or consisting of a crosslinking matrix or crosslinking units of at least one vegetable protein and 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.

[0425] The microcapsules according to the present invention comprise a core surrounded or encapsulated by a capsule shell or capsule wall. Any material suitable for inclusion in a microcapsule can be used as a core material for preparing the microcapsules according to the present invention. The material to be encapsulated is preferably a hydrophobic, water-insoluble or water-immiscible liquid or solid and a suspension.

[0426] In the context of this specification, the core material is a hydrophobic active ingredient, i.e., a substance having a specific effect or causing a specific reaction, such as a drug, a plant protection agent, a cosmetic active ingredient, a food active ingredient, etc., as described above. The term "hydrophobic active ingredient" means that the active ingredient to be encapsulated is in the inner non-aqueous phase and does not mix with the outer aqueous phase during the preparation of the microcapsules.

[0427] The polymerization and / or crosslinking of the functional groups of vegetable proteins and / or polysaccharides with polyisocyanates produces a stable capsule wall formed by an alternating and dense and therefore stable crosslinking matrix or crosslinking units based on polyureas and polyurethanes and soluble or insoluble complexes of proteins and polysaccharides.

[0428] In a preferred embodiment, the capsule shell comprises or consists of a cross-linked matrix or cross-linked units formed by polymerization and / or cross-linking of at least one vegetable protein with the first and optionally the additional cross-linking agent, and / or a cross-linked matrix or cross-linked units formed by polymerization and / or cross-linking of at least one polysaccharide with the first and optionally the additional cross-linking agent.

[0429] The cross-linked matrix or cross-linked units formed by the polymerization and / or cross-linking of at least one vegetable protein with the first and optionally the additional cross-linking agent is mainly a network based on polyurea, and the cross-linked matrix or cross-linked units formed by the polymerization and / or cross-linking of at least one polysaccharide with the first and optionally the additional cross-linking agent is mainly a network based on polyurethane, as well as a soluble or insoluble complex formed by vegetable protein and polysaccharide.

[0430] In addition to the polyurea formation and / or polyurethane formation described above, the above crosslinking step produces byproducts due to the reactivity of the polyisocyanates, such as ureas, allophanates, biuret, uretdione, carbodiimide, uretonimines, etc., as described in MF Sonnenschein, Introduction to Polyurethane Chemistry, Polyurethanes: Science, Technology, Markets, and Trends, First Edition, 2015, John Wiley & Sons, pp. 105 to 126, the disclosure of which is incorporated herein by reference in its entirety. These byproducts are part of the capsule shell or capsule wall.

[0431] The structure of the capsule wall is based on several individually defined and alternating crosslinking matrices or crosslinking units, making it possible to prepare particularly stable microcapsules with excellent organoleptic properties while significantly reducing the number of shell components.

[0432] In addition to the main components listed above, the capsule shell may optionally also comprise a protective colloid and / or optionally further crosslinking agents.

[0433] It is particularly advantageous that the vegetable protein-based microcapsules contain hyaluronic acid. Surprisingly, it has been found that this can significantly improve the stability properties of the vegetable protein-based microcapsules. In addition, such vegetable protein-based microcapsules surprisingly show improved organoleptic properties. It has also been found that the amount of polyisocyanates used in the preparation of these vegetable protein-based microcapsules containing hyaluronic acid can be reduced.

[0434] In a preferred variant of the second aspect, the microcapsules according to the invention are in the form of a dispersion or slurry, wherein the microcapsules are dispersed in the external aqueous phase. The weight proportion of the microcapsules in the dispersion or slurry is about 20 to 60% by weight, in particular about 25 to 55% by weight, more preferably about 33 to 50% by weight.

[0435] Surprisingly, despite the reduced polyisocyanate content in the microcapsule wall, the vegetable protein-based microcapsules prepared according to the process of the invention have comparable stability and comparable content of unintentional leakage of fragrance oils as the microcapsules of the prior art.

[0436] Due to the excellent stability and excellent release capacity of the microcapsules and the possibility of encapsulating a wide range of hydrophobic active ingredients with the microcapsules according to the invention, the vegetable protein-based microcapsules according to the invention can be used for a wide range of applications for perfuming and flavoring.

