Process for preparation of microcapsules

Abstract

To provide a process for the preparation of a biodegradable polysaccharide-based microcapsule, biodegradable microcapsule or microcapsule slurry obtainable by the process, and use of the microcapsule slurry.SOLUTION: There is provided a process for the preparation of microcapsules comprising the steps of: providing an internal non-aqueous phase comprising at least one first crosslinking agent and at least one hydrophobic active ingredient; providing an external aqueous phase comprising at least one polysaccharide and optionally at least one protective colloid; emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase, optionally in the presence of at least one stabilizer and / or at least one emulsifier, to obtain an oil-in-water emulsion or dispersion; first crosslinking by addition of at least one catalyst to obtain a microcapsule slurry; curing the microcapsule slurry at a temperature of at least 60°C; and cooling the microcapsule slurry.SELECTED DRAWING: Figure 1a

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to a microcapsule according to the state of the art. Compared with cellulose, biodegradable microfibers have a balanced biodegradability, stability and performance. Capsules, in particular biodegradable protein and / or polysaccharide-based microcapsules, and A dispersion of such microcapsules (microcapsules) encapsulating at least one hydrophobic active ingredient is A capsule slurry of preferably a flavor or fragrance-containing polysaccharide and protein-based microorganism. In addition, the present invention relates to a process for the preparation of black capsules. Biodegradable microcapsules containing at least one hydrophobic active agent obtainable by In another aspect, the present invention relates to a household product, a textile care product, a laundry detergent, , fabric softeners, cleaning agents, liquid or solid fragrance enhancers or fragrance enhancers, cosmetics, in osmotic care products, fragrance compositions, agricultural products, pharmaceuticals, or printing coatings for paper. Finally, the present invention relates to the use of the microcapsules and dispersions as ingredients in a pharmaceutical composition. The present invention relates to consumer products comprising such microcapsules or microcapsule dispersions. [Background technology]

[0002] A microcapsule is a particle that includes a core and a wall material surrounding the core, where the core is , a solid, liquid, or polymer surrounded by a dense permeable or semi-permeable wall material During production, the starting polymer undergoes emulsification and coacervation. or after interfacial polymerization, deposited on the material to be encapsulated. The core is also called the internal phase. Other names used for the wall include outer phase, shell, or coating. Micro The diameter of the microcapsules typically varies in the range of 1 to 1000 μm. The wall thickness is typically , 0.5 to 150 μm, but can vary in the range of 5·10 -9 m to 5·10 -6 m. Typically, usage amounts of 25 to 95 wt.% are possible, but usage amounts of 1 to 99 wt.% are also possible.

[0003] Encapsulation of the active ingredient with a suitable wall material (coating material) can be carried out for several reasons: - Conversion of a liquid into an easily handled powder form (e.g., coating of vegetable oils); - Time-controlled release of substances (dosage control, depot effect of pharmaceuticals, pesticides, and fertilizers); - Masking of taste, odor, and color (e.g., bitter substances or pungent fragrance substances); - Protection against light, oxidation, heat, acids or bases (e.g., vitamins, fragrance substances); - Moisture protection (e.g., hygroscopic salts or minerals); - Delay of loss of volatile components (e.g., fragrance substances); - Prevention of premature chemical reactions with other mixed components; - Improvement of handling before or during processing (flowability, formation of dust); - Protection of personnel from harmful or unpleasant substances (chemicals, fragrance concentrates); or improvement of solubility / suspensibility by surface modification - Improvement of solubility / suspensibility by surface modification.

[0004] Hydrophobic active ingredients such as aromatic or fragrance substances can be easily incorporated into formulations for a number of diverse applications by encapsulation.

[0005] The contents of the microcapsules can be released in various ways, in particular based on one of the mechanisms described below. ​ - The capsule is mechanically broken by grinding or shearing. This mechanism is used, for example, in reactive carbonless paper. - The capsule is broken by melting the wall material. Based on this mechanism, components such as an expanding agent or a flavoring are released into the firing mixture only, for example, during the firing process. - The capsule is broken by dissolving the wall material. This mechanism is used, for example, in powdered detergents, and the encapsulated components such as enzymes are released only during the washing process. - The capsule remains intact and the contents of the capsule are released more

[0006] gradually by diffusion through the capsule wall. Based on this mechanism, for example, drug components can be released slowly and uniformly in the body. Based on their properties, microcapsules are used particularly in the printing industry, the food industry (vitamins, flavorings, plant extracts, enzymes, microorganisms), agrochemistry

[0007] (fertilizers, pesticides), the feed industry (minerals, vitamins, enzymes, drugs, microorganisms), the pharmaceutical industry, the detergent industry, and the cosmetics industry. Today, many everyday-use products such as detergents, fabric softeners, powdered detergents, liquid detergents, shower gels, shampoos, deodorants, body lotions, etc. are scented with aromatic substances or mixtures of aromatic substances. In very many cases, the aromatic

[0008] substances interact with other components of the formulation or the more volatile components Provide the possibility to reduce or completely prevent the evaporation of highly volatile aromatic components.

[0009] For the production of microcapsules, various capsule wall or coating materials are known to be. The capsule wall can be made of either natural materials, semi-synthetic materials, or synthetic materials. Examples of natural shell materials include gum arabic, agar, agarose, maltodextrin, alginate or its salts, such as sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolysates, sucrose, and waxes. Examples of semi-synthetic capsule wall materials include chemically modified cellulose, especially cellulose esters, and cellulose ethers, such as cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose, as well as starch derivatives, especially starch ethers and starch esters. Examples of synthetic shell materials are polymers such as polyacrylates, polyamides, polyvinyl alcohol, or polyvinylpyrrolidone.

[0010] Depending on the type of capsule wall material and the manufacturing process, microcapsules with different characteristics regarding diameter, size distribution, as well as physical and / or chemical properties are formed in each case.

[0011] Between polyisocyanates and polyamines and / or diols or polyols Polyurea microcapsules or polyurea / polyurethane microcapsules formed by coincidence The capsules are well-known capsules used in various technical fields including perfumes.

[0012] The polyurea microcapsules obtained by reacting two polyisocyanates with a polyamine are described, for example, in WO2011 / 161229 or WO2011 / 160 733. According to WO2011 / 161229 or WO2011 / 16073 3, the polyurea microcapsules are prepared in the presence of polyvinylpyrrolidone ( PVP) as a protective colloid. WO2012 / 107323 discloses polyurea microcapsules having a polyurea shell containing a reaction product of a polyisocyanate with guanazole (3,5-diamino-1,2,4-triazole) and an amino acid in the presence of an anionic stabilizer or a surfactant such as anionic polyvinyl alcohol. EP0 537467B describes microcapsules prepared from a polyisocyanate containing a polyethyleneoxy group in the presence of a stabilizer such as polyvinyl alcohol. According to W O2007 / 096592, microencapsulation can be carried out in an oil phase emulsified in a continuous aqueous phase generally stabilized by a surfactant system such as polyvinyl alcohol or its carboxylated and sulfonated derivatives. The exemplary delivery systems of the above latest prior art exhibit both good stability, i.e., the ability to retain the active ingredient, and thus the ability of the capsules to avoid loss of volatile components, and good performance, e.g., aroma release in the case of fragrance or odorant capsules.

[0013]

[0014] However, the microcapsules according to the above latest prior art have the drawback that the polymer capsule wall or the capsule shell material requires a large polymer content to ensure sufficient stability and avoid excessive loss of the active ingredient. In addition, the microencapsulation process introduces plastics into the environment and may cause problems as "microplastics", potentially causing environmental damage or adverse health effects as required. Plastic particles are increasingly under public criticism for their environmental impact, and as social pressure regarding environmental considerations is increasing, there is a growing demand for bio-based and biodegradable

[0015] solutions, so there is a need to develop new materials for microencapsulation to reduce microplastics in the environment. Here, bio-based biodegradable materials are attracting attention. Therefore, from this perspective, there is a need to increasingly use biodegradable capsule wall materials in the preparation of bio-based biodegradable materials, while at the same time providing microcapsules that exhibit excellent stability and release characteristics for the problem applications. It is important that not only the polymer material of the capsule wall itself but also each fragment formed during disintegration is biocompatible.

[0016] However, the issue of reducing the amount of microplastics in the environment by using biodegradable materials is not obvious in the case of microencapsulation. Toxicological stability, as a desired function of microcapsules such as olfactory characteristics and positive secondary characteristics such as high stability, contradicts the requirement for rapid biodegradability in many applications.

[0017]

[0018] Manufacturing microcapsules having both good stability and good release of the active ingredient is particularly difficult. The ability to retain the active ingredient, and thus avoid loss of volatile components of the capsule depends particularly on the stability of the capsule in the product base. However, particularly capsules with good stability do not necessarily exhibit good biodegradability.

[0019] As the degree of crosslinking increases, the stability of the microcapsules increases, but at the same time the ability of the capsule shell to biodegrade decreases. In the case of very stable microcapsules, the number of microcapsules that break and open to release the active ingredient due to pressure, friction etc. decreases, so performance such as sensory performance decreases. If they are too unstable, they are already destroyed during storage and do not function either.

[0020] Therefore, the present invention is based on the complex problem of providing microcapsules that preferably meet one, several, or preferably all of the following requirements: - Improvement of biodegradability, - No toxic effects on humans and the environment; - Maintenance of sufficient stability, - Compatibility with a wide variability regarding the active ingredient to be encapsulated, - Excellent release behavior of the encapsulated active ingredient, and - Accessible by known microcapsule manufacturing processes, and - The components are readily available, i.e., can be produced from raw materials produced in a bio-based or sustainable manner and - Can be produced from the resulting raw materials.

[0021] Surprisingly, by interfacial polymerization, in the presence of a catalyst, polysaccharides and / or preparing microcapsules from proteins and crosslinking agents can solve this problem. By crosslinking, biodegradable and stable capsule shells or capsule walls can be formed, which can be used to encapsulate a wide range of hydrophobic or lipophilic active ingredients respectively. It has been found that this problem can be solved. By crosslinking, biodegradable and stable capsule shells or capsule walls can be formed, which can be used to encapsulate a wide range of hydrophobic or lipophilic active ingredients respectively. It becomes possible to form a biodegradable and stable capsule shell or capsule wall that can be used to encapsulate a wide range of hydrophobic or lipophilic active ingredients respectively. / or preparing microcapsules from proteins and crosslinking agents can solve this problem. By crosslinking, biodegradable and stable capsule shells or capsule walls can be formed, which can be used to encapsulate a wide range of hydrophobic or lipophilic active ingredients respectively.

Summary of the Invention

Means for Solving the Problem

[0022] This problem is solved by the object of the independent patent claim. Preferred embodiments are apparent from the wording of the dependent claims and the following description. It is apparent from the wording of the dependent claims and the following description.

[0023] Therefore, a first object of the present invention is a process for preparing biodegradable protein and / or polysaccharide microcapsules, comprising the following steps: (i) providing an internal non-aqueous phase comprising at least one first crosslinking agent and at least one hydrophobic active ingredient, and optionally at least one further crosslinking agent; (ii) providing an external aqueous phase comprising at least one protein and / or at least one polysaccharide, and optionally at least one protective colloid, and optionally adjusting the pH value of the aqueous phase to a pH value lower than the isoelectric point of the protein; (iii) emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase in the presence of optionally at least one stabilizer and / or at least one emulsifier to obtain an oil-in-water emulsion / dispersion; (iv) optionally adding at least one further polysaccharide and / or at least one further protein. (ii) providing an external aqueous phase comprising at least one protein and / or at least one polysaccharide, and optionally at least one protective colloid, and optionally adjusting the pH value of the aqueous phase to a pH value lower than the isoelectric point of the protein; (iii) emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase in the presence of optionally at least one stabilizer and / or at least one emulsifier to obtain an oil-in-water emulsion / dispersion; (iv) optionally adding at least one further polysaccharide and / or at least one further protein. (iii) emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase in the presence of optionally at least one stabilizer and / or at least one emulsifier to obtain an oil-in-water emulsion / dispersion; (iv) optionally adding at least one further polysaccharide and / or at least one further protein. (iv) optionally adding at least one further polysaccharide and / or at least one further protein. (iv) optionally adding at least one further polysaccharide and / or at least one further protein. (v) adding at least one catalyst to effect a first crosslinking to obtain a microcapsule slurry step of obtaining; (vi) curing the microcapsule slurry at a temperature of at least 60 °C and optionally adding at least one additional polysaccharide and / or at least one additional protein step; (vii) effecting a second crosslinking by adding at least one second crosslinking agent upon cooling and optionally step of performing; and (viii) optionally separating the microcapsules from the microcapsule slurry and optionally drying the microcapsules or adjusting the viscosity of the microcapsule slurry by adding at least one thickening agent step in this order. It relates to a process comprising

[0024] In a second aspect, the present invention relates to microcapsules containing at least one lipophilic active ingredient or to a microcapsule slurry prepared according to the process of the present invention.

[0025] (a) a core comprising or consisting of at least one hydrophobic activator; (b) a crosslinked matrix or unit of at least one polysaccharide and / or at least one protein and at least one first crosslinking agent; and optionally at least one first protective colloid and / or optionally a crosslinked matrix or unit of at least one additional crosslinking agent providing biodegradable microcapsules comprising or consisting of a capsule shell is also an object of the present invention.

[0026] Finally, in another aspect, the use of the microcapsules according to the invention or of a dispersion comprising the microcapsules according to the invention for the preparation of household products, toiletry-style care products, laundry detergents, fabric softeners, cleaning agents, odor boosters, liquid or solid perfume lotions or odor intensifiers, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals, or printing coatings for paper is concerned. Surprisingly, in the context of the present invention, in the preparation of the microcapsules, the combination of polysaccharides and / or proteins and subsequent crosslinking with at least two or more polyisocyanates having isocyanate groups results in stable microcapsules, and thus efficient encapsulation of lipophilic active ingredients and subsequent targeted release of these active ingredients are ensured. At the same time, the microcapsules have been found to exhibit good biodegradability due to biobased and biodegradable building blocks. By using polysaccharides and / or proteins, the polyisocyanate content of the capsule wall or capsule shell material can be reduced, i.e., replaced by biobased capsule wall components, and thus the proportion of biobased capsule wall components can be increased without sacrificing the stability of the microcapsule wall. These and other aspects, features and advantages of the present invention will become apparent to those skilled in the art by considering the following detailed description and the scope of the claims. In this regard, any feature or modification from one aspect of the present invention can be used or substituted in another aspect of the present invention.

[0027]

[0028]

[0029] It is possible. Furthermore, the examples disclosed in this specification illustrate and exemplify the present invention, but are not intended to limit the present invention. In particular, it is understood that the present invention is not limited to these examples.

[0030] Unless otherwise indicated, all percentages are by weight. Numerical examples given in the form "from x to y" include the said values. When multiple preferred numerical ranges are given in this form, it is understood that all ranges resulting from combinations of the various endpoints are also included.

[0031] As used herein, the terms "at least 1" or "1 or more" refer to 1 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9 or greater.

[0032] The term "and / or" represents the existence of a combination or the provision of an alternative.

[0033] Numerical examples given in the form "x to y" include the given values. When multiple preferred numerical ranges are specified in this form, all ranges created by combining the various endpoints are also included.

Brief Description of the Drawings

[0034] Figure

Figure 1a - 1d

Figure 1e

[0035]

Figure 2

[0036]

Figure 3

[0037]

Figure 4

[0038]

Figure 5

[0039]

Figure 6

[0040]

Figure 7

Mode for Carrying Out the Invention

[0041] In FIGS. 2 to 6, a dot was used as the decimal point symbol.

[0042] Detailed Description of the Invention In a first aspect, the present invention is a process for preparing biodegradable protein and / or polysaccharide microcapsules ules, comprising the following steps, namely (i) At least one first crosslinking agent and at least one hydrophobic active ingredient, and optionally, at least one further crosslinking agent, and optionally, at least one catalyst to provide an internal non-aqueous phase; (ii) Providing an external aqueous phase containing at least one protein and / or at least one polysaccharide, and optionally, at least one protective colloid, and optionally adjusting the pH value of the aqueous phase to a pH value lower than the isoelectric point of the protein; (iii) Emulsifying or dispersing the internal non-aqueous phase in the external aqueous phase in the presence of optionally at least one stabilizer and / or at least one emulsifier to obtain an oil-in-water emulsion / dispersion; (iv) Optionally adding at least one further polysaccharide and / or at least one further protein; (v) Performing a first crosslinking by adding at least one catalyst to obtain a microcapsule slurry; (vi) Curing the microcapsule slurry at a temperature of at least 60 °C and optionally adding at least one further polysaccharide and / or at least one further protein; (vii) Performing a second crosslinking by adding at least one second crosslinking agent during cooling and optionally ; and (viii) Optionally separating the microcapsules from the microcapsule slurry and optionally drying the microcapsules or adjusting the viscosity of the microcapsule slurry by adding at least one thickening agent in this order.