[0437] In addition, the microcapsules according to the present invention are universal capsules that can be used to encapsulate a wide range of aromas or flavors, even aromas or flavors having aldehyde, carboxylic acid or ester functional groups, so that there is no limitation on the individual active ingredients.

[0438] Due to their advantageous properties, in particular their stability and the targeted release of the active ingredients, the vegetable protein-based microcapsules according to the invention are suitable for a wide range of applications and in particular for household products, textile care products, detergents, fabric softeners, cleaning agents, fragrance boosters, fragrance emulsions and perfumers, cosmetics, personal care products, agricultural products, pharmaceutical products or paper printing coatings and the like.

[0439] In a further aspect, the present invention therefore relates to the use of the vegetable protein-based microcapsules according to the invention or dispersions (microcapsule slurries) formed from the vegetable protein-based microcapsules according to the invention for the manufacture of household products, textile care products, detergents, fabric softeners, cleaning agents, fragrance boosters, fragrance emulsions and flavor enhancers in liquid or solid form, cosmetics, personal care products, agricultural products, pharmaceutical products or paper printing coatings. The microcapsules according to the invention are particularly suitable for including hydrophobic fragrances or flavorings that can be used in various household and textile care products.

[0440] Finally, the present invention relates to household products, fabric care products, laundry detergents, fabric softeners, cleaning products, fragrance boosters, fragrance emulsions and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceutical products or paper printing coatings, etc., which contain the vegetable protein-based microcapsules according to the present invention or a dispersion formed by the vegetable protein-based microcapsules according to the present invention.

[0441] The proportion of the microcapsules in the above-mentioned products is 0.05 to 15% by weight, preferably 0.2 to 5% by weight, based on the total weight of the product.

[0442] The present invention also relates to a microcapsule slurry comprising the microcapsules according to the present invention in combination with a thickener and / or a preservative.

[0443] Example

[0444] The vegetable protein-based microcapsules according to the present invention and their advantageous properties are described in more detail with reference to the following examples.

[0445] The stability data below relate to tests carried out at 40° C. in commercially available formulations (eg fragrance boosters or fabric softeners).

[0446] The vegan microcapsules according to the present invention are prepared from a variety of plant proteins, namely pea protein, soy protein, sunflower protein and pumpkin protein. The preparation process using pea protein is described below as an example.

[0447] The pea protein can be Pea protein F858F (Roquette). The soy protein may or may not be Soya Protein Isolate SolPro 921 (Solbar Ningbo Technology Co., Ltd.). The pumpkin protein may or may not be Pumpkin Protein 60 (All Organic Treasures GmbH).

[0448] The non-aqueous internal phase comprises TAKENATE TM The invention relates to a polyisocyanate mixture of Desmodur N 3400, D-120N, STABIO D370N and Desmodur N 3400. The three polyisocyanates are used in equal parts. In addition to the pea protein, the aqueous external phase also contains tannins, CMC and glycerol (86.5% in water). The pH of the aqueous external phase is adjusted to 3.3 with formic acid. After the emulsion is formed, hyaluronic acid, maltodextrin and DABCO are added. In the last step, curing is carried out at 70°C for 3 hours.

[0449] Particularly stable microcapsules are obtained if curing is carried out at a temperature between 70° C. and 80° C. for 2 to 4 hours.

[0450] In particular, curing at 80° C. for 2 hours is also possible to obtain particularly stable microcapsules with very good organoleptic properties.

[0451] 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 collected samples were measured using GC-MS. The results indicate how much of the encapsulated oil was transferred to the isopropanol or was not fully encapsulated. Therefore, the free oil content indicates whether the method itself is effective, i.e., whether the fragrance oil has been fully encapsulated and / or whether the capsule shell is sufficiently stable to prevent the fragrance oil from oozing out into the isopropanol. Values ​​below 1% are considered to be an indicator of successful encapsulation and a stable capsule shell.