[0043] In the context of the present invention, a microcapsule contains at least one or more active ingredients as the core material inside the capsule and is surrounded by a capsule shell or capsule wall and is understood to be a microparticle. The active ingredient is preferably a hydrophobic or lipophilic active ingredient. Such active ingredients are insoluble or poorly soluble in water but are readily soluble in fats and oils. The terms "microcapsule" and "capsule" or "hydrophobic" and "lipophilic" are used synonymously within the context of the present invention.

[0044] In the context of the present invention, the capsule shell or capsule wall preferably consists of several cross-linked matrices or cross-linked units, and these cross-linked matrices or cross-linked units preferably have different compositions and are generated by several process steps or process sequences during the preparation of the microcapsules according to the present invention, especially by the cross-linking step. The cross-linked matrix contains or consists of at least one polysaccharide and / or at least one protein. These capsule wall components are cross-linked to each other by a cross-linking agent and a catalyst through an interface polymerization via a mechanism that is selectively catalyzed to form a three-dimensional network of polysaccharide, protein, and cross-linking agent.

[0045] In the first step (i) of the process according to the present invention, an internal non-aqueous phase is provided that contains at least one cross-linking agent, at least one hydrophobic activator to be encapsulated, and optionally an additional cross-linking agent.

[0046] The first and / or second The first crosslinking agent according to the aspect is an aliphatic, alicyclic, hydroaromatic, aromatic or heterocyclic poly isocyanate selected from the group consisting of isocyanates having two or more isocyanate groups , a crosslinking agent selected from the group consisting of substituted products thereof, and a mixture of two or more of the aforementioned first crosslinking agents.

[0047] At least one isocyanate or polyisocyanate having two or more isocyanate groups used in the process according to the present invention for preparing biodegradable protein and / or polysaccharide microcapsules forms a polymer network by polymerization to form a capsule shell or a capsule wall and contains at least two isocyanate groups. At least one isocyanate or polyisocyanate having two or more isocyanate groups used in the process according to the present invention for preparing biodegradable protein and / or polysaccharide microcapsules forms a polymer network by polymerization to form a capsule shell or a capsule wall and contains at least two isocyanate groups. At least one isocyanate or polyisocyanate having two or more isocyanate groups used in the process according to the present invention for preparing biodegradable protein and / or polysaccharide microcapsules forms a polymer network by polymerization to form a capsule shell or a capsule wall and contains at least two isocyanate groups. At least one isocyanate or polyisocyanate having two or more isocyanate groups used in the process according to the present invention for preparing biodegradable protein and / or polysaccharide microcapsules forms a polymer network by polymerization to form a capsule shell or a capsule wall and contains at least two isocyanate groups. At least one isocyanate or polyisocyanate having two or more isocyanate groups used in the process according to the present invention for preparing biodegradable protein and / or polysaccharide microcapsules forms a polymer network by polymerization to form a capsule shell or a capsule wall and contains at least two isocyanate groups.

[0048] The polyisocyanate is an R-substituted organic derivative (R-N= C=O) of isocyanic acid (HN=C=O). The organic isocyanate is a compound in which the isocyanate group (-N=C=O) is bonded to an organic radical. The polyfunctional isocyanate or polyisocyanate is a compound containing at least two or more, that is, 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. The polyisocyanate having two isocyanate groups is also called a diisocyanate. 11, 12, 13, 14, 15, 20, 50, 100, 200 or even more isocyanate groups (-N=C=O) in the molecule. The polyisocyanate having two isocyanate groups is also called a diisocyanate. 11, 12, 13, 14, 15, 20, 50, 100, 200 or even more isocyanate groups (-N=C=O) in the molecule. The polyisocyanate having two isocyanate groups is also called a diisocyanate. 11, 12, 13, 14, 15, 20, 50, 100, 200 or even more isocyanate groups (-N=C=O) in the molecule. The polyisocyanate having two isocyanate groups is also called a diisocyanate. 11, 12, 13, 14, 15, 20, 50, 100, 200 or even more isocyanate groups (-N=C=O) in the molecule. The polyisocyanate having two isocyanate groups is also called a diisocyanate.

[0049] The polyisocyanate can be classified as an aliphatic, alicyclic, hydroaromatic, aromatic or heterocyclic isocyanate or polyisocyanate. Furthermore, the polyisocyanate according to the present invention can be linear or branched. The polyisocyanate can be classified as an aliphatic, alicyclic, hydroaromatic, aromatic or heterocyclic isocyanate or polyisocyanate. Furthermore, the polyisocyanate according to the present invention can be linear or branched. The polyisocyanate can be classified as an aliphatic, alicyclic, hydroaromatic, aromatic or heterocyclic isocyanate or polyisocyanate. Furthermore, the polyisocyanate according to the present invention can be linear or branched.

[0050] Polyisocyanates, especially aromatic polyisocyanates, are highly reactive compounds. The polyaddition reaction of polyisocyanates with diols or polyols forms the basis of polyurethane chemistry, and the polyaddition reaction of polyisocyanates with amines forms the basis of polyurea chemistry.

[0051] According to the present invention, at least bifunctional, preferably polyfunctional polyisocyanates are used, i.e., all aliphatic, cycloaliphatic and aromatic isocyanates are suitable as long as they have at least two reactive isocyanate groups.

[0052] Aliphatic, cycloaliphatic, hydroaromatic, aromatic or heterocyclic polyisocyanates, their substituted products and mixtures of the aforementioned monomeric or oligomeric compounds are particularly preferred. Among the polyisocyanates specified above, it is preferred to use aliphatic and / or aromatic compounds.

[0053] In a preferred embodiment of the process according to the present invention, the polyisocyanate contains on average 2 to 5 functional groups -N=C=O groups. These include, for example, aliphatic, cycloaliphatic and aromatic di-, tri- and higher polyisocyanates.

[0054] Among the above-mentioned polyisocyanates, diisocyanates and polyisocyanates having three functional groups -N=C=O groups are particularly preferred and are therefore mainly used in the practice of the present invention. Preferably, diisocyanates having the general structure O=C=N-R-N=C=O (wherein R represents an aliphatic, cycloaliphatic or aromatic group) are used. Preferably, rad ​Karl has 5 or more carbon atoms.

[0055] In a preferred embodiment of the process according to the invention, at least one polyisocyanate having two or more isocyanate groups is selected from the group consisting of aliphatic polyisocyanates and / or aromatic polyisocyanates. In a further preferred variant of the process according to the invention, at least one polyisocyanate is a combination of two different aliphatic polyisocyanates, or a combination of an aliphatic and an aromatic polyisocyanate.

[0056] Depending on the number of functional groups, an optimal crosslinking or network of the capsule wall is achieved, providing microcapsules that exhibit a long-term sustained release of the active ingredient and good stability in consumer products.

[0057] In a preferred variant of the process according to the invention, the polyisocyanate is an aliphatic polyisocyanate.

[0058] The term "aliphatic polyisocyanate" refers to any polyisocyanate molecule that is not aromatic. Further, the molecule contains 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 directly bonded to the corresponding number of different C atoms of the same aliphatic molecule, and derivatives of such compounds.

[0059] 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, and derivatives thereof. The above aliphatic polyisocyanate molecules containing isocyanate groups may further be linear, branched or cyclic, and may have, for example, one or more heteroatoms such as aliphatic substituents, aromatic substituents, nitrogen, oxygen, phosphorus and / or sulfur, halogens such as fluorine, chlorine, bromine and / or iodine, and / or other functional groups such as alkoxy groups, and may have any substituents. The linear aliphatic polyisocyanate molecules are preferably selected from C2- to C20-linear alkyls, preferably C3- to C15-linear alkyls, C4- to C12-linear alkyls, C5- to C10-linear alkyls, C6- to C9-linear alkyls, or C7- to C8-linear alkyls. Preferably, the linear aliphatic molecules do not contain an aromatic structure. The branched aliphatic polyisocyanate molecules are preferably selected from C2- to C20-branched alkyls, preferably C3- to C15-branched alkyls, C4- to C12-branched alkyls, C5- to C10-branched alkyls, C6- to C9-branched alkyls, C7- to C8-branched alkyls. The shorter the carbon chain of the polyisocyanate molecule, the faster the reaction rate compared to longer analogs of the chain. The cyclic aliphatic polyisocyanate molecules contain at least one, i.e., 1, 2, 3, 4 or more non-aromatic ring structures, and the ring structure itself preferably consists of only C atoms. Of course, the C atoms of the ring structure may have suitable substituents. At least one ring structure is preferably

[0060] The above aliphatic polyisocyanate molecules containing isocyanate groups may further be linear, branched or cyclic, and may have, for example, one or more heteroatoms such as aliphatic substituents, aromatic substituents, nitrogen, oxygen, phosphorus and / or sulfur, halogens such as fluorine, chlorine, bromine and / or iodine, and / or other functional groups such as alkoxy groups, and may have any substituents. The linear aliphatic polyisocyanate molecules are preferably selected from C2- to C20-linear alkyls, preferably C3- to C15-linear alkyls, C4- to C12-linear alkyls, C5- to C10-linear alkyls, C6- to C9-linear alkyls, or C7- to C8-linear alkyls. Preferably, the linear aliphatic molecules do not contain an aromatic structure. The branched aliphatic polyisocyanate molecules are preferably selected from C2- to C20-branched alkyls, preferably C3- to C15-branched alkyls, C4- to C12-branched alkyls, C5- to C10-branched alkyls, C6- to C9-branched alkyls, C7- to C8-branched alkyls. The shorter the carbon chain of the polyisocyanate molecule, the faster the reaction rate compared to longer analogs of the chain.

[0061] The cyclic aliphatic polyisocyanate molecules contain at least one, i.e., 1, 2, 3, 4 or more non-aromatic ring structures, and the ring structure itself preferably consists of only C atoms. Of course, the C atoms of the ring structure may have suitable substituents. At least one ring structure is preferably The linear aliphatic polyisocyanate molecules are preferably selected from C2- to C20-linear alkyls, preferably C3- to C15-linear alkyls, C4- to C12-linear alkyls, C5- to C10-linear alkyls, C6- to C9-linear alkyls, or C7- to C8-linear alkyls. Preferably, the linear aliphatic molecules do not contain an aromatic structure. The branched aliphatic polyisocyanate molecules are preferably selected from C2- to C20-branched alkyls, preferably C3- to C15-branched alkyls, C4- to C12-branched alkyls, C5- to C10-branched alkyls, C6- to C9-branched alkyls, C7- to C8-branched alkyls. The shorter the carbon chain of the polyisocyanate molecule, the faster the reaction rate compared to longer analogs of the chain.

[0062] The cyclic aliphatic polyisocyanate molecules contain at least one, i.e., 1, 2, 3, 4 or more non-aromatic ring structures, and the ring structure itself preferably consists of only C atoms. Of course, the C atoms of the ring structure may have suitable substituents. At least one ring structure is preferably The shorter the carbon chain of the polyisocyanate molecule, the faster the reaction rate compared to longer analogs of the chain.

[0063] The cyclic aliphatic polyisocyanate molecules contain at least one, i.e., 1, 2, 3, 4 or more non-aromatic ring structures, and the ring structure itself preferably consists of only C atoms. Of course, the C atoms of the ring structure may have suitable substituents. At least one ring structure is preferably The shorter the carbon chain of the polyisocyanate molecule, the faster the reaction rate compared to longer analogs of the chain. The cyclic aliphatic polyisocyanate molecules contain at least one, i.e., 1, 2, 3, 4 or more non-aromatic ring structures, and the ring structure itself preferably consists of only C atoms. Of course, the C atoms of the ring structure may have suitable substituents. At least one ring structure is preferably Alternatively, it independently consists of a 3-membered, 4-membered, 5-membered, 6-membered, 7-membered or 8-membered ring. Preferably, the ring The cyclic aliphatic molecule contains 2 to 20 C atoms, for example, 3 to 15 C atoms, 4 to 12 C atoms atoms, 5 to 10 C atoms, 6 to 9 C atoms, or 7 to 8 C atoms.

[0064] In another variant of the process according to the invention, the polyisocyanate is an aromatic polyisocyanate The term "aromatic polyisocyanate" means any polyisocyanate compound in which two or more isocyanate groups are directly bonded to aromatic C atoms and which contains, for example, phenyl, tolyl, xylyl, naphthyl or diphenyl moieties as aromatic components, as well as derivatives of such polyisocyanate compounds.

[0065] Aromatic polyisocyanates react significantly faster than aliphatic polyisocyanates and are preferably used in the process according to the invention.

[0066] Linear, branched or cyclic aliphatic or aromatic polyisocyanates can exist as monomers or polymers, respectively. A monomeric polyisocyanate is a molecule that is not bonded to another molecule, in particular not bonded to another molecule via one or more crosslinking agents. A polymeric polyisocyanate contains at least two monomers linked by one or more crosslinking agents. The at least two monomers do not necessarily have to be the same monomer and may be different. The polymeric polyisocyanate preferably contains at least two or more monomers, i.e., at least 2, 3, 4, 5, 10, 20, 30, 40, 50, 100 or more monomers bonded to each other via at least one crosslinking agent. It contains the monomer above.

[0067] Linear, branched, or cyclic aliphatic or aromatic polyisocyanates are preferably of a limited size / limited molecular weight that enables reactivity with one or more crosslinking agents. Examples of suitable molecular weights are preferably about 100 g / mol to 5·10 g / mol, preferably 120 g / mol to 2·10 4 g / mol, 140 g / mol to 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 may be mentioned .

[0068] Any number of different linear, branched and / or cyclic aliphatic and / or aromatic poly isocyanates can be used. For example, at least one, i.e., at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different linear aliphatic polyisocyan ates are used. For example, at least one, i.e., at least 1, 2, 3, 4, 5 , 6, 7, 8, 9 or 10 different branched aliphatic polyisocyanates are used. For exam ple, at least one, i.e., at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different (branched) cyclic aliphatic polyisocyanates are used.

[0069] Preferably, derivatives of linear, branched and / or cyclic aliphatic polyisocyanates are used. As used herein, derivatives are understood in the broadest sense as compounds derived from a compound by a chemical reaction. Examples of derivatives include the above-mentioned linear or branched oligomers and / or adducts of aliphatic polyisocyanates. Preferred oligomers are biuret, isocyanurate, uretdione, iminooxadiazinedione and a preferred adduct is a trimethylolpropane adduct. These oligomers / adducts are well known in the art and are disclosed, for example, in U.S. Patent No. 4,855,490(A) or U.S. Patent No. 4,144,268(A).

[0070] Preferably, the aliphatic polyisocyanate is present only in monomeric form and / or in dimerized form (as isocyanate) or in oligomeric form.

[0071] Derivatives of linear, branched or cyclic polyisocyanates and / or mixtures thereof can also be obtained by reacting the polyisocyanate with a polyalcohol (such as glycerol), a polyamine, a poly thiol (such as dimercaprol).

[0072] The isocyanate compounds defined above, when present, specifically include various isomers, 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).

[0073] Exemplary aliphatic polyisocyanates include fats based on hexamethylene diisocyanate aliphatic water-dispersible polyisocyanates, BAYHYDURN 304 and BAYHYD UR N3Q5, low-viscosity polyfunctional hexamethylene diisocyanate-based aliphatic polyisocy anates such as DESMODUR N3400, DESMODUR N3600, DES MODUR N3700, and DESMODUR N3900, and hexamethyl ene diisocyanate-based aliphatic polyisocyanates such as DESMODUR 3600 and DESMODUR N100, etc., commercially available ones are included, and each of these is available from Bay er Corporation, Pittsburgh, PA.

[0074] According to another preferred variation of the present invention, the linear or branched aliphatic polyisocyanate is , pentamethylene diisocyanate (PDI such as Stabio D-370N or D-376N manufactured by Mitsui Chemicals Inc., J apan), hexamethylene diisocyanate (HDI), lysine triisocyanate ethyl ester, lys ine diisocyanate ethyl ester, and derivatives thereof, or selected from the group consisting of and selected, preferably, each of the derivatives contains more than one isocyanate group and further contains one or more groups selected from the group consisting of biuret, isocyanurate, uretdione, iminooxadiazinedione and trimethylolpropane adducts as required, and / or here, the cycloaliphatic polyisocyanate is isophor one diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane as required, and / or here, the cycloaliphatic polyisocyanate is isophor one diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane (Mitsui Chemicals Inc., Japan-made Takenate 600 such as H6XDI), 1,2-bis(isocyanatomethyl)cyclohexane, 1, 4-bis(isocyanatomethyl)cyclohexane, methylene bis(cyclohexyl is ocyanate) (H12MDI) and derivatives thereof, or selected from the group consisting of selected, preferably, each of said derivatives contains more than one isocyanate group, and biu let, isocyanurate, uretdione, iminooxadiazinedione, trimethylolpropane adduct of H6XDI (such as TMP adduct), especially Mitsui Chemica ls Inc., Japan-made Takenate D-120N, or one or more groups selected from the group consisting of further contain, if necessary.

[0075] Renewable raw materials, for example, aliphatic poly isocyanates obtained from PDI (Stabio D-370N or D-376N made by Mitsui Chemicals Inc., Japan) are particularly preferred. Such aliphatic poly isocyanates obtained from renewable raw materials have been found not to affect the quality / characteristics of the core-shell capsules .

[0076] Other suitable commercially available polyisocyanates include LUPRANA TM20 (BASF) with an average n of 0.7; PA PI 27 (Dow Chemi cal) with an average n of 0.7; MONDUR MR (Bayer) with an average n of 0.8; MONDUR MR Light (Bayer) with an average n of 0. 8; MONDUR 489 (Bayer) with an average n of 1.0; poly-[(phenyl isocyanate)-co-formaldehyde ​ Rudehyde (Aldrich Chemical, Milwaukee, WI), DESM ODUR N3200 (Bayer) and TAKENATE D110-N (Mits ui Chemicals Corporation, Rye Brook, NY), etc. Other isocyanate monomers such as these can be mentioned. Other typical polyisocyanates include , TAKENATE D-110N (Mitsui), DESMODUR L75 (Ba yer), and polyisocyanates called DESMODUR IL (Bayer) can be mentioned.

[0077] In a preferred variant, the polyisocyanate used in the preparation of the polyurea / polyurethane microcapsules according to the invention is used as the only polyisocyanate component, i.e., without mixing it with other different polyisocyanate components. used as the only polyisocyanate component, i.e., without mixing it with other different polyisocyanate components. is used without mixing it with other different polyisocyanate components.

[0078] Examples of monomeric polyisocyanates that can be used according to the invention and contain at least two polyisocyanate groups are: ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene di isocyanate, 1,6-hexamethylene diisocyanate, ethylene diisothiocyan ate, tetramethylene diisothiocyanate, hexamethylene diisothiocyanate, cycl obutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cy clohexane-1,4-diisocyanate, 1,3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, a mixture of 1,3-phenylene diisocyanate and 1,4-phen ylene diisocyanate, p-phenylene diisothiocyanate, xylylene- diisocyanate, etc. 1,4 - Diisothiocyanate, 2,4 - tolylene diisocyanate, 2,6 - tolylene diisocyanate, a mixture of 2,4 - tolylene diisocyanate and 2,6 - tolylene di isocyanate, xylylene - 1,4 - diisocyanate, xylylene - 1,3 - diisocyanate, and a mixture of xylylene - 1,4 - diisocyanate and xylylene - 1,3 - diisocyanate, 2,4 - hexahydrotoluene diisocyanate, 2, 6 - hexahydrotoluene diisocyanate, a mixture of 2,4 - hexahydrotoluene diiso cyanate and 2,6 - hexahydrotoluene diisocyanate, hexahydro - 1,3 - phenylene diisocyanate, hexahydro - 1,4 - phenylene diisocy anate, a mixture of hexahydro - 1,4 - phenylene diisocyanate and hexahydro - 1,4 - phenylene diisocyanate, 1,3 - diisocyanatobenzene, 1,3,5 - trimethylbenzene - 2,4 - diisocyanate, 1,3,5 - triisopropylbenzene - 2,4 - diisocyanate, diphenylmethane - 4,4’ - diisocyanate, 3, 3’ - dimethyldiphenylmethane - 4,4’ - diisocyanate, 4,4’ - diphenyl propane diisocyanate, naphthylene - 1,4 - diisocyanate, naphthylene - 1, 5 - diisocyanate, triphenylmethane - 4,4’,4’’ - triisocyanate, toluene - 2,4,6 - triisocyanate, dimethyldiphenylmethane - 2,2’, 5,5’ - tetraisocyanate, or a mixture of the aforementioned compounds is.

[0079] As the polymerizable compound containing at least two polyisocyanate groups, preferably, Di- and polyisocyanates produced on a large scale, for example, TDI: toluylene diiso cyanate (isomer mixture of 2,4- and 2,6-toluylene diisocyanate in a ratio of 80:20), HDI: hexamethylene diisocyanate-(1,6), IPDI: isophorone diiso cyanate or DMDI: diphenylmethane-4,4'-diisocyanato are preferably preferred.

[0080] Other particularly preferred monomeric polyisocyanate compounds are diisocyanates, for example 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-di isocyanatocyclohexane, 1-polyisocyanato-3,3,5-trimethyl-5-po lyisocyanatomethylcyclohexane (isophorone diisocyanate), 4,4'-di isocyanatodicyclohexylmethane, 2,4- and 2,6-diisocyanatomethylcyclo hexane and mixtures thereof. In principle, aromatic polyisocyanates, for example toluylene diisocyanate or 4,4'-diisocyanatodiphenylmethane can also be used.

[0081] Other specific examples of diisocyanates include, for example, 1,5-naphthylene diisocyanato , 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MD I), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXD1), 4,4'-diphenyldimethylmethane diisocyanate, di- and te Trialkyl diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate , 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, if necessary in a mixture, isomers of toluene diisocyanate (TDI), 1-methyl-2, 4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethyl hexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanato methyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinated and brom inated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1, 4-diisocyanate, (HDI), dicyclohexylmethane diisocyanate, cyclo hexane-1,4-diisocyanate, ethylene diisocyanate, bisisocyanato ethyl phthalate, and also 1-chloromethylphenyl-2,4-diisocyanate, 1-bromomethyl-phenyl-2,6-diisocyanate, 3,3-bis(chloromethyl)e ther-4,4'-diphenyldiisocyanate and other polyisocyanates having reactive halogen atoms are mentioned.

[0082] Surprisingly, especially when using long-chain aliphatic diisocyanates having 6, 7, 8, 9, 10 or more carbon atoms it has been found that a more stable capsule shell or capsule wall is formed.

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

[0084] Proportionately modifying the above-mentioned diisocyanates or mixtures thereof in a known manner. For example, uretdione, urethane, isocyanurate, bicarbonate, etc. Derivatives of polyisocyanates containing ethyl and / or allophanate groups are also disclosed in the present invention. It can be used in a variety of processes.

[0085] a combination of at least two different, preferably aliphatic, polyisocyanates, or At least one aliphatic polyisocyanate and at least one aromatic polyisocyanate The combination with is very particularly preferred.

[0086] In such combinations, the different reaction rates of polyisocyanates are utilized: Aromatic polyisocyanates react significantly faster than aliphatic polyisocyanates, and the reaction rate Compared to their long-chain analogues, short-chain aliphatic polyisocyanates, i.e., those with 1 to 5 carbons, Aliphatic polyisocyanates having 1 to 5 carbon atoms are faster.

[0087] Therefore, in a further preferred embodiment of the present invention, different aliphatic and / or The aromatic or aromatic polyisocyanates may also have different chain lengths. The isocyanate is preferably 6, 7, 8, 9, 10, 11, 12, 13, 14, 20 , 25 or more carbon atoms, but even more preferably they have 6 to 12 The shorter chain polyimides have 1 to 8 carbon atoms, and more preferably 6 to 8 carbon atoms. The isocyanate is a polyisocyanate having 1 to 5 carbon atoms, preferably 3 to 5 It is understood to be a polyisocyanate having carbon atoms of

[0088] According to the present invention, preferably, a short-chain aliphatic polyisocyanate (C1, C2, C3, C4, C5) and a long-chain aliphatic polyisocyanate (C6, C7, C8, C9, C10, C1 1, C12, C13, C14, C15, C20, C25 or more), or a short-chain aliphatic polyisocyanate (C1, C2, C3, C4, C5) and a long-chain aromatic group polyisocyanate (C6, C7, C8, C9, C10, C11, C12, C13, C 14, C15, C20, C25 or more), or a combination of a long-chain aliphatic poly isocyanate (C6, C7, C8, C9, C10, C11, C12, C13, C14 C15, C20, C25 or more) and a short-chain aromatic polyisocyanate. In the present context, particularly preferred is the use of a mixture of different aliphatic poly isocyanates having two or more isocyanate groups having a chain length of 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms, particularly preferably 4

[0089] to 7 carbon atoms for the preparation of the biodegradable microcapsules according to the present invention.

[0090] Aliphatic polyisocyanates are particularly preferred in the present context due to their chemical relationship with biological systems. For example, both lysine and 1,5-diisocyanatopentane have 1,5-diaminopentane, which is the same

[0091] degradation product, and thus are particularly suitable for use in the preparation of bio-based biodegradable microcapsules in consideration of environmental concerns.​​​​​The main embodiments include any mixture of long-chain diisocyanates with short-chain diisocyanates. More preferably, the mixing ratio of the long-chain diisocyanate to the short-chain diisocyanate is in the range of 4:1 to 1:4, and particularly preferably in the range of 2:1 to 1:2.

[0092] Examples of preferred specific mixtures of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate include the mixture of the biuret of hexamethylene diisocyanate and the trimethylol adduct of xylylene diisocyanate, the mixture of the biuret of hexamethylene diisocyanate and the polyisocyanurate of diisocyanate, and also the mixture of the biuret of hexamethylene diisocyanate and the trimethylolpropane adduct of toluene diisocyanate.

[0093] According to the present invention, in the combination of the above-mentioned short-chain aliphatic polyisocyanate and long-chain aliphatic polyisocyanate, or in the combination of the short-chain aliphatic polyisocyanate and long-chain aromatic polyisocyanate, or in the combination of the long-chain aliphatic polyisocyanate and short-chain aromatic polyisocyanate, the polyisocyanates are present as mixtures in monomer or oligomer or polymer form, respectively.

[0094] Preferably, this results in the following combinations for use in the process according to the present invention using the above-mentioned short-chain and long-chain definitions: - Short-chain aliphatic polyisocyanate (monomer or oligomer or polymer) and short-chain aliphatic polyisocyanate (monomer or oligomer or polymer); - Short-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and long-chain aliphatic polyisocyanates (monomers or oligomers or polymers); - Short-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and short-chain aromatic polyisocyanates (monomers or oligomers or polymers); - Short-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and long-chain aromatic polyisocyanates (monomers or oligomers or polymers); - Long-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and short-chain aliphatic polyisocyanates (monomers or oligomers or polymers); - Long-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and long-chain aliphatic polyisocyanates (monomers or oligomers or polymers); - Long-chain aliphatic polyisocyanates (monomers or oligomers or polymers) and short-chain aromatic polyisocyanates (monomers or oligomers or polymers); - Long-chain aliphatic polyisocyanates (monomers) and long-chain aromatic polyisocyanates ( oligomers or polymers).

[0095] By the selection of at least two aliphatic polyisocyanates with different chain lengths and degrees of polymerization, or the selection of a mixture of aliphatic and aromatic polyisocyanates, due to the differences in the reaction rate, dissociation, and cross-linking structure of the polyisocyanate components, a significant improvement in stability and performance (aromatic release in the case of fragrances or odor-capturing capsules) was observed.

[0096] The combinations of the aforementioned polyisocyanates or two different aliphatic polyisocyanates or a polyisocyanate mixture of one aliphatic polyisocyanate and one aromatic polyisocyanate can be used to form a particularly stable and better, i.e., more densely branched crosslink inside the capsule shell.

[0097] Therefore, high-performance (aroma-releasing) microcapsules produced from either a mixture of aliphatic and aromatic polyisocyanates or a mixture of two different aliphatic polyisocyanates can be prepared based on the process described herein. Such microcapsules are very stable and are characterized by excellent aroma storage properties, and thus they are reflected in the better performance (aroma release) of the capsules, for example, in the field of odorants or fragrance encapsulation. As shown in the following embodiments, the use of two different polyisocyanates results in microcapsules that further exceed the stability of microcapsules produced from a single polyisocyanate system.

[0098] Microcapsules composed of an aliphatic-aliphatic polyisocyanate mixture are as good as microcapsules composed of an aliphatic-aromatic polyisocyanate mixture, as shown in the following embodiments. Therefore, in principle, a combination of at least two different polymerizable (preferably aliphatic and / or aromatic) polyisocyanates is preferred in the present invention.

[0099] The proportion of the first crosslinking agent in the internal non-aqueous phase is in the range of 0.1 to 5 wt.%, preferably in the range of 0.15 to 2.5 wt.%, based on the total weight of the non-aqueous phase. Most preferably, the first

[0100] %​​​​ The crosslinking agent is provided to the internal non-aqueous phase in the range of 0.5 to 1 wt.% based on the total weight of the non-aqueous phase. to be.

[0101] The first crosslinking agent is added to the internal non-aqueous phase as such, for example as a solid or in the form of an aqueous solution. to add.

[0102] The first crosslinking agent is present in the aqueous solution at a concentration of 0.01 to 2 mol / l, preferably 0.1 to 1 .5 mol / l, most preferably 0.5 to 1.0 mol / l. The solution has a pH value of 7 to 14, preferably a pH value of 12.

[0103] To improve the crosslinking of at least one polysaccharide and / or at least one protein, at least one additional crosslinking agent is added to the internal non-aqueous phase as needed. Further The crosslinking agent is different from the first crosslinking agent. The additional crosslinking agent is selected from the group consisting of transglutaminase, peroxidase, secondary plant substances,

[0104] secondary plant substances which are polyphenols, especially tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde aldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned crosslinking agents. selected from the group consisting of. The crosslinking agent is selected from the group consisting of transglutaminase, peroxidase, secondary plant substances, polyphenols, especially tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned crosslinking agents.

[0105] Transglutaminase as an enzyme catalyzes crosslinking via isopeptide bonds between two amino acids, namely glutamine and lysine. The phenolic groups of secondary plant compounds crosslink peptides via hydrogen bonds. Aldehydes, cinnamaldehyde, and vanillin react covalently with the free amino groups of proteins via reactive aldehyde groups. bonds. Aldehydes, cinnamaldehyde, and vanillin react covalently with the free amino groups of proteins via reactive aldehyde groups. react covalently with the free amino groups of proteins via reactive aldehyde groups.

[0106] Among the aforementioned further crosslinking agents, particularly preferred are cinnamaldehyde, tannin, and gallic acid.

[0107] A particularly advantageous combination of the first crosslinking agent and the further crosslinking agent is polyisocyanate and transglutaminase; polyisocyanate and peroxidase; polyisocyanate and polyphenol; polyisocyanate and tannin; polyisocyanate and gallic acid; polyisocyanate and ferulic acid; polyisocyanate and hesperidin; polyisocyanate and cinnamaldehyde; polyisocyanate and vanillin; polyisocyanate and carvacrol; or polyisocyanate and a mixture of two or more of the above-mentioned further crosslinking agents is.

[0108] The content of the further crosslinking agent in the internal non-aqueous phase is in the range of 0.05 to 5 wt.%, preferably in the range of 0.1 to 2 wt.%, based on the total weight of the non-aqueous phase. Most preferably, the further crosslinking agent is used in the internal non-aqueous phase in the range of 0.15 to 1 wt.%, based on the total weight of the non-aqueous phase. is used.

[0109] The further crosslinking agent is added directly to the internal non-aqueous phase, for example, as a solid or in the form of an aqueous solution. is added.

[0110] The further crosslinking agent is present in the aqueous solution at a concentration of 0.01 to 2 mol / l, preferably 0.1 to 1.5 mol / l, and most preferably 0.5 to 1.0 mol / l. The solution has a pH value of 7 to 14, preferably a pH value of 12.

[0111] By using at least one first crosslinking agent and at least one additional crosslinking agent that are different from each other in combination, the stability of the microcapsules is significantly improved, and thus the proportion of the leaking essential oil is reduced. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture.