[0452] Example 1: Stability of plant protein-based microcapsules in use according to the present invention

[0453] The stability of the microcapsules according to the invention and the microcapsules according to the prior art prepared as described above or analogously was measured in the target application. The stability test was carried out using a representative softener, into which the microcapsule slurry was incorporated in an amount of 1% by weight and stored in each case at room temperature and 40° C. Samples were taken at defined intervals and the stability was measured. The identification of the fragrance components was based on an internal database of fragrance formulations and commercially available analytical databases. This results in a certain percentage of the fragrance oil remaining in the capsule. For example, a result of 98% means that 2% of the fragrance oil originally used is no longer contained in the capsule.

[0454] In the tables and figures shown below, the commonly used abbreviations "d" for "day" and "w" for "week" are used.

[0455] Table 1 below shows that the vegetable protein-based microcapsules according to the present invention prepared using only aliphatic polyisocyanates as crosslinking agents have significantly better stability compared to vegetable protein-based microcapsules in which aromatic and aliphatic polyisocyanates are used.

[0456] Table 1:

[0457]

[0458] According to the results in Table 1, it is also shown Figure 1 middle.

[0459] Furthermore, it can be seen from the stability data and comparison shown in Table 1 that without exception all vegetable proteins used, i.e. pea protein, sunflower protein, pumpkin protein, lead to very good stability properties of the vegetable protein-based microcapsules according to the invention. This is not the case when animal proteins are used, as can be seen from the example using gelatin. When only aliphatic polyisocyanates are used, the stability of the microcapsules containing gelatin is reduced compared to the microcapsules according to the invention.

[0460] Table 2:

[0461]

[0462] In Table 2 above, "Polyisocyanate 1" is TAKENATE TM D-120N. "Polyisocyanate 2" is STABIOD 370N. "Polyisocyanate 3" is Desmodur N 3400 and "Polyisocyanate 4" is 100741 Desmodur 44M Flakes. As is well known, the latter is an aromatic polyisocyanate. The stability shown all relates to the stability based on pea proteins, which was obtained as described above.

[0463] From the data in Table 2 it can be inferred that the vegetable protein-based microcapsules have extremely poor stability when only one, and only aromatic polyisocyanates, are used as crosslinkers (polyisocyanate 4). In contrast, if aliphatic polyisocyanates (polyisocyanate 2 or polyisocyanate 3) are used, a significant improvement in the stability of the vegetable protein-based microcapsules according to the invention can be achieved. Surprisingly, the best results in terms of stability can be achieved when alicyclic polyisocyanates (polyisocyanate 1) are used as crosslinkers to prepare vegetable protein-based microcapsules. This applies in particular to long-term stability, i.e. stability over 4 weeks.

[0464] The stability of the vegetable protein-based microcapsules according to the present invention was further studied using a polyisocyanate mixture as a crosslinking agent. The data and results are shown in Table 3 below. Similar to the above description, the "polyisocyanate 1" named in Table 3 is TAKENATE TM D-120N. "Polyisocyanate 2" is STABIO D370N. "Polyisocyanate 3" is Desmodur N 3400 and "Polyisocyanate 4" is Desmodur 44M Flakes. The stability shown all relates to pea protein based microcapsules.

[0465] Table 3

[0466]

[0467] Surprisingly, it has been found that in the context of the present invention, very good stability of the vegetable protein-based microcapsules according to the invention can also be achieved when only aliphatic isocyanates are used (as shown in Table 2 above). As soon as aromatic isocyanates are used even in proportion or in part, the stability decreases accordingly. It is therefore important for the present invention that at least one aliphatic polyisocyanate is used as crosslinking agent in step (i), and in particular no aromatic polyisocyanates are used.

[0468] Furthermore, it has surprisingly been found that particularly good stability of the vegetable protein-based microcapsules according to the invention is achieved when two aliphatic isocyanates are used, in particular a cycloaliphatic (polyisocyanate 1) and an aliphatic (polyisocyanate 2 or polyisocyanate 3) polyisocyanate.

[0469] Since the organoleptic properties, i.e. the release of fragrances or odorants, are poor in the case of polyisocyanate 1, very good stability can be achieved, while at the same time very good organoleptic properties, when a mixture of two or more polyisocyanates is used as crosslinker, one of which is a cycloaliphatic polyisocyanate and one of which is an aliphatic polyisocyanate. Therefore, in view of these two factors, stability and organoleptic properties, it is preferred to use two or more polyisocyanates as crosslinkers in the preparation of microcapsules based on vegetable proteins. A further advantage of using two or more polyisocyanates as crosslinkers compared to only one aliphatic crosslinker is that the biodegradability of the microcapsules based on vegetable proteins prepared in this way according to the invention is higher and, in addition, a smaller amount of polyisocyanate must be used overall.