[0112] Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Since the proportion of the polyisocyanate component is low, according to the present invention, it is possible to prepare protein-based and / or polysaccharide-based microcapsules, where the absolute proportion of the polyisocyanate is only 1 / 50 of the total capsules containing at least one lipophilic active ingredient to be encapsulated. Thus, protein and / or polysaccharide-based microcapsules having a polyisocyanate content of only 0.6 wt.% based on the total weight of the capsules can be prepared by the process according to the present invention. Preferably, the polyisocyanate content is about 1.8 wt.% of the capsules. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability. Despite the low polyisocyanate content, the microcapsules according to the present invention are characterized by high stability.

[0113] In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. In step (i) of the process according to the present invention, first, at least one crosslinking agent is substantially dissolved together with at least one or more active ingredients to be encapsulated, optionally in an inert non-aqueous solvent or a solvent mixture of an inert non-aqueous solvent. The term "substantially dissolved" means that at least 90 wt.%, preferably at least 98 wt.%, more preferably 99.9 wt.% of the aforementioned components are dissolved in the solvent or solvent mixture and can be used in this process. Preferably, at least one polyisocyanate and at least one active ingredient to be encapsulated are dissolved in the solvent or solvent mixture. Dissolve it completely. If the solvent does not provide sufficient solubility for the isocyanate, this drawback can be overcome by using a suitable solubility promoter.

[0114] Preferred solvents for the internal non-aqueous phase are immiscible with water, do not react with the isocyanate component or the active ingredient, and have little or no odor at the amount used.

[0115] The term "solvent" in the context of the present invention includes all types of oily substances or oil components, particularly vegetable oils such as canola oil, sunflower oil, soybean oil, olive oil, modified vegetable oils such as alkoxylated sunflower oil or soybean oil, synthetic (tri)glycerides such as industrial mixtures of mono-, di-, and triglycerides of C6-C22 fatty acids, fatty acid alkyl esters such as methyl or ethyl esters of vegetable oils (Agnique® ME18 RD-F, Agnique® ME18 SD-F, Agnique® ME12C-F, Agnique® ME1270), fatty acid alkyl esters based on these C6-C22 fatty acids, mineral oils, and mixtures thereof. Examples of suitable and preferred lipophilic solvents are as follows: geranylgeraniol based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of straight-chain C6-C22 fatty acids and straight-chain or branched-chain C6-C22 fatty alcohols, or esters of branched-chain C6-C13 carboxylic acids and straight-chain or branched-chain C6-C22 fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate. Lystyl, cetyl myristate, cetyl palmitate, cetyl stearate, isostear cetyl phosphate, cetyl oleate, cetyl behenate, cetyl lactate, stearyl myristate stearyl palmitate, stearyl stearate, stearyl isostearate stearyl oleate, stearyl erucate, isostearyl myristate isostearyl palmitate, isostearyl stearate, isostearyl isostearate isostearyl oleate, isostearyl behenate, myristyl oleate palmityl oleate, stearyl oleate, isostearyl oleate oleyl oleate, behenyl oleate, erucyl oleate, myristyl behenate behenyl palmitate, behenyl stearate, behenyl isostearate behenyl oleate, behenyl behenate, erucyl behenate, myristyl erucyl, palmityl erucyl stearyl erucyl, isostearyl erucyl, oleyl erucyl behenyl erucyl, and erucyl erucyl.

[0116] Also, esters of linear C6-C22 fatty acids and branched-chain fatty alcohols, especially 2-ethyl hexanol, esters of C18-C38 alkyl hydroxycarboxylic acids and linear or branched C6- C22 fatty alcohols, especially dioctylalate e), esters of linear and / or branched fatty acids and polyhydric alcohols (e.g., propylene glycol l, dimer diol or trimer triol) and / or geraniol, triglycerides based on C6-C10 fatty acids, liquid mono esters of C6-C18 fatty acids / di / triglyceride, C6-C22 fatty alcohol and / or geraniol and esters with aromatic carboxylic acids, especially benzoic acid, esters with C2-C12 dicarboxylic acids and linear or branched alcohols containing 1 to 22 carbon atoms, or esters with polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear or branched C6-C22 fatty alcohols carbonates, such as dicaprylyl carbonate (Cetiol® CC), geranyl carbonates based on fatty alcohols containing 6 to 18, preferably 8 to 10 carbon atoms, benzoic acid esters with linear or branched C6-C22 alcohols, linear or branched, symmetric or asymmetric dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicone methicone gum, etc.), aliphatic or naphthenic hydrocarbons, such as squalane, squalene, or dialkylcyclohexanes, and / or mineral oils are also suitable. Preferred solvents also include esters of linear C6-C22 fatty acids and branched fatty alcohols, esters of C18-C38 alkyl hydroxycarboxylic acids and linear or branched C6-C22 fatty alcohols, esters with linear or branched C6-C22 fatty alcohols, especially dioctyl maleate, linear and / or branched fatty acids and polyhydric alcohols, such as propylene glycol, dimer diol or trimer triol, and / or geraniol

[0117] ​​​​​​​​​esters with, triglycerides based on C6-C10 fatty acids, based on C6-C18 fatty acids liquid mono / di / triglycerides, C6-C22 fatty alcohols and / or gels based on esters of bearberry alcohol with aromatic carboxylic acids, especially benzoic acid, esters of C2-C12 dicarboxylic acids with esters with linear or branched alcohols containing 1 to 22 carbon atoms or esters with polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C2 2 fatty alcohol carbonates, for example dicaprylyl carbonate (Cetiol (trade mark) CC), gel carbonates based on fatty alcohols containing 6 to 18, preferably 8 to 10 carbon atoms esters of benzoic acid with linear or branched C6-C22 alcohols, linear or branched, symmetric or asymmetric dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, for example dicaprylyl ether etc. (Cetiol (trade mark) OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils ( cyclomethicone, silicone methicone type etc.) and / or aliphatic or naphthenic hydrocarbons, for example squalane, squalene, or dialkylcyclohexane are included are included.

[0118] Furthermore, liquid linear and / or branched and / or saturated or unsaturated hydrocarbons or any mixture thereof can be used as solvents within the scope of the present invention. These can be, for example, alkanes having 4 to 22, preferably 6 to 18 carbon atoms, or any mixture thereof.

[0119] Particularly preferably suitable as an inert solvent for the internal non-aqueous phase is alkyl aromatic hydrocarbon hydrogen, for example, diisopropylnaphthalene or substituted biphenyl, chlorinated diphenyl, etc. paraffin, chlorinated paraffin, natural vegetable oil, such as cottonseed oil, peanut oil, palm oil, etc. tricresyl phosphate, silicone oil, dialkyl phthalate, dialkyl adipate, partially hydrogenated terphenyl, alkylated biphenyl, alkylated naphthalene, diaryl ether, aryl alkyl ether, and higher alkylated benzene, benzyl benzoate, isopropyl myristate, and any mixture of these hydrophobic solvents, and a single or a plurality of these hydrophobic solvents and kerosene, paraffin, and / or isoparaffin mixture.

[0120] Preferably, vegetable oil triglyceride, benzyl benzoate or isopropyl myristate is used as a solvent for providing the internal non-aqueous phase. Most preferably, palm oil, soybean oil, canola oil, sunflower oil, palm kernel oil, cottonseed oil, peanut oil, corn germ oil, coconut oil, olive oil, sesame oil, linseed oil, safflower oil, modified vegetable oil, and a vegetable oil selected from the group consisting of mixtures thereof.

[0121] The aforementioned solvents are used individually or as a mixture of two or more solvents in the process according to the present invention.

[0122] In another preferred variant of the process according to the present invention, at least one polyisocyanate is directly dissolved in at least one active ingredient, preferably a solution of one or more aromatic or fragrance substances / substances or perfume oils, and thus, as described above, the micro- according to the present invention There is essentially no solvent in the core of the capsule. Avoiding the solvent in the microcapsule core is advantageous in terms of reducing manufacturing costs and addressing environmental issues.

[0123] In particular, aromatic or fragrant substances are dissolved in solvents commonly used in the perfume or fragrance industry. Since alcohol reacts with isocyanate, the solvent is preferably not alcohol. Examples of suitable solvents include diethyl phthalate, isopropyl myristate, Abalyn (registered trademark) (a colophony resin available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes or isoparaffins. Preferably, the solvent is highly hydrophobic. Preferably, the aromatic or fragrant substance solution contains less than 30% solvent. More preferably, the aromatic or fragrant substance solution contains less than 20%, even more preferably less than 10% solvent, and all of these percentages are defined by weight relative to the total weight of the aromatic or fragrant substance solution. Most preferably, the aromatic or fragrance is substantially free of solvent.

[0124]

[0125] If at least one hydrophobic active ingredient is already mixed with a solvent or solvent mixture, the use of an inert solvent or solvent mixture is not necessary. In such cases, at least one first crosslinking agent can be directly mixed with the hydrophobic activator to obtain an internal non-aqueous phase.

[0125] As an active ingredient to be encapsulated or as a core material for the preparation of microcapsules according to the present invention, basically any material suitable for inclusion in the microcapsules can be considered in the process according to the present invention. Preferably, hydrophobic, i.e., water-insoluble ​​a non-polar or water-immiscible liquid or solid, as well as suspensions, can be considered with the active ingredient to be encapsulated These are mainly non-polar substances. Such hydrophobic substances are almost always lipophilic, i.e., they dissolve well in fats and oils.

[0126] In the context of this specification, the core material is a hydrophobic active substance, i.e., a substance having a specific effect or causing a specific reaction, such as a drug, an insecticide, a cosmetic active ingredient, a food active ingredient, etc.

[0127] At least one active ingredient to be encapsulated used in the process according to the invention is a hydrophobic or lipophilic active ingredient. This ensures that the active ingredient to be encapsulated is in the internal non-aqueous phase during the preparation of the microcapsules according to the invention and does not mix with the external aqueous phase. Otherwise, an emulsion will not be formed and the deposition of the capsule wall material on the droplet surface will not occur. Thereby, during the subsequent emulsification and cross-linking of the capsule wall components, the lipophilic drug is completely encapsulated as the core material within the microcapsules. The thus-formed internal non-aqueous phase is characterized by its organic hydrophobicity and oiliness.

[0128] In a particularly preferred variant of the invention, at least one lipophilic or hydrophobic active ingredient is in particular a lipophilic or hydrophobic aromatic or fragrance substance, or a lipophilic or hydrophobic essential oil or fragrance (aromatic or fragrance mixture), a coolant, a TRPV1 or TRPV3 modulator, a substance that causes a pungent, warm or hot sensation on the skin or mucous membrane, or a substance that causes a tingling sensation in the mouth or throat, or an active ingredient having an astringent effect, an insecticide, ​​​​​​Substances from the group of biocides, insecticides, repellents, food additives, active ingredients of cosmetics, active ingredients of pharmaceuticals , dyes, dye precursors; agricultural chemicals, dyes, luminescent paints, fluorescent brighteners, solvents, waxes , silicone oils, lubricants, printing coatings for paper, or a mixture of two or more of the aforementioned active ingredients.

[0129] In a preferred variant of the present invention, the hydrophobic or lipophilic active ingredients include, in particular, hydrophobic aromatic substances or an aromatic mixture of two or more aromatic substances (essential oils) or hydrophobic fragrance substances or two or more fragrance substances (flavors) of the fragrance substance mixture, or biological components are also included.

[0130] In a preferred embodiment according to the first and / or second aspect of the present invention, the microcapsules have a core material in the form of a hydrophobic single aromatic substance or a single odorant substance, and the core material is from the following groups: extracts of natural raw materials, and their fractions, or components isolated therefrom ; a single aromatic substance 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, pentanoates, hexanoates of acyclic terpene alcohols, crotonates, tiglinates and 3-methyl-2-butenoates; acyclic terp enals and ketones, and their dimethyl and diethyl acetals; formates, acetates, propionates, isobutyrates, butyrates of cyclic terpene alcohols, isovalerates, pentanoates, hexanoates, crotonates, tiglinates , isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates of cyclic terpene alcohols, isovalerates, pentanoates, hexanoates, crotonates, tiglinates - Butyl and 3-methyl-2-butenoate; cyclic terpene aldehydes and ketones; cyclic and alicyclic ethers; cyclic and macrocyclic ketones; alicyclic aldehydes; alicyclic ketones; cyclic esters of alcohols; esters of alicyclic carboxylic acids; aromatic hydrocarbons; araliphatic a lcohols; esters of araliphatic alcohols and aliphatic carboxylic acids; araliphatic ethers ; aromatic and araliphatic aldehydes; aromatic and araliphatic ketones; aromatic and ar 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, at least one single aromatic or single odorant or mixtures thereof selected from one or more of

[0131] Fragrances and flavorings suitable for the preparation of the capsules according to the present invention are described in the literature.