[0470] In addition, the use of three polyisocyanates as shown in Table 4 below can also produce very stable vegetable protein-based microcapsules according to the present invention.

[0471] When a mixture of three polyisocyanates is used, particularly good stability is achieved if at least one cycloaliphatic polyisocyanate is present. In order to improve the organoleptic properties and biodegradability, at least one aliphatic polyisocyanate is present.

[0472] In the case where the ratio of the three polyisocyanates is 60:20:20, as shown in Table 4, when the alicyclic polyisocyanate and the aliphatic polyisocyanate are each used in equal amounts and the other aliphatic polyisocyanate is used in three times the amount of the alicyclic polyisocyanate (thus the ratio is 20:60:20, see the last column of Table 4), improved sensory properties and improved biodegradability can be obtained.

[0473] Within the scope of the present invention, the molar ratios specified herein may also be replaced by quantitative ratios, and vice versa.

[0474] Surprisingly, very good results with regard to stability and organoleptic properties were achieved when the three polyisocyanates were used in equal proportions, based on the respective amounts.

[0475] Table 4:

[0476]

[0477] Similar to the above statement, the "polyisocyanate 1" named in Table 4 is TAKENATE TM D-120N. "Polyisocyanate 2" is STABIO D370N. "Polyisocyanate 3" is Desmodur N 3400 and "Polyisocyanate 4" is 100741 Desmodur 44 M Flakes. The stability shown all relates to pea protein based microcapsules.

[0478] The developers have also found that the stability of the vegetable protein-based microcapsules according to the invention can also be positively influenced by the addition of other substances. Surprisingly, it has been found that the addition of hyaluronic acid, in particular the addition of hyaluronic acid after the emulsification step, has a significant positive effect on the stability of the prepared microcapsules, as shown in the following Table 5. In Table 5, the percentage of isocyanate relates to the total amount of wall-forming agent in the vegetable protein-based microcapsules.

[0479] Table 5

[0480]

[0481] Thus, the addition of hyaluronic acid has a positive effect on stability, whereby significantly less polyisocyanate is required as a crosslinking agent. Therefore, the use of hyaluronic acid in the process according to the invention for preparing microcapsules based on vegetable proteins is also advantageous, since the microcapsules obtained have improved biodegradability. In addition, the use of hyaluronic acid also improves the organoleptic properties.

[0482] The results in Table 5 also show Figure 5 middle.

[0483] Table 6 shows the results of further investigations on the stability behavior of the vegetable protein based microcapsules according to the present invention.

[0484] Table 6:

[0485]

[0486] The results in Table 6 also show Figure 7 middle.

[0487] Surprisingly, it has been found that the further addition of glycerol to pea protein-based microcapsules that already contain hyaluronic acid (see above) also has a positive effect on the stability of the microcapsules according to the invention. It is particularly advantageous with regard to the addition of both glycerol and hyaluronic acid that the amount of polyisocyanate can be reduced. When the amount of isocyanate (crosslinker) is reduced, the biodegradability increases.

[0488] With regard to the vegetable proteins used, pea proteins, sunflower proteins and pumpkin proteins are particularly preferred in the present invention with regard to the stability of the microcapsules obtained in each case. These four preferred vegetable proteins achieve correspondingly good stability compared to other vegetable proteins. High stability is also achieved with soybean protein and broad bean protein, as can be seen from the following Tables 7 and Figure 4 It can be seen in.

[0489] Table 7:

[0490]

[0491] Example 2: Sensory evaluation of the plant protein-based microcapsules according to the present invention

[0492] The sensory evaluation was carried out as follows: The above-mentioned microcapsules were each incorporated into a fabric softener (Perfüm Tomcap) with a slurry concentration of 0.4% by weight and then washed. The capsules were loaded with 17.5% perfume oil (+17.5% vegetable oil=total loading 35%) and a dosage of 0.4% capsule slurry resulted in a dosage of pure perfume oil in the comparative fabric softener of 0.07% perfume oil. 30 g of fabric softener were used for 2 kg of laundry (including terry towels). The washing instructions were as follows: Place the laundry items including terry towels (cotton towels) in the washing machine and place the fabric softener in the fabric softener compartment. Start the washing program "Express 20; 900 rpm. The terry towels were then dried overnight at room temperature.