[0132] Preferably, the microcapsules according to the present invention each have a core material in the form of a hydrophobic single aroma or single scent, and the core material is from the following group - Hydrocarbons, such as 3-carene; α-pinene; beta-pinene; alpha-terpin ene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; ced rene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; ( (E,Z)-1,3,5-undecatriene; - Aliphatic alcohols, such as hexanol; octanol; 3-octanol; 2, 6-dimethylheptanol; 2-methylheptanol; 2-methyloctanol; (E) -2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol - Rule: 3,4,5,6,6 - pentamethyl - 3,4 - hepten - 2 - ol and 3,5 ,6,6 - tetramethyl - 4 - methyleneheptan - 2 - ol mixture; (E,Z) - 2 ,6 - nonadienol; 3,7 - dimethyl - 7 - methoxyoctan - 2 - ol; 9 - de cenol; 10 - undecenol; 4 - methyl - 3 - decen - 5 - ol; - aliphatic aldehydes and their acetals, such as hexenal; 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 - u ndecadienal; heptanal - diethylacetal; 1,1 - dimethoxy - 2,2, 5 - trimethyl - 4 - hexene; citronellyloxyacetaldehyde; - aliphatic ketones and their oximes, such as 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; - aliphatic sulfur - containing compounds, such as 3 - methylthiohexanol; 3 - methylthiohe xyl acetate; 3 - mercaptohexanol; 3 - mercaptohexyl acetate; 3 - mercaptohexyl butyrate; 3 - acetylthiohexyl acetate; 1 - menthe n - 8 - thiol; - aliphatic nitriles, such as 2 - nonenoic acid nitrile; 2 - tridecenoic acid nitrile; 2, 12 - tridecenoic acid nitrile; 3,7 - dimethyl - 2,6 - octadienoic acid nitrile; 3 ,7-dimethyl-6-octenenitrile; - aliphatic carboxylic acids and their esters, such as (E)- and (Z)-3-he xenyl 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; isoamyl 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-isoamyloxyacetate; methyl-3,7-dimethyl -2,6-octadienoate; - acyclic terpene alcohols, such as citronellol; geraniol; nerol; linalool ; lavandulol; nerolidol; farnesol; tetrahydrolinalool ; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6 -dimethyl octan-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-octatriene-3-ol; 2,6-dimethyl-2, 5,7-octatriene-1-ol; and their formates; acetates; pro pionates; isobutyrates; butyrates; isovalerates; pentanoates; hexano ates; crotonates; tiglinates and 3-methyl-2-butenoates; - Acyclic terpene aldehydes and ketones, such as geranial; neral; citro neral; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-di methyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl aceto none; and dimethyl and diethyl acetals of geranial; neral and 7-hydroxy-3,7-dimethyloctana l; - Cyclic terpene alcohols, such as menthol; isopulegol; α-terpineol ; terpinene-4; menthan-8-ol; menthan-1-ol; menthan-7-o l; borneol; isoborneol; linalool oxide; nopol; cedrol ; ambroxol; vetiverol; guaiol; and their formates; acetates ; propionates; isobutyrates; butyrates; isovalerates; pentanoates ; hexanoates; crotonates; tiglinates and 3-methyl-2-butenoates; - Cyclic terpene aldehydes and ketones, such as menthone; isomenthone; 8-mer captomenthan-3-one; carvone; camphor; fenchone; α-ionone; β-i onone; α-n-methyli onone; β-n-methyli onone; α-isomethyli onone; β-isomethyli onone; α-iron; β-iron; α-damascon; beta-damascon ; Gamma-damascenone; d-Damascenone; 1-(2,4,4-trimethyl-2-cyclohex en-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro- 1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one ; Nootkatone; Dihydronootkatone; α-Cinenal; β-Cinenal; Acety lated cedarwood oil (methyl cedryl ketone); - Cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5- trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9- trimethyl-(Z2,Z5,E9)-cyclododecatrien-1-ol; 2-isobutyl -4-methyltetrahydro-2H-pyran-4-ol; Alicyclic alcohols, such as 3,3,3-trimethyl-cyclohexylmethanol; 2-methyl-4-(2,2,3- trimethyl-3-cyclopenta-1-yl)butanol; 2-methyl-4-(2,2,3 -trimethyl-3-cyclopenta-1-yl)-2-buten-1-ol; 2-ethyl- 4-(2,2,3-trimethyl-3-cyclopenta-1-yl)-2-buten-1-ol ; 3-methyl-5-(2,2,3-trimethyl-3-cyclopenta-1-yl)-pen tan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopenta-1 -yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl -3-cyclopenta-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethyl cyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclo hexyl)hexan-3-ol from the group of; - Cyclic and alicyclic ethers, such as cineole; cedryl methyl ether; cyclo dodecyl methyl ether; 1,1 - dimethoxycyclododecane; (ethoxymethoxy)cyclo dodecane; α - cedrene epoxide; 3a,6,6,9a - tetramethyldodecahydro naphtho[2,1 - b]furan; 3a - ethyl - 6,6,9a - trimethyldodecahydro naphtho[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 - dio xane; - Cyclic ketones, such as 4 - tert - butylcyclohexanone; 2,2,5 - trimethyl 5 - pentylcyclopentanone; 2 - heptylcyclopentanone; 2 - pentylcyclo pentanone; 2 - hydroxy - 3 - methyl - 2 - cyclopenten - 1 - one; 3 - methyl - cis - 2 - penten - 1 - yl - 2 - cyclopenten - 1 - one; 3 - methyl - 2 - pentyl - 2 - cyclopenten - 1 - one; 3 - methyl - 4 - cyclopentadecenone ; 3 - methyl - 5 - cyclopentadecenone; 3 - methylcyclopentadecanone; 4-(1 - ethoxyvinyl)-3,3,5,5 - tetramethylcyclohexanone; 4 - tert - pentylcyclohexanone; 5 - cyclohexadecen - 1 - one; 6,7 - dihydro - 1 ,1,2,3,3 - pentamethyl - 4(5H)-indanone; 9 - cyclo - heptadecen - 1 - one; cyclopentadecanone; cyclohexadecanone; - Alicyclic aldehydes, such as 2,4 - dimethyl - 3 - cyclohexenecarbaldehyde ; 2 - methyl - 4 - (2,2,6 - trimethylcyclohexen - 1 - yl)-2 - butene - l; 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde - d; 4-(4-Methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde ; - Alicyclic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten- -1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl )-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4 -penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7, 8-octahydro-2-naphthalenylmethyl ketone; methyl 2,6,10-trimethyl- 2,5,9-cyclododecatrienyl ketone; tert-butyl(2,4-dimethyl-3 -cyclohexen-1-yl) ketone; - Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate ; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohex yl acetate; 4-tert-pentylcyclohexyl acetate; decahydro-2 -naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate ; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-me thano-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-inden yl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-inden yl isobutyrate; 4,7-methanooctahydro-5 or 6-inden yl acetate; - Esters of alicyclic carboxylic acids, such as allyl 3 - cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmonate; methyl jas monate; methyl 2 - hexyl - 3 - oxocyclopentanecarboxylate; ethyl 2 - ethyl - 6,6 - dimethyl - 2 - cyclohexenecarboxylate; ethyl 2,3,6 ,6 - tetramethyl - 2 - cyclohexene - carboxylate; ethyl 2 - methyl - 1, 3 - dioxolan - 2 - acetate; - Aromatic hydrocarbons, such as styrene and diphenylmethane; - Aromatic aliphatic alcohols, such as benzyl alcohol; 1 - phenylethyl alcohol ; 2 - phenylethyl alcohol; 3 - phenylpropanol; 2 - phenylpropanol ; 2 - phenoxyethanol; 2,2 - dimethyl - 3 - phenylpropanol; 2, 2 - dimethyl - 3 - (3 - methylphenyl)propanol; 1,1 - dimethyl - 2 - phe nylethyl alcohol; 1,1 - dimethyl - 3 - phenylpropanol; 1 - ethyl - 1 - methyl - 3 - phenylpropanol; 2 - methyl - 5 - phenylpentanol; 3 - me thyl - 5 - phenylpentanol; 3 - phenyl - 2 - propen - 1 - ol; 4 - meth oxybenzyl alcohol; 1 - (4 - isopropylphenyl)ethanol; - Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, such as benzyl acetate ; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2 - phenylethyl acetate; 2 - phenylethyl propionate; 2 - phenylethyl i sobutyrate; 2 - phenylethyl isovalerate; 1 - phenylethyl acetate; α - Trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxy ethyl isobutyrate; 4-methoxybenzyl acetate; - Aromatic aliphatic ethers, such as 2-phenylethyl methyl ether; 2-phenyle thyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether; phenyl acetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaldehyde dimethyl acetal; phenylacetaldehyde glycerol a cetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5 ,9b-tetrahydroinden[1,2-d]-m-dioxin; 4,4a,5,9b- tetrahydro-2,4-dimethylinden[1,2-d]-m-dioxin; - Aromatic and aromatic aliphatic aldehydes, such as benzaldehyde; phenylacetal dehyde; 3-phenylpropanal; hydroatropaldehyde; 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-ter t-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyde ; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5 -phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxy benzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylene -Dioxibenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3 -(4-methoxyphenyl) propanal; 2-methyl-3-(4-methylenedioxyp enyl) propanal; - Aromatic and araliphatic ketones, such as acetophenone; 4-methylacetophen one; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophen one; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl) ethanone; benzophenone; 1,1,2,3,3,6-hexa methyl-5-indanyl methyl ketone; 6-t-butyl-1,1-dimethyl-4-ind anyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1 -methyl-ethyl)-1H-5-indenyl] ethanone; 5’,6’,7’,8’-tet rahydro-3’,5’,5’,6’,8’,8’-hexamethyl-2-acetonaphthone; - Aromatic and araliphatic carboxylic acids and their esters, such as benzoic acid; ph enylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benz yl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phe nyl acetate; phenyl ethyl phenylacetate; methyl cinnamate; ethyl cin namate; benzyl cinnamate; phenyl ethyl cinnamate; cinnamyl cinnamate ; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hex yl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate ; benzyl salicylate; phenyl ethyl salicylate; methyl-2,4-dihydroxy - 3,6 - Dimethylbenzoate; Ethyl - 3 - phenylglycidate; Ethyl - 3 - meth thyl - 3 - phenylglycidate; - Nitrogen - atom - containing aromatic compounds, for example 2,4,6 - trinitro - 1,3 - dimethyl - 5 - tert - butylbenzene; 3,5 - dinitro - 2,6 - dimethyl - 4 - tert - butylacetophenone; Cinnamic acid nitrile; 5 - phenyl - 3 - methyl - 2 - pentenoic acid nitrile; 5 - phenyl - 3 - methylpentenoic acid nitrile; Methyl anthranilate; Me thyl - N - methylanthranilate; The Schiff base of 7 - hydroxy - 3,7 - dimethyloctanal and methyl anthranilate; 2 - methyl - 3 - (4 - tert - butylpheny l) propanal or 2,4 - dimethyl - 3 - cyclohexenecarboxaldehyde; 6 - i sopropylquinoline; 6 - isobutylquinoline; 6 - sec.-butylquinoline; Ind ole; Skatole; 2 - methoxy - 3 - isopropylpyrazine; 2 - isobutyl - 3 - me thoxypyrazine; 4 - (4,8 - dimethyl - 3,7 - nonadienyl) - pyridine; - Phenol; Phenyl ether and phenyl ester, for example estragole; Anethole; Eugenol; Eugenyl methyl ether; Isoeugenol; Isoeuge nol 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 - cresyl phenylacetate ; Cyclic 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 from the group of; - lactones, such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1 ,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undec anolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1,1 5-pentadecanolide; cis- and trans-11-pentadecen-1,15-o lide; cis- and trans-12-pentadecen-1,15-olide; 1,16- hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-he xadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16 -hexadecanolide; ethylene-1,12-dodecanedioate; ethylene-1,13- tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin; as well as stereoisomers, enantiomers, positional isomers, diastereomers, cis / trans isomers, epimers of one or more selected from at least one single fragrance or single odor containing .

[0133] The above single fragrance or single odor substance that can be encapsulated within the scope of the spirit of the present invention Among them, aldehyde fragrances or odorants having aldehyde, carboxylic acid or ester functional groups are particularly preferred for use .

[0134] Aldehyde fragrances or odorants containing the corresponding acetals as well as esters and lactones also include the following group, namely (i) Aliphatic aldehydes and their acetals; (ii) Alicyclic aldehydes; (iii) Aromatic or araliphatic aldehydes; (iv) Aliphatic, aromatic or araliphatic esters; and (v) Lactones; and these can be separated into each of these mixtures respectively.

[0135] The aforementioned aromatic and odoriferous substances having aldehyde, carboxylic acid or ester functional groups, and mixtures thereof are in the following groups: - Aliphatic aldehydes and their acetals, such as hexenal; 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 ; heptanal-diethyl acetal; 1,1-dimethoxy-2,2, 5-trimethyl-4-hexene; citronellyloxyacetaldehyde; - Alicyclic aldehydes, such as 2,4-dimethyl-3-cyclohexenecarbaldehyde ; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal ; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde ; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde ; ; - Aromatic and araliphatic aldehydes, such as benzaldehyde; phenylacetaldehyde ; 3-phenylpropanal; hydroatropaldehyde; 4-methylbenzaldehyde Rudelhyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2 -dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal ; 2-methyl-3-(4-tert-butylphenyl)propanal; 3-(4-ter t-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyd e; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5 -phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methox ybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxy benzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3- (4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphen yl)propanal; - aliphatic carboxylic acid esters, such as (E)- and (Z)-3-hexenyl form ate; 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 buty rate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)-and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalera te; 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-isoamyloxyacetate; methyl-3,7-dimethyl-2,6-octadienoate ; - esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate ; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate ; 4-tert-pentylcyclohexyl acetate; decahydro-2-naphthyl acetate ; 3-pentyltetrahydro-2H-pyran-4-yl acetate ; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate ; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate ; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate ; 4,7-methanooctahydro-5 or 6-indenyl acetate ; ; - esters of araliphatic alcohols and aliphatic carboxylic acids, such as 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 ; ; - Esters of alicyclic carboxylic acids, such as allyl 3 - cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmonate; methyl jas monate; methyl 2 - hexyl - 3 - oxocyclopentanecarboxylate; ethyl 2 - ethyl - 6,6 - dimethyl - 2 - cyclohexenecarboxylate; ethyl 2,3,6 ,6 - tetramethyl - 2 - cyclohexene - carboxylate; ethyl 2 - methyl - 1, 3 - dioxolan - 2 - acetate; - Aromatic and araliphatic carboxylic acid esters, such as methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate ; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; pheny lethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salic ylate; cis - 3 - hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl - 2,4 - dihydroxy - 3,6 - dimethylbenzoate; ethyl - 3 - phenylglycidate; ethyl - 3 - methyl - 3 - phenylglycidate, among which one or more are selected.

[0136] Below, aldehydes, acetals, esters, and lactones are listed together with their trade names, and these are particularly preferred as representatives of groups (i) - (v) in the meaning of the process according to the present invention: Aldehydes: 2 - methylpentanal; Aldehyde C12MNA HM; Aldehyde C4 in the meaning of the process according to the present invention: Aldehydes: 2 - methylpentanal; Aldehyde C12MNA HM; Aldehyde C4 ; Aldehyde C5; Aldehyde C6; Aldehyde C7; Aldehyde C8; Aldehyde C9 ; Aldehyde C10; Aldehyde C11 iso; Aldehyde C11 MOA PURE; Ald ehyde C11 undecanal; Aldehyde C11 undecylenic acid; Aldehyde C12;; Aldehyde C12 MNA; Aldehyde C13; Aldehyde mandarin; Amyl cinnamual dehyde alpha; Anisal aldehyde - O; Anisyl aldehyde; Benzaldehyde NAT.; Bergamal; Boronal; Bourgenol (BOURGENOAL); Can pholen aldehyde; Citral; Citronellal HM; Citronellyloxyacetaldehyde ; Citrilal; Citroylal E HM; Cortex aldehyde; Cortex aldehyde 50PCT PEMOSA; Crotonic aldehyde; Cuminal aldehyde; Sy clamen aldehyde; Decadienal TRANS,TRANS - 2,4, Decanal CIS -4; Decanal TRANS - 2; Decanal TRANS - 2 NAT; Decanal TR ANS - 4; Decanal - 9,1; Dodecandienal 2,6; Dodecanal TRANS - 2 ; Dupical; Epoxydecenal - 4,5 - 2 10% tri; Ethylhexanal; F ARENAL (registered trademark); Florhydral; Gel aldehyde; Helional; Helopa ne; Heliotropin; Heptadienal TRANS,TRANS,2 - 4; Heptanal CIS - 4; Heptanal TRANS - 2; Hexenal TRANS - 2; Hexyl cinnamic acid aldehyde alpha; Hydroatropic acid aldehyde; Hydroxycitronellal; In trelleven aldehyde SPEC.; Isononyl aldehyde; Isovaleric aldehyde; Remo Neral H&R JS I; Lyrar; Linalool; Liral; Majantol; Mand Linalool; Mandraldehyde 10% IN TEC BHT; Mefenal; ME LONAL (R); Methyldihydrocitronellal; Methylbutyraldehyde; Methylcinnamic aldehyde alpha; Methylphenylpentenal-4,2,2; Methylthiopropanal-3 Methyltridecanal-12 10% VT; Methyl-3-buten-2-al; Methyl-5-phenyl-2-hexen-2-al; Mugental 50 DPG; Neocitral Nonadienal; TRANS, CIS-2,6; Nonenal CIS-6 ; Nonenal TRANS-2; ONCIDAL (R) 3 / 060251; Pentenal TRANS-2 ; EgoMaldehyde; Phenylacetaldehyde; Phenylbutenal TRANS-2,2 ; Phenylpropylaldehyde; Pinonaldehyde; Profenal ; Propionaldehyde 2-(P-tolyl); Propionaldehyde; P S-Iraldine X NEU; Safranal; Salicylic aldehyde FG; Sylval; Tetrahydrocitral; Tiglic aldehyde-2,2; Tolualdehyde PARA FG; Tridecenal TRANS-2; Triferal; Undecadienal-2,4 ; Undecenal TRANS-2; Bernal; Beltocitral; Beltomarl ; Beltiprenal; Vetral crude; Cinnamaldehyde NAT.HM; Acetal: Jasmal; Jasemal; Karismal ; Floropar; Heptanal diethyl acetal; Nonandienal diethyl acetal ; Okoumal; Phenylacetaldehyde glycerin acetal; Phenylacetaldehyde dimethyl acetal; Ester: Jasmal; Jasemal; Karismal ; Floropar; Heptanal diethyl acetal; Nonandienal diethyl acetal ; Okoumal; Phenylacetaldehyde glycerin acetal; Phenylacetaldehyde dimethyl acetal ; Ester: Jasmal; Jasemal; Karismal ;TIRAMISONE (registered trademark).

[0137] In a further variant of the process according to the invention, the fragrance substance can also be encapsulated in the form of a single fragrance as the core material, and the core material contains at least one single fragrance substance or a mixture thereof as the active ingredient.

[0138] Typical examples of fragrance substances that may be encapsulated according to the invention are acetophenone; a ril caproate; alpha-ionone; beta-ionone; anisaldehyde; anisi l acetate; anisyl formate; benzaldehyde; benzothiazole; benzyl a cetate; benzyl alcohol; benzyl benzoate; butyl butyrate; butyl cap ronate; butylidene phthalide; carvone; camphene; caryophyllene; cineole; cinnamyl acetate; citral; citronellol; citronellal; citronellyl a cetate; cyclohexyl acetate; cymene; damascone; delta-decalactone; di acetyl; dihydrocoumarin; dimethyl anthranilate; dodecalactone; ethoxy e thyl acetate; ethyl butyrate; ethyl butyrate; ethyl caprylate; ethyl caproate -ate; ethyl crotonate; ethyl furaneol; ethyl guaiacol; ethyl isob utyrate; ethyl isovalerianate; ethyl lactate; ethyl methyl butyrate; e thyl propionate; eucalyptol; eugenol; ethyl heptylate; geranio ol; geranyl acetate; methyl dihydrojasmonate (e.g. Hedion (registered trademark)); heliotropin; 2-heptanone; 3-heptanone; 4-heptanone; tran s-2-Heptenal; cis-4-Heptenal; trans-2-Hexenal; c is-3-Hexenol; trans-2-Hexenoic acid; trans-3-Hexenoic acid; cis-3-Hexenyl acetate; cis-3-Hexenyl caproate; trans -2-Hexenyl caproate; cis-3-Hexenyl formate; para-hydroxybe nzyl acetone; Isoamyl alcohol; Isoamyl isovalerate; Isobutyl b utyrate; Isobutyl aldehyde; Isoeugenol methyl ether; Isopropyl meth yl thiazole; Lauric acid; Levulinic acid; Linalool ; Linalool oxide; Linalyl acetate; Menthol; Menthofuran; Methyl an tranilate; Methyl butanol; Methyl butyric acid; 2-Methylbutyl acetate; Methyl ca proate; Methyl cinnamate; 5-Methylfurfural; 3,2,2-Methylcyclo pentenolone; 6,5,2-Methylheptenone; Methyl jasmonate; 2-Methylmethyl butyrate; 2-Methyl-2-pentenoic acid; Methyl thiopropionate; 3,1-Methylthiohexanol; 3-Methylthiohexyl acetate ; Nerol; Neryl acetate; trans,trans-2,4-Nonadienal; 2 ,4-Nonadienol; 2,6-Nonadienol; Nootkatone; Delta octalactone ; Gamma octalactone; 2-Octanol; 3-Octanol; 1,3-Octenol ; 1-Octyl acetate; 3-Octyl acetate; Palmitic acid; Paraldehyde; Farnandrene; Pentanedione; Phenylethyl acetate; Phenylethyl alcohol ; Phenylethyl isovalerate; Propionaldehyde; Propyl butyrate; Pregone; pregol; cinensal; sulfrole; terpinene; terpineol; te lupinol; 8,3-thiomenthanone; 4,4,2-thimethylpentanone; thymol; delta-undecalactone; gamma-undecalactone; valencene; valeric acid; vanillin ; acetoin; ethyl vanillin; ethyl vanillin isobutyrate (3-ethoxy-4-i sobutyryloxybenzaldehyde); 2,5-dimethyl-4-hydroxy-3(2H) -furanone and its derivatives (preferably homofuraneol (2-ethyl-4-hydroxy -5-methyl-3(2H)-furanone), homofluronol (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 malt ol); coumarin and coumarin derivatives; gamma-lactone (preferably gamma-und ecalactone; gamma-nonalactone; gamma-decalactone); delta-lactone (pre ferably 4-methyldelta-decalactone; masoillactone; delta-decalactone; tu berolactone); methyl salicylate; dibanillin; 4-hydroxy-2(or 5)-eth yl-5(or 2)-methyl-3(2H)furanone; 2-hydroxy-3-methyl-2 -cyclopentenone; 3-hydroxy-4,5-dimethyl-2(5H)furanone; acetic acid i soamyl ester; ethyl butyrate; n-butyl butyrate; isoamyl butyrate e ster; ethyl 3-methylbutyrate; ethyl n-hexanoate; allyl n-hexanoate; n-butyl n-hexanoate; ethyl n-octanoate est er; n-hexanoic acid n-butyl ester; n-octanoic acid ethyl ester; Ru; Ethyl-3-methyl-3-phenylglycidate; Ethyl-2-trans-4-c is--decadienoate; 4-(p-hydroxyphenyl)-2-butanone; 1,1- Dimethoxy-2,2,5-trimethyl-4-hexane; 2,6-dimethyl-5-heptene -1-ol (2,6-dimethyl-5-heptene-1-al); Phenyl acetaldehyde; 2-methyl-3-(methylthio)furan; 2-methyl-3-furanti ol; Bis(2-methyl-3-furyl)disulfide; Furfuryl mercaptan; Methi onal; 2-acetyl-2-thiazoline; 3-mercapto-2-pentanone; 2,5- dimethyl-3-furanthiol; 2,4,5-trimethylthiazole; 2-acetylthia zole; 2,4-dimethyl-5-ethylthiazole; 2-acetyl-1-pyrroline; 2- methyl-3-ethylpyrazine; 2-ethyl-3,5-dimethylpyrazine; 2-ethyl-3 ,6-dimethylpyrazine; 2,3-diethyl-5-methylpyrazine; 3-isopropyl- 2-methoxypyrazine; 3-isobutyl-2-methoxypyrazine; 2-acetylpyrazine ; 2-pentylpyridine; (E,E)-2,4-decadienal; (E,E)-2,4- nonadienal; (E)-2-octenal; (E)-2-nonenal; 2-undecena -ol; 12-methyltridecanal; 1-penten-3-one; 4-hydroxy-2,5 -dimethyl-3(2H)-furanone; Guaiacol; 3-hydroxy-4,5-dimethy l-2(5H)-furanone; 3-hydroxy-4-methyl-5-ethyl-2(5H)-f ranone; Cinnamaldehyde; Cinnaalcohol; Methyl salicylate; Isopregol ; And stereoisomers, enantiomers of these substances not explicitly mentioned in this specification - A positional isomer, a diastereomer, a cis / trans isomer or an epimer; and the aforementioned is selected from the group consisting of mixtures of substances.

[0139] In another embodiment according to the present invention, the microcapsules according to the present invention are used as an active ingredient to be encapsulated or as a core material, respectively, with an aromatic substance mixture or an essential oil, or a scent mixture or a fragrance. These are compositions containing at least one aromatic substance or one fragrance substance. Such compositions, particularly aromatic mixtures or essential oils, preferably contain 2, 3, 4, 5, 6, 7, 8, 9, 10 or more aromatic substances. Each of the aromatic mixture or essential oil is preferably an extract from natural raw materials, for example, essential oils, concentrated solid fragrances, absolutes, resins, resinous substances, balsams, tinctures, for example, amber -gris oil; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; phlox absolute; bay oil; yomogi oil; benzoin resin; bergamot oil; honey wax absolute; birch tar oil; bitter almond oil; savory oil; box leaf oil; cubeb oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cassia oil; cassia absolute; castoreum absolute; hinoki oil ; cedarwood oil; citrus oil; citronella oil; citron oil; copaiba balsam; copaiba resam oil; coriander oil; costus root oil; cumin oil; itosugi oil; davana oil; dill herb oil; dill seed oil; orris absolute; oakmoss absolute; elemi oil; tarragon oil; eucalyptus citriodora leaf oil; eucalyptus oil; fennel oil; torreya Coniferous oil; chaulmoogra oil; chaulmoogra resin; geranium oil; grapefruit oil; guaiacwood oil ; gurjun balsam; gurjun balsam oil, helichrysum absolute; helichry sum oil; ginger oil; Japanese butterbur absolute; Japanese butterbur oil; jasmine absolute ; butterbur oil; chamomile oil blue; chamomile oil roman; carrot root oil; cassia oil; cedarwood oil; caraway seed oil; labdanum oil; labdanum absolute; labdanum resin; ravintsara absolute; ravintsara oil; lavender absolute; lavender oil; lemongrass oil; lavandin oil; lime oil distilled; lime oil pressed; linseed oil; litsea cubeba oil; bay leaf oil; mace oil; marjoram oil; mandarin oil; massoia bark oil; mimosa absolute; musk granule oil; musk tincture; muscat oil; myrrh absolute; myrrh oil; cinnamon bark oil; clove leaf oil; clove flower oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange flower absolute ; orange oil; oregano oil; palmarosa oil; patchouli oil; perilla oil; peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; allspice oil; pine oil; patchouli oil; rose absolute; rosewood oil; rose oil ; rosemary oil; sage oil dalmatia; sage oil spain; frankincense oil; celery seed oil; spicy lavender oil; star anise oil; euonymus oil; marigold oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka absolute ; tuberose absolute; vanilla extract; violet leaf absolute; viburnum oil; vetiver oil; juniper berry oil; wine yeast oil; mugwort oil; wintergreen oil; ila Clove oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil; and those fractions or components isolated therefrom, selected from the group.

[0140] Most preferably used in the process according to the invention is agrumex LC; ag lunitrile; aldehyde C11 undecylenate; aldehyde C12 laurate; aldehyde C12 MNA; aldehyde C14 SOG; aldehyde C16 SOG.; allyl amyl g lycolate; allyl caproate; allyl cyclohexyl propionate; allyl hept ylate; AMBROCENIDE® 10TEC; AMBROCENIDE® KRIST.10% IPM; ambroxide; anethole NAT.EX sternal nis; anisaldehyde pure; APRIFLOREN®; benzyl acetone; benzyl salicylate; borneol L / isoborneol 65 / 35; bucco blatteroel (BUCCOBLAETTEROEL); citronellol 950; clonal; cyclo hexyl salicylate; simool para supra; damascone delta; dihydro myrsenol; dimethyl benzyl carbinyl butyrate; dinascone; ethylene brassile ate; butyrate-2 ethyl methyl; ethyl safronate; eucalyptol NAT.; eucalyptus oil 80 / 85%; eugenol NAT.; FARENAL®; u ikyo oil aromatic sweet NAT.; filbertone 10% IPM; filbertone; floro pearl; galvascon; geraniol 60; GLOBANONE®; hedyo ne; herbaflo rate; herbaneate; herbil propionate; hexenyl acetate C ; IS-3; Hexenyl salicylate CIS-3; Hexyl acetate; Hexyl acetate ate; Hexyl isobutyrate; Hexyl salicylate; Isoamyl butyrate; Isobor nyl acetate; Isopropyl methyl butyrate-2; Isoraldein 70; Javanol ; Camphor DL; Cresol methyl ether P (CR <10PPM); Remonil; Lil estral; Linalool; Manganate; Melonal; Methyl heptine carbonate ; Methyl octyne carbonate; Musk senone; Neocyclocitral; Nerolin b romelia; Nerolin ylang ylang CRYST.; Nerolione; Norlinalool; Orange no el; Olibone; Ozonyl; Patchouli ENTF.; Vegetable oil triglyceride; Ferrandole fraction EX eucalyptus oil; PHENIRAT (registered trademark); Phenylethyl acetate; L inalool oxide HIGH CIS; SANDRANOL (registered trademark); Styrene acetate ; SULTANENE (registered trademark); Terpene gamma; Tetrahydrolinalool; Timber -silk; Triethyl citrate; Undecabeltol; Belt citral; Belt f ix; YSAMBER (registered trademark) K, and a mixture of the above active ingredients selected from the group consisting of aromatic substances or fragrance substances.

[0141] In the production of the microcapsules according to the present invention, representative cooling agents used as hydrophobic active ingredients include menthol and menthol derivatives (e.g., L-menthol, D- menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol ), menthyl ethers (e.g., (1-menthoxy)-2-propanediol, (1-m enthoxy)-2-methyl-1,2-propanediol, 1-menthyl methyl ether), Menthylesters (e.g., menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl lactate, L-menthyl lactate, L-menthyl lactate, D-menthyl lactate, menthyl-(2-methoxy)-acetate, menthyl-(2-methoxyethoxy)-acetate, menthyl pyroglutamate), menthyl carbonate (e.g., menthyl propylene glycol carbonate, menthyl ethylene glycol carbonate, menthyl glycerol carbonate or mixtures thereof), semi-esters of menthol and dicarboxylic acids or derivatives thereof (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinamide), menthane carboxamide (e.g., N-ethylamide of menthane carboxylic acid [WS3], N-α-(methanecarbonyl)glycine ethyl ester [WS5], menthane carboxylic acid-N-(4-cyanophenyl)-amide, menthane carboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butanoic acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butanoic acid-N-methylamide [WS23]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-(methyl)-2-(1-pyrrolidinyl)- ), menthyl-(2-methoxy)-acetate, menthyl-(2-methoxyethoxy)-acetate, menthyl pyroglutamate), menthyl carbonate (e.g., menthyl propylene glycol carbonate, menthyl ethylene glycol carbonate, menthyl glycerol carbonate or mixtures thereof), semi-esters of menthol and dicarboxylic acids or derivatives thereof (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinamide), menthane carboxamide (e.g., N-ethylamide of menthane carboxylic acid (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinamide), menthane carboxamide (e.g., N-ethylamide of menthane carboxylic acid [WS3], N-α-(methanecarbonyl)glycine ethyl ester [WS5], menthane carboxylic acid-N-(4-cyanophenyl)-amide, menthane carboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butanoic acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butanoic acid-N-methylamide [WS23]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-(methyl)-2-(1-pyrrolidinyl)- WS3], N-α-(methanecarbonyl)glycine ethyl ester [WS5], menthane carboxylic acid-N-(4-cyanophenyl)-amide, menthane carboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butanoic acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butanoic acid-N-methylamide [WS23]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-(methyl)-2-(1-pyrrolidinyl)- ), menthyl-(2-methoxy)-acetate, menthyl-(2-methoxyethoxy)-acetate, menthyl pyroglutamate), menthyl carbonate (e.g., menthyl propylene glycol carbonate, menthyl ethylene glycol carbonate, menthyl glycerol carbonate or mixtures thereof), semi-esters of menthol and dicarboxylic acids or derivatives thereof (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinamide), menthane carboxamide (e.g., N-ethylamide of menthane carboxylic acid [WS3], N-α-(methanecarbonyl)glycine ethyl ester [WS5], menthane carboxylic acid-N-(4-cyanophenyl)-amide, menthane carboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butanoic acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butanoic acid-N-methylamide [WS23]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-(methyl)-2-(1-pyrrolidinyl)- ), menthyl-(2-methoxy)-acetate, menthyl-(2-methoxyethoxy)-acetate, menthyl pyroglutamate), menthyl carbonate (e.g., menthyl propylene glycol carbonate, menthyl ethylene glycol carbonate, menthyl glycerol carbonate or mixtures thereof), semi-esters of menthol and dicarboxylic acids or derivatives thereof (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinamide), menthane carboxamide (e.g., N-ethylamide of menthane carboxylic acid [WS3], N-α-(methanecarbonyl)glycine ethyl ester [WS5], menthane carboxylic acid-N-(4-cyanophenyl)-amide, menthane carboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butanoic acid derivatives (e.g., 2 - Cyclopenten - 1 - one) or tetrahydropyrimidin - 2 - one (e.g., W illin or related compounds described in O2004 / 026840). Other cooling agents include menthol (L - menthol, D - menthol, racemic menthol, isom enthol, neoisomenthol, neomenthol), L - menthyl methyl ether, formic menthyl, menthyl acetate), menthone, isopulegol, L - (-)-isopulegol a cetate) and cubebol, which have the effect of cooling the taste. Suitable cooling agents are well - known in the art, for example, U.S. Patent Application Publication No. 2017 / 216802 (A1), U.S. Patent Application Publication No. 2010 / 273887(A1), EP203368 8(A2) and EP1958627(A2).

[0142] In an alternative embodiment, a TRPV1 or TRPV3 modulator is used as an encapsulated active ingredient or as a core material in the polyurea / polyurethane microcapsules according to the present 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 a hot sensation related to capsaicin and piperine . The TRPV3 protein belongs to a family of non - selective cation channels that function in various processes, including temperature sensation and blood vessel regulation . The TRPV3 channel is directly activated by some natural compounds such as carvacrol, thymol, and eugenol. It causes a sensation of warmth or skin ... ... ... Several other monoterpenoids that are skin-feeling substances can also open channels. Mono terpenoids also induce agonist-specific desensitization of the TRPV3 channel in a calcium-independent manner.

[0143] In another variant, the polyurea / polyurethane microcapsules according to the invention use, as the active ingredient to be encapsulated or as the core material, an active ingredient selected from the group consisting of substances that cause an irritating taste, heat, or a heat sensation on the skin or mucous membranes, or a tingling sensation in the mouth or throat, or an active ingredient that is pungent, acrid, or astringent. astringent) active ingredient.

[0144] The heat-inducing or irritating active ingredients are preferably paprika powder, chili powder, paprika extract, pepper extract, chili extract, ginger root extract, grains of paradise ( Aframomum melegueta) extract, paracress (Jambu o leoresin; Spilanthes acmella, or Spilant hes oleracea) extract, Japanese pepper (Zanthoxylum piperitu m) extract, Kaempferia galanga extract, Alpinia galanga extract, water pepper ( Polygonium hydropiper) extract, capsinoids, especially capsa icin, dihydrocapsaicin or nonivamide; gingerol, especially gingerol- 6], gingerol-[8], or gingerol-

[10] ; shogaol, especially sh ogaol-[6], shogaol-[8], shogaol-

[10] ; gingerdiol, especially gingerdiol-[6], gingerdiol-[8], or ginger erone-[6], gingerone-[8], or ginger​​​​​ - Gingerone -

[10] ; paradol, especially paradol - [6], paradol - [8], and also paradol -

[10] ; dehydrogingerdione, especially 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 - phen yl) acetate and mixtures thereof selected from the group consisting of.