[0493] Sixteen testers evaluated the fragrance intensity of the washed towel fabrics on a scale from 1 (no odor) to 9 (very strong odor) by testing in pairs the corresponding free fragrance oil levels in the fabric softeners.

[0494] The fragrance was released in three steps. The first step describes the smell of the untreated cloth. The second step describes the smell of the gently kneaded cloth; for this purpose, the cloth was subjected to a slight mechanical stress by moving it back and forth several times between the hands, causing the capsules to break. The third step describes the smell after the cloth was rubbed vigorously, causing the capsules to break. After each step, the aroma intensity was evaluated.

[0495] Table 8 shows the results of the sensory evaluation.

[0496] In general, it should be noted that the vegetable proteins used are preferably pea proteins, pumpkin proteins, sunflower proteins, each of which makes it possible to provide microcapsules based on vegetable proteins according to the invention, whereby good organoleptic properties can always be achieved (see also Figure 3 ). According to the core idea of ​​the present invention, when aliphatic polyisocyanates are used as cross-linking agents, the sensory properties of those microcapsules based on vegetable proteins are better (see Table 8, rows 2 and 8).

[0497] Table 8:

[0498]

[0499] The results in Table 8 also show Figure 2 middle.

[0500] Based on the above, it has surprisingly been found that in the process of preparing the vegetable protein-based microcapsules according to the invention using at least one aliphatic polyisocyanate as a crosslinking agent, the addition of hyaluronic acid has a positive effect on the organoleptic properties. It is particularly surprising to note that good organoleptic properties can be achieved by adding hyaluronic acid and at the same time the amount of isocyanate can be reduced (see Table 9 below, rows 5 and 6). Reducing the amount of polyisocyanate in this way can improve biodegradability.

[0501] Table 9:

[0502]

[0503] The results in Table 9 also show Figure 6 middle.

[0504] Surprisingly this was found to be associated with the addition of glycerol and hyaluronic acid (see Table 10, rows 8 and 9).

[0505] Based on the above, it has surprisingly been found that in the process of preparing the vegetable protein-based microcapsules according to the invention using at least one aliphatic polyisocyanate as crosslinking agent, the addition of hyaluronic acid and glycerol has a positive effect on the organoleptic properties. It is particularly surprising to note that good organoleptic properties can be achieved by adding hyaluronic acid and glycerol, and at the same time the amount of isocyanate can be reduced (see Table 10 below, lines 8 and 9). This reduction in polyisocyanate can improve biodegradability.

[0506] The results in Table 10 also show Figure 8 middle.

[0507] Table 10:

[0508]

[0509] Example 3: Further results on the stability of the microcapsules based on vegetable proteins according to the present invention in use and further sensory evaluation of the microcapsules based on vegetable proteins according to the present invention

[0510] However, the vegetable protein-based microcapsules according to the invention having very good stability properties and very good organoleptic properties are not limited to pea proteins. On the contrary, surprisingly it has been found that microcapsules prepared using soy 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 shown below.

[0511] Table 11:

[0512]

[0513] The results in Table 11 also show Fig. 9 middle.

[0514] However, the vegetable protein-based microcapsules according to the invention having very good stability properties and very good organoleptic properties are not limited to pea proteins. On the contrary, surprisingly, it has been found that microcapsules prepared using soy protein or pumpkin protein instead of pea protein also have very good organoleptic properties and very good stability properties, which even exceed the stability properties, as can be seen from Tables 11 and 12 below.

[0515] Table 12:

[0516]

[0517] The results in Table 12 also show Fig.10 middle.

[0518] It has surprisingly been found that if the at least one first polysaccharide and / or the at least one further polysaccharide is selected from hyaluronic acid, carrageenan, gellan gum, agar, alginates, xanthan gum, microcapsules with particularly good organoleptic properties can be obtained, as can be seen from the table below.

[0519] Table 13:

[0520]

[0521] The results in Table 13 also show Fig.11 middle.

Claims

1. A method for preparing microcapsules based on vegetable proteins, the method comprising the following steps performed in sequence: (i) providing an inner non-aqueous phase comprising at least one aliphatic polyisocyanate as crosslinking agent and at least one hydrophobic reactive ingredient and optionally at least one further crosslinking agent; (ii) providing an external aqueous phase comprising at least one vegetable protein, preferably pumpkin protein, soy protein, sunflower protein, pea protein; and optionally at least one first polysaccharide and / or at least one additional cross-linking agent and / or at least one polyhydroxyphenol and / or at least one protective colloid, and further optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the vegetable protein; (iii) emulsifying or dispersing the inner non-aqueous phase in the outer aqueous phase to obtain an oil-in-water emulsion or dispersion, the emulsification or dispersing optionally being carried out in the presence of at least one stabilizer and / or at least one emulsifier; (iv) optionally adding at least one additional polysaccharide and / or at least one additional vegetable 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 additional polysaccharide and / or additional vegetable protein; (vii) cooling and optionally further cross-linking by adding at least one additional cross-linking agent; and (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 thickener.

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

3. The process according to claim 1 , wherein the total amount of polyisocyanates, based on the amount of wall formers, is 10 to 70% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 35% by weight, or wherein the total amount of polyisocyanates used together as crosslinkers is 0.5 to 4%, preferably 1 to 3%, particularly preferably 1.5 to 2.5%, based on the total amount of hydrophobic active ingredients used, preferably fragrances or odorants, in particular in the core of the capsule.

4. The method according to any one of claims 1 to 3, wherein the polysaccharide or the at least one additional polysaccharide is hyaluronic acid, or wherein the polyhydroxyphenol is tannin.

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

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

85.

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

85.

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

9. The process according to one or more of claims 1 to 8, wherein at least one further cross-linking agent is added in step (i) and / or in step (ii) and / or in step (vii), wherein the at least one further cross-linking agent and / or the further cross-linking agent is selected from transglutaminases, peroxidases, secondary plant substances selected from polyphenols, polyhydroxyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the above cross-linking agents.

10. The method according to one or more of claims 1 to 9, wherein the at least one hydrophobic active ingredient is selected from the group consisting of fragrances or odorants, flavorings, cooling agents, TRPV1 and TRPV3 modulators, substances that produce a pungent taste or a warm or hot sensation on the skin or mucous membranes, or substances that produce a tingling or stinging sensation in the mouth or throat, or active ingredients with a pungent or irritating or astringent effect, pesticides, biocides, insecticides, substances from the group of insect repellents, food additives, cosmetic active substances, pharmaceutical active substances, agrochemicals, dyes, colorants, dye precursors; luminescent coatings, optical brighteners, solvents, waxes, silicone oils, lubricants, paper printing coatings and mixtures of two or more of the above active ingredients.

11. The method according to one or more of claims 1 to 10, wherein the at least one first polysaccharide and / or the at least one additional polysaccharide is selected from indigestible fibres and dietary fibres, in particular insoluble dietary fibres, in particular cellulose, cellulose derivatives, such as hydroxyethylcellulose, in particular quaternized hydroxyethylcellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), hemicelluloses, lichenin, chitin, chitosan, lignin, xanthan gum, vegetable fibres, in particular cereal fibres, potato fibres, apple fibres, citrus fibres, bamboo fibres, extracted beet fibres; oat fibres and soluble dietary fibres, in particular inulin, in particular natural inulin, highly soluble inulin, granulated inulin, high-performance inulin, pectin, alginates, agar, tragacanth, carrageenan, gum arabic, konjac gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, dextran and lactulose; - starches, in particular 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 fructo-oligosaccharides; - sugar alcohols, in particular sorbitol, mannitol, isomalt, maltitol, maltitol syrup, lactitol, xylitol, erythritol; - Gellan gum; glucose, - Glycosaminoglycans, especially hyaluronic acid and mixtures of the above polysaccharides.