[0145] The active ingredient perceived as pungent or acrid is preferably an aromatic isothiocy anate, especially phenylethyl isothiocyanate, allyl isothiocyanate, cyclopro pyl isothiocyanate, butyl isothiocyanate, 3 - methylthiopropyl isothi ocyanate, 4 - hydroxybenzyl isothiocyanate, 4 - methoxybenzyl isothi ocyanate and mixtures thereof selected from the group consisting of.

[0146] The active ingredient that causes a tingling sensation (tingling feeling) is 2E,4E - decadienoic acid - N - isobutylamide trans - pelletierine), especially those described in WO2004 / 043906 ; 2E,4Z - decadienoic acid - N - isobutylamide (cis - pelletierine) , especially those described in WO2004 / 000787; 2Z,4Z - decadienoic acid - N - iso butylamide; 2Z,4E - decadienoic acid - N - isobutylamide; 2E,4E - decad enoic acid - N - ([2S] - 2 - methylbutyl) amide; 2E,4E - decadienoic acid - N - ([2S] - 2 - methylbutyl) amide; 2E,4E - decadienoic acid - N - ([2R] - 2-Methylbutyl amide); 2E,4Z-decadienoic acid-N-(2-methylbutyl) amide d; 2E,4E-decadienoic acid-N-piperide (achilleamid e)); 2E,4E-decadienoic acid-N-piperide (salmentin); 2E-decenoic acid- N-isobutyl amide; 3E-decenoic acid-N-isobutyl amide; 3E-nonenoic acid-N- isobutyl amide; 2E,6Z,8E-decatrienoic acid-N-isobutyl amide (spira ntol); 2E,6Z,8E-decatrienoic acid-N-([2S]-2-methylbutyl) amide (homospirantol); 2E,6Z,8E-decatrienoic acid-N-([2R]- 2-methylbutyl) amide; 2E-decene-4-ynoic acid-N-isobutyl amide; 2Z- decene-4-ynoic acid-N-isobutyl amide; 2E,6Z,8E,10E-dodecatetra enoic acid-N-(2-methylpropyl) amide (α-sanshool); 2E,6Z,8E ,10E-dodecatetraenoic acid-N-(2-hydroxy-2-methylpropyl) amide ( α-hydroxy sanshool); 2E,6E,8E,10E-dodecatetraenoic acid-N -(2-hydroxy-2-methylpropyl) amide (γ-hydroxy sanshool); 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N-(2-hydroxy- 2-methylpropyl) amide (γ-hydroxy sanshool); 2E,4E,8E,1 0E,12E-tetradecapentaenoic acid-N-(2-hydroxy-2-methylpropyl) amide (γ-hydroxy isosanshool); 2E,4E,8Z,10E,12E-te tradecapentaenoic acid-N-(2-methyl-2-propenyl) amide (gamma-dehydro sanshool); 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N- (2-Methylpropyl)amide (γ-sanshool); 2E,4E,8Z,11Z-tetra decatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide (bungeanol); 2E,4E,8Z,11E-tetradecatetraenoic acid-N-(2-hydroxy -2-methylpropyl)amide (isobungeanol); 2E,4E,8Z-tetradeca trienoic acid-N-(2-hydroxy-2-methylpropyl)amide (dihydrobungeanol) and 2E,4E-tetradecadienoic acid-N-(2-hydroxy-2-methylpro pyl)amide (tetrahydrobungeanol) and mixtures thereof selected from the group consisting of

[0147] The active ingredient having astringent activity is preferably catechin, such as epicatechin, gallocate chin, epigallocatechin and their respective gallic acid esters, especially epigallocate chin gallate or epicatechin gallate, their oligomers (procyanidin, pro anthocyanidin, prodelphinidin, procyaniline, thearubigenin, theogallin ) as well as their C- and O-glycosides; dihydroflavonoid, such as dihydro myricetin, taxifolin, and their C- and O-glycosides, flavonoid l, such as myricetin, quercetin and their C and O-glycosides, such as quercetrin, rutin, gallic acid esters of carbohydrates, such as tannins, pentagalloyl glucose or their reaction products, such as ellagitannin, aluminum salts, such as alum, and mixtures thereof selected from the group consisting of.

[0148] ​​​In another variant according to the first and / or second aspect of the invention, a biological component can also be used as the core material and encapsulated, and the core material contains at least one biological component or a mixture thereof .

[0149] Biological components refer to active ingredients with biological activity, such as tocopherol, tocopherol acetate , tocopherol palmitate, ascorbic acid, carnitine, carnosine, caffeine , (deoxy)ribonucleic acid and fragments thereof, β-glucan, retinol, bisabolol , allantoin, phytantriol, panthenol, AHA acid, amino acids, ceramides , pseudoceramides, essential oils, plant extracts, as well as vitamin complexes.

[0150] In a further variant of the process according to the invention, substances for printing coatings for paper are also used as the active ingredient to be encapsulated or as the core material, respectively, as described in U.S. Patent No. 28 00457(A), the disclosure of which in this regard is hereby incorporated by reference in its entirety into this specification.

[0151] The internal non-aqueous phase contains, for example, 20 to 80 wt.%, preferably 25 to 75 wt.%, even more preferably 33 to 50 wt.% of the encapsulated hydrophobic active ingredient, 0.1 to 5 wt.%, preferably 0.15 to 3.5 wt.%, and even more preferably 0.5 to 2.5 wt.% of the first cross-linking agent, and additionally up to 100 wt .% of a hydrophobic solvent may be contained.

[0152] Thus, using the process according to the invention, it is possible to achieve a high usage amount of the active ingredient in the microcapsules according to the invention. ​

[0153] In a further step (ii) of the process according to the invention, at least one tamp rotein and / or at least one polysaccharide, and optionally at least one protective co loid are provided in an external aqueous phase.

[0154] 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 include glycerol, 1,2-propanediol, 1,3-propanediol, ethanediol, diethylene glycol, triethylene glycol, and other analogs. However, preferably the solvent is water.

[0155] According to the invention, at least one protein is selected from the group consisting of proteinogenic L-amino acids, animal or plant proteins, in particular animal or plant proteins in the form of protein isolates, fractions, partial or complete hydrolysates or intermediates produced by physicochemical processes or fermentation or enzymatic treatment of proteins, in particular meat (mammals , birds, reptiles, amphibians, fish), crabs, crustaceans, mussels, mollusks, insects, eggs, milk, in particular casein and whey, rennet casein, 80% whey protein concentrate, gelatin, algae, grains, in particular wheat, barley, rye, spelt, gluten, in particular wheat gluten , rapeseed, sunflower, rice, potato, corn, soybean, bean, pea, lentil, lupinus, peanut, alfalfa, hemp, and proteins from other edible plants, chitosan, and mixtures thereof.

[0156] ​​​​Of the above proteins, gelatin, milk protein, whey protein, pea protein Proteins are particularly preferred.

[0157] Amino acids are proteinogenic L-amino acids. L-amino acids include 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 It is selected.

[0158] Of the above amino acids, L-glutamine and L-lysine are particularly preferred.

[0159] In a preferred variant, one of the above proteins is treated with one or more free L-amino acids. A preferred combination is milk protein with L-glutamine and and / or L-lysine. Such a combination allows for the synthesis of both large and small molecules. The more the protein is incorporated into the network, the more stable it becomes. In addition, the amino acids L-glutamine and and / or L-lysine are particularly readily cross-linked by enzymatic cross-linking agents such as transglutaminase. It can be easily crosslinked.

[0160] The protein has the advantageous effect of exhibiting an emulsifying effect. Their emulsifying effect contributes to the stabilization of emulsions. Proteins are amphiphilic. They are surface active due to a certain degree of structural flexibility and their differently charged regions within the molecule. For example, proteins can be modified by physical or chemical modification to increase the molecular The secondary and / or tertiary structure can be changed. Thus, the influence on the emulsifying properties can be achieved 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, in the process according to the invention , additional emulsifiers or protective colloids can be omitted.

[0161] The proportion of at least one protein in the external aqueous phase is 0 .25 to 5.0 wt.%, preferably 0.5 to 3.0 wt.%, based on the total weight of the external aqueous phase. Most preferably, at least one protein is used in the range of 1.0 to 1 .5 wt.% based on the total weight of the external aqueous phase.

[0162] According to the first and second aspects of the invention, at least one polysaccharide is - indigestible fibers and dietary fibers, especially insoluble dietary fibers, especially cellulose, cellulose derivatives such as hydroxyethyl cellulose, especially quaternized hydroxyethyl cellulose, carboxymethyl cellulose (CMC) and microcrystalline cellulose (MCC), hemicellulose , lichenin, chitin, chitosan, lignin, xanthan, plant fibers, especially cereal fibers, potato fibers, apple fibers, citrus fibers, bamboo fibers, sugar beet extract fibers ; embac fibers and soluble dietary fibers, especially inulin, especially native inulin, highly soluble inulin, granular inulin, high-performance inulin, pectin, alginate, agar, carrageenan , arabic gum (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose , xylose, polydextrose, and lactulose; ; embac fibers and soluble dietary fibers, especially inulin, especially native inulin, highly soluble inulin, granular inulin, high-performance inulin, pectin, alginate, agar, carrageenan , arabic gum (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose , arabic gum (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose , arabic gum (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose , xylose, polydextrose, and lactulose; - Starches, especially those derived from wheat, potato, corn, rice, tapioca and oats starches, modified starches, and starch derivatives such as dextrins or maltodextrins, especially those derived from wheat, potato, corn, rice, pea and oats dextrins and maltodextrins, especially maltodextrin DE8-10, DE 17-20, DE18-20, cyclodextrins, oligosaccharides, especially oligofructose ; and - sugar alcohols, especially sorbitol, mannitol, isomalt, maltitol, maltitol syrup, lactitol, xylitol, erythritol ; - glucose and mixtures of two or more of the above polysaccharides selected from the group consisting of.

[0163] Among the above polysaccharides, gum arabic and maltodextrin are particularly preferred. Most preferably is maltodextrin DE8-10 potato; DE17-20 corn; DE17-20 potato and DE18-20 wheat.

[0164] The proportion of at least one polysaccharide in the external aqueous phase is in the range of 0.5 to 7.0 wt.%, preferably in the range of 1.5 to 6.0 wt.%. Most preferably is that at least one polysaccharide is used in the range of 3.0 to 5.0 wt.% based on the total weight of the external aqueous phase. range.

[0165] Preferably, the external aqueous phase is provided with both main components of the capsule shell, namely, at least 1 protein and at least one polysaccharide. Combine protein and polysaccharide When used in this way, soluble or insoluble protein-polysaccharide complexes are formed. In this way The emulsions thus formed are less likely to form aggregates, so in the process according to the invention There is no need to add a protective colloid or an additional emulsifier.

[0166] For constructing the capsule wall or capsule shell, the following combinations of proteins and polysaccharides are particularly preferred: whey protein and maltodextrin; milk protein and malt odextrin; whey protein and gum arabic; gelatin and maltodextrin; milk protein, L-glutamine, L-lysine, and maltodextrin; and gelatin in, milk protein, and maltodextrin.

[0167] Most preferred for constructing the capsule shell is the combination of gelatin and maltodextrin D E8-10 potatoes, or the combination of milk protein, L-glutamine and / or or L-lysine and maltodextrin. Such a capsule shell Microcapsules prepared using the material result in microcapsules with a free oil content of ≦ 1% in isopropanol of the microcapsules.

[0168] The foregoing and exemplified components for constructing the capsule wall, protein and polysaccharides are readily available from biological sources. Furthermore, they are readily biodegradable as such ru. of.

[0169] In an alternative variant of the process according to the invention, the external aqueous phase provides only one of the main components of the capsule shell, protein or polysaccharide. In this variant, the other main component The addition of polysaccharides or proteins, if necessary, is carried out after emulsification / dispersion and after the addition of the catalyst in process step (v ) and in step (iv), before or together with the addition of the catalyst in process step (v).

[0170] By using at least one protein and at least one polysaccharide, the content of the crosslinking agent polyisocyanate in the capsule shell can be preferably or up to a maximum of 50 wt.% isocyanate content, more preferably up to a maximum of 20 w t.% isocyanate content, reduced based on the capsule shell compared to microcapsules of the state-of-the-art with a high polyisocyanate content t.% isocyanate content, and a capsule wall or capsule shell can be constructed as a component for replacing polyisocyanate with protein and / or polysaccharide so that the polyisocyanate content in the microcapsules is reduced and the degree of crosslinking decreases.

[0171] Surprisingly, however, as shown in the following embodiments, this lower degree of crosslinking results in, on the one hand, stable microcapsules and, on the other hand, microcapsules with better biodegradability.

[0172] A protective colloid may be added to the external aqueous phase if necessary.

[0173] The protective colloid is a polymer system that prevents aggregation (aggregation, coagulation, clotting) of the emulsifying, suspending, or dispersing components in a suspension or dispersion. In solvation, the protective colloid binds a large amount of water and generates a high viscosity in the aqueous solution depending on the concentration. In the preparation of an oil-in-water emulsion, the protective colloid ​​​​​​The ID is a hydrophobic moiety that attaches itself to the primary particles and turns its polarity, i.e., the hydrophilic molecular moiety, towards the water phase. By this attachment to the interface, the interfacial tension is lowered, preventing the aggregation of the primary particles. In addition, this stabilizes the emulsion, promotes the formation of relatively small droplets, and also promotes the formation of the corresponding microcapsules.

[0174] In the process according to the invention, the protective colloid exhibits emulsifying properties in addition to the above-mentioned properties. Protective colloids, for example, carboxymethyl cellulose, acid-modified starch, polyvinyl alcohol ammonium derivatives of polyvinyl alcohol, polystyrene sulfonate, poly vinylpyrrolidone, polyvinyl acrylate, etc., when having sufficient emulsifying properties, thereby advantageously, in the downstream emulsification / dispersion step (iii) of the process according to the invention, it is also possible to omit the use of an emulsifier. For example, in the case of quail egg-based microcapsules, preferably polyvinyl alcohol is preferably the only protective colloid added to the aqueous phase.

[0175] The protective colloid used in the process according to the invention is - diols, especially ethanediol, 1,2-propanediol, 1,3-propanediol 1,2-butanediol, isobutanediol, 1,2-pentanediol, 1, 2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2- dodecanediol, and - polyols, preferably triols, especially glycerin, and its ethoxylated and propoxylated products, trimethylolpropane and its ethoxylated and prop Ropoxylated products, polyvinyl alcohol (PVOH) and its derivatives, especially ammo nium or sulfonate-functionalized polyvinyl alcohol, polyphenols, preferably 1 ,3,5-trihydroxybenzene, polysaccharides, especially glucose, starch, or chemically, mechanically and / or enzymatically modified starch, cellulose derivatives, such as hydroxy ethyl cellulose, especially quaternized hydroxyethyl cellulose, and carboxymethyl cellulose, - polyvinylpyrrolidone, vinyl maleate copolymer, sodium lignosulfonate , maleic anhydride / styrene copolymer, ethylene / maleic anhydride copolymer, ethylene oxide, copolymer of propylene oxide and acid ester of polyethoxylated sorbitol , sodium dodecyl sulfate, - animal and plant polymers, especially gum arabic (Senegal type and Seyal type), tan nins, gelatin, olibanum resin, shellac, lignin, chitosan, saponin as well as mixtures of the above compounds selected from the group consisting of.

[0176] Starch, especially modified starch, or animal or plant polymers are biodegradable natural substances that exist. Therefore, in combination with the polyisocyanates described herein , this process can provide a biodegradable, bio-based capsule shell. Thus, in the process according to the invention, starch as well as animal and plant polymers also function as so-called bio-crosslinking agents.

[0177] The starch used in the process according to the invention is corn starch, potato de Glutinous rice starch, high amylose corn starch, wheat starch, barley starch, oat starch, rice starch , selected from the group consisting of pea starch, tapioca starch, and mixtures thereof .

[0178] Preferably, the chemically modified starch is acid-modified starch, alkali-modified starch, oxidized starch , acetylated starch, succinylated starch, or octenyl succinylated starch .