12. The method according to one or more of claims 1 to 11, wherein the at least one vegetable protein or the at least one further vegetable protein is selected from the group consisting of protein isolates, vegetable proteins in fraction form, partial or complete hydrolysates or intermediates produced by physicochemical processes or fermentation or enzymatic treatment of proteins, in particular vegetable proteins from the group consisting of cereals, in particular wheat, barley, rye, spelt, gluten, in particular wheat gluten, rapeseed, rice, potato, corn, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, bean, pea, pumpkin and sunflower, other proteins from edible plants, chitosan and mixtures thereof.

13. The method according to one or more of claims 1 to 12, wherein the at least one protective colloid is selected from - diols, in particular ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, isobutylene glycols, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and - polyols, preferably triols, in particular glycerol and ethoxylation products thereof, trimethylolpropane and ethoxylation products thereof, polyvinyl alcohol (PVOH) and derivatives thereof, in particular ammonium-functionalized or sulfonate-functionalized polyvinyl alcohol, polyphenols, preferably 1,3,5-trihydroxybenzene, polysaccharides, in particular glucose, starch or chemically, mechanically and / or enzymatically modified starch, cellulose derivatives, for example hydroxyethylcellulose, in particular quaternized hydroxyethylcellulose, and carboxymethylcellulose, - polyvinyl pyrrolidone, maleic acid vinyl copolymer, sodium lignin sulfonate, maleic anhydride / styrene copolymer, ethylene / maleic anhydride copolymer, copolymers of ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitan, sodium lauryl sulfate, - vegetable polymers, especially gum arabic (Senegal and Seychelles types), proteins, mastic, shellac, lignin, chitosan, saponins, and mixtures of the above compounds; and / or the protective colloid is used in combination with starch.

14. The method according to one or more of claims 1 to 13, wherein in step (v) the first crosslinking is carried out by adding at least one catalyst to obtain a microcapsule slurry; wherein the at least one catalyst is selected from diazabicyclo[2.2.2]octane (DABCO), bismuth catalysts and tin catalysts and mixtures of two or more of the above catalysts.

15. The process according to claim 1 , wherein the total amount of crosslinker added as polyisocyanate, in particular in step (i), is 0.5 to 4%, preferably 1 to 3%, in particular 1.5 to 2.5%, based on the total amount of hydrophobic active ingredients, in particular fragrances or odorants, used in step (i).

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

17. A plant protein-based microcapsule comprising or consisting of: (a) a core comprising or consisting of at least one hydrophobic active ingredient; (b) a capsule shell comprising or consisting of: a crosslinking matrix or crosslinking units of at least one vegetable protein and 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.

18. The microcapsule according to claim 16, wherein the capsule shell comprises or consists of: A cross-linked matrix or cross-linked unit formed by polymerizing and / or cross-linking a mixture of at least one vegetable protein and at least two different cross-linking agents, and a cross-linked matrix or cross-linked unit formed by polymerizing and / or cross-linking a mixture of at least one polysaccharide and at least two different cross-linking agents.

19. The microcapsule according to claim 16 or 17, wherein at least two of the crosslinking agents are respectively different aliphatic or alicyclic polyisocyanates having two or more isocyanate groups.

20. Microcapsules according to one or more of claims 16 to 19, wherein the total amount of polyisocyanates used together as crosslinkers is 0.5 to 4%, preferably 1 to 3%, particularly preferably 1.5 to 2.5%, based on the total amount of hydrophobic active ingredients used, preferably fragrances or odorants, in particular in the core of the capsules.

21. Microcapsules according to one or more of claims 16 to 20, wherein the microcapsules comprise hyaluronic acid.

22. Use of microcapsules according to one or more of claims 16 to 21 or microcapsule slurries according to claim 16 for the manufacture of household products, textile care products, detergents, fabric softeners, cleaning agents, fragrance enhancers or flavor enhancers in liquid or solid form, cosmetics, personal care products, fragrance compositions, agricultural products, pharmaceutical products or paper printing coatings.

23. A household product, a fabric care product, a laundry detergent, a fabric softener, a cleaning agent, a fragrance enhancer and perfumer, a cosmetic, a personal care product, a fragrance composition, an agricultural product or a pharmaceutical product comprising the microcapsules according to any one of claims 16 to 21 or the microcapsule slurry according to claim 16.

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