[0179] Preferably, the external aqueous phase contains at least one protective colloid selected from polyvinylpyrrolidone, polyvinyl alcohol, and mixtures thereof. Polyvinylpyrrolidone is particularly preferred. Commercially available standard polyvinylpyrrolidone has a molecular weight in the range of about 2500 - 75 0000 g / mol. .

[0180] Even more preferably, a polyol, a polyphenol or a starch, especially a modified starch is used as the protective colloid. Particularly preferably, polyvinyl alcohol or its ammonium derivative, 1,3,5-trihydroxybenzene, modified starch or carboxymethyl cellulose is used as the protective colloid for the preparation of the microcapsules according to the invention . .

[0181] According to the invention, a combination of two or more different protective colloids can also be used in the preparation of the microcapsules according to the invention .

[0182] In the process according to the invention, it has been found to be particularly advantageous to use in the external aqueous phase a combination of one of the above protective colloids and starch as a further protective colloid . Such combinations stabilize the emulsion due to the large number of functional hydroxyl groups and, on the other hand, act favorably on the reaction between the protective colloid and the polyisocyanate, whereby the reaction equilibrium of the reaction between the protective colloid and the polyisocyanate shifts towards the product, i.e., the poly urethane side. Furthermore, the large number of functional hydroxyl groups in the starch enables the formation of spatially particularly prominent crosslinks.

[0183] Depending on the number of functional groups and / or the size of the protective colloid, the above-mentioned protective colloid exhibits different reaction rates with the isocyanate groups of at least one polyisocyanate. For example glycerin, due to its size, reacts faster with isocyanate groups than, for example, starch. Therefore, the crosslinking of the protective colloid by the isocyanate groups of the polyisocyanate can be controlled by the selection of the protective colloid.

[0184] Particularly advantageous combinations are combinations of glycerin with starch or modified starch or combinations of glycerin with quaternized hydroxyethyl cellulose or gum arabic type which have proven to be such that by such combinations, the aforementioned properties of both protective colloids, i.e., on the one hand the high reaction rate of glycerin and on the other hand the large number of polymerizable functional groups of the other protective colloid, can be utilized.

[0185] The protective colloid used in the process according to the invention has, on the one hand, a dual function of acting as a protective colloid and thus preventing the aggregation of the emulsifying, suspending or dispersing components and subsequently stabilizing the formed emulsion promoting the formation of small droplets and finally the formation of the Stabilize the microcapsule dispersion.

[0186] Therefore, the amount of protective colloid used or the combination of protective colloids used is in the range of 1 to 6 wt.%, preferably 2 to 4 wt.%, more preferably in the range of 2 to 3 wt.%, based on the total weight of the external aqueous phase.

[0187] The external aqueous phase is preferably prepared under stirring by continuously adding a polysaccharide and / or a protein, and optionally a protective colloid, or vice versa, to the external aqueous phase, or by adding the components simultaneously to the external aqueous phase.

[0188] To improve the solubility of the protein, the pH value of the external aqueous phase is adjusted, if necessary, to a pH value lower than the isoelectric point of the protein, i.e., lower than the isoelectric point of the protein used.

[0189] 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 are in equilibrium in an ampholyte or zwitterion (e.g., amino acids and proteins). This value is a constant characteristic of each amino acid and depends on the pKs values of the functional groups. In addition to amino acids, peptides and proteins also have an isoelectric point. At the isoelectric point, amino acids, and thus proteins, also exhibit the lowest water solubility.

[0190] Preferably, the pH value of the aqueous phase is adjusted to a pH value in the range of 2.0 to 7.0, more preferably in the range of 2.0 to 6.0, and most preferably to a slightly acidic pH value in the range of 3.0 to 5.0, as a function of the isoelectric point of the protein used. A pH below the isoelectric point When the pH value is adjusted to a value, i.e., a pH value below the isoelectric point of the protein, such a pH value has the advantage that the emulsifying properties and solubility of the protein are highest.

[0191] The pH value of the external aqueous phase is adjusted by adding an organic acid. For this purpose, an organic acid, such as formic acid or acetic acid, is added to the external aqueous phase before the emulsification step and adjusted to a pH value within the above range to be.

[0192] An internal non-aqueous phase containing at least one first cross-linking agent and at least one hydrophobic active ingredient is emulsified or dispersed in the external aqueous phase in a further process step (iii) to form an oil-in-water emulsion / dispersion.

[0193] The oil-in-water emulsion is prepared by mixing the internal non-aqueous phase and the external aqueous phase. The weight ratio of the internal non-aqueous phase to the external aqueous phase is preferably in the range of 70:30 to 60:40, preferably in the range of 30:70 to 60:40.

[0194] To promote the formation of an emulsion or dispersion from the internal non-aqueous phase and the external aqueous phase, and to stabilize the formed emulsion or dispersion respectively, and to prevent the separation of the internal non-aqueous phase (oily / organic / hydrophobic) from the external aqueous phase (hydrophilic), a stabilizer and / or an emulsifier or an emulsification aid is added to the emulsion or dispersion as required in the process according to the present invention.

[0195] Preferably, a stabilizer that stabilizes the emulsion / dispersion and prevents the separation of the internal non-aqueous (oily) phase from the external aqueous phase is added to the external aqueous phase.

[0196] A preferred stabilizer for preparing the polysaccharide and protein-based microcapsules according to the present invention ​The agent is mainly an acrylic copolymer having a sulfonate group. Also, acrylamide copolymers with acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone , for example LUVISKOL® K15, K30, or K90 (BASF); sodium polycarboxylate, sodium polystyrene sulfonate, vinyl and methyl vi nyl ether-maleic anhydride copolymer, and ethylene, isobutylene or sty rene-maleic anhydride copolymer, for example commercially available under the name VIVAPUR® microcrystalline cellulose, diutan gum, xanthan gum or carboxymethylcellu lose are also suitable.

[0197] The amount of stabilizer used may be in the range of 0.01 to 10 wt.%, preferably 0.1 to 3 wt.%, based on the external aqueous phase respectively.

[0198] If necessary, an emulsifier, preferably an O / W-emulsifier, is used in the process according to the invention so that a uniform distribution of the oil droplets of the internal non-aqueous phase in the external aqueous phase is possible and the emulsion is stabilized. The same applies when mixing a solid insoluble active ingredient into the external aqueous phase to stabilize the dispersion thus obtained.

[0199] The addition of an emulsifier is carried out if necessary, especially when the emulsifying properties of the protein or protective colloid are completely absent or low, i.e. insufficient. When using an emulsifying protein and / or a protective colloid, the use of an emulsifier can advantageously be omitted in the process according to the invention.

[0200] Suitable emulsifiers include, for example, the following groups:​​​ - Adhesion products to linear fatty alcohols having 8 to 22 C atoms in the alkyl group, to fatty acids having 12 to 22 C atoms, to alkylphenols having 8 to 15 C atoms, and to alkylamines having 8 to 22 carbon atoms in the alkyl radical, of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide ; - Alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alkyl(alkenyl) radical and their ethoxylated analogues; - Addition products of 1 to 15 mol of ethylene oxide to castor oil and / or hydrogenated castor oil; ; - Addition products of 15 to 60 moles of ethylene oxide to castor oil and / or hydrogenated castor oil; ; - Partial esters of glycerin and / or sorbitan with unsaturated straight-chain or saturated branched-chain fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms, and their adducts with 1 to 30 moles of ethylene oxide; ; - Partial esters of polyglycerin (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 straight-chain or branched-chain fatty acids containing 12 to 22 carbon atoms and / or hydroxycarboxylic acids containing 3 to 18 carbon atoms, and their adducts with 1 to 30 mol of ethylene oxide, preferably Cremophor ; ; ; ; ; ; ; ; ; ; ; Registered trademark); - Mixed esters of pentaerythritol, fatty acids, citric acid and aliphatic alcohols, and / or mixed esters of fatty acids containing 6 to 22 carbon atoms, methyl glucose and poly ols, preferably glycerin or polyglycerin; - Mono-, di- and trialkyl phosphates, and mono-, di- and / or tri-PEG-alkyl phosphates and their salts; - Wool wax alcohol; - Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; - Block copolymers, for example, polyethylene glycol-30 dipolyhydroxystearate; - Polymer emulsifiers, for example, pemulene grades (TR- 1, TR-2) manufactured by Goodrich or Cosmedia® SP manufactured by Cognis; - At least one nonionic surfactant selected from polyalkylene glycols and glycerin carbonate is included.

[0201] Typical anionic emulsifiers that 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, such as palmitic acid, stearic acid, or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, such as azelaic acid or sebacic acid.

[0202] Furthermore, zwitterionic surfactants can be used as emulsifiers in the process according to the invention for preparing polysaccharide and protein-based microcapsules. Zwitterionic ​​​​The cationic surfactant is a surfactant compound having at least one quaternary ammonium group, at least one carboxylate group, and one sulfonate group in the molecule. In particular preferred zwitterionic surfactants are so-called betaines, such as N-alkyl-N,N- dimethylammonium glycinate, such as cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, such as cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl- 3-hydroxyethylimidazoline having 8 to 18 C atoms in the alkyl or acyl group, respectively, and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. Particularly preferred is the fatty acid amide derivative known by the CTFA name cocamidopropyl betaine.

[0203] Also, suitable emulsifiers are amphoteric surfactants. Amphoteric surfactants mean surfactant compounds that contain at least one free amino group and at least one -COOH or -SO3H group in addition to the C8 / 18 alkyl or acyl group in the molecule and can form an internal salt. Examples of suitable amphoteric surfactants are, respectively, N-alkylglycine, N-alkylpropionic acid, N-alkyl aminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkyl amidepropyl glycine, N-alkyltaurine, N-alkylsarcosine, 2-alkyl aminopropionic acid, alkylaminoacetic acid, each having about 8 to 18 C-atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coconut alkyl aminopropionate, cocosacyl aminoethyl (cocosacyl aminoethyl) aminopropionate and C12 / 18 acyl sarcosine.

[0204] Finally, cationic surfactants can also be used as emulsifiers, such as ester quats type, preferably methyl quaternized di-fatty acid triethanolamine ester salt, quaternized hydroxyethyl cellulose, chitosan modified with propylene glycol and epichlorohydrin quaternized distearyldimethylammonium chloride (DSDMAC), benzalkonium chloride, benzethonium chloride, cetylalconium chloride, cetylpyridinium chloride, cetyltrimethylammonium bromide (cetrimonium bromide), decyltrimethylammonium chloride are particularly preferred.

[0205] The emulsifiers can be added to the external aqueous phase in an amount of about 0.5 to about 10 wt.%, and preferably about 1 to about 5 wt.%, based on the total weight of the external aqueous phase.

[0206] Emulsion formation (for liquid active ingredients) or dispersion formation (for solid active ingredients), i.e., the emulsification or dispersion of the internal non-aqueous or oil phase and the external 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 resulting microcapsules. The preparation of microcapsules can be carried out continuously or discontinuously. As the viscosity of the aqueous phase increases or the viscosity of the oil phase decreases, the size of the capsules generally decreases.

[0207] The process according to the invention for preparing polysaccharide-based and protein-based microcapsules can be carried out, for example, according to the "in-line" technique, whereby forced metering The inner non-aqueous phase and the outer aqueous phase are first fed separately to the emulsification turbine by the pump. Just before entering the bin or at a throughput of 1200-1500 l / hour In addition, polysaccharide and protein microcapsules are prepared. The process according to the invention for preparing the dispersion or emulsification products can also be carried out in conventional dispersion or emulsification equipment. do.

[0208] The emulsification or dispersion of the external aqueous phase and the internal non-aqueous phase is the basis for the preparation of microcapsules according to the present invention. For this purpose, for example, an emulsification turbine (IKA Eurostar 20 high-speed agitator) is used. cormorant.

[0209] The emulsification or dispersion process in the process according to the present invention is carried out at 1000 rpm to 500 rpm. 0 rpm, preferably 3000 rpm to 4000 rpm, for 30 seconds to 20 minutes, 10 to 50 μm ± 5 μm, preferably for 1 to 4 minutes, and most preferably for 1 to 2.5 minutes Advantageously, this is carried out until a capsule size of 100 μm is obtained.

[0210] After the emulsification or dispersion step (iii) is completed, the inner oil containing the active ingredient to be encapsulated is An oil-in-water emulsion in which the aqueous phase is finely emulsified or dispersed in the form of droplets in an external aqueous phase or A dispersion is present.

[0211] In an alternative variant of the process according to the invention, as previously described, the emulsification or dispersion step (i After ii), the addition of at least one polysaccharide or at least one protein is performed in step In process step (ii), a small amount of the external aqueous phase is added. When providing only at least one protein main component, the addition of at least one polysaccharide is carried out in process step (iv). On the other hand, when the external aqueous phase in process step (ii) contains only at least one polysaccharide main component, the addition of at least one protein is carried out in process step (iv). By separate addition, multiple layers are formed ( "one layer at a time"), and the individual layers are cross-linked with each other in subsequent process step (v). Thereby, for example, the charge of the emulsion, and thus the aggregation stability, can be controlled. This is carried out in process step (iv). On the other hand, when the external aqueous phase in process step (ii) contains only at least one polysaccharide main component, the addition of at least one protein is carried out in process step (iv). By separate addition, multiple layers are formed ( "one layer at a time"), and the individual layers are cross-linked with each other in subsequent process step (v). Thereby, for example, the charge of the emulsion, and thus the aggregation stability, can be controlled. When providing only at least one polysaccharide main component, the addition of at least one protein is carried out in process step (iv). By separate addition, multiple layers are formed ( "one layer at a time"), and the individual layers are cross-linked with each other in subsequent process step (v). Thereby, for example, the charge of the emulsion, and thus the aggregation stability, can be controlled. This is carried out in process step (iv). By separate addition, multiple layers are formed ( "one layer at a time"), and the individual layers are cross-linked with each other in subsequent process step (v). Thereby, for example, the charge of the emulsion, and thus the aggregation stability, can be controlled. This is carried out in process step (iv). By separate addition, multiple layers are formed ( "one layer at a time"), and the individual layers are cross-linked with each other in subsequent process step (v). Thereby, for example, the charge of the emulsion, and thus the aggregation stability, can be controlled. Thereby, for example, the charge of the emulsion, and thus the aggregation stability, can be controlled.

[0212] Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. Alternatively, at least one protein from process step (ii) and / or at least one polysaccharide that is the same or different, or has a different charge, or whose charge changes when the pH value changes, can be added in process step (iv) as needed. By adding another protein and / or polysaccharide, additional layers ( "one layer at a time") are constructed, and the individual layers are cross-linked with each other in subsequent process step (v). This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules. This results in a denser and more stable network of capsule wall components, and as a result, a more stable capsule shell is obtained, thereby improving the stability of the microcapsules.

[0213] The additional protein and / or additional polysaccharide is selected from the group of proteins and / or polysaccharides already defined in detail above for process step (ii). The same applies to the preferred variants or preferred combinations of the proteins and / or polysaccharides described herein. The additional protein and / or additional polysaccharide is selected from the group of proteins and / or polysaccharides already defined in detail above for process step (ii). The same applies to the preferred variants or preferred combinations of the proteins and / or polysaccharides described herein. The additional protein and / or additional polysaccharide is selected from the group of proteins and / or polysaccharides already defined in detail above for process step (ii). The same applies to the preferred variants or preferred combinations of the proteins and / or polysaccharides described herein. The additional protein and / or additional polysaccharide is selected from the group of proteins and / or polysaccharides already defined in detail above for process step (ii). The same applies to the preferred variants or preferred combinations of the proteins and / or polysaccharides described herein.

[0214] In a subsequent process (v) of the process according to the invention, while stirring in the same manner, the first crosslinking of the material of the coacervate or the capsule wall is carried out.

[0215] The first crosslinking is carried out by adding a catalyst in order to crosslink the above-described layer of the capsule wall component ( "layer by layer") after emulsification or dispersion and to stabilize the resulting capsule shell. By this way, on the one hand, a polymerization reaction between the carboxyl group and / or sulfonic group and / or hydroxyl group of the polysaccharide and the amino group of the protein is catalyzed, and on the other hand, the isocyanate group of the first crosslinking agent causes an interfacial polymerization at the interface between the external aqueous phase and the dispersed internal phase, that is, at the interface of the emulsified or dispersed oil droplets surrounding the encapsulated active component. Similarly, when the catalyst has already been added to the internal non-aqueous phase, the crosslinking occurs in the same way after emulsification or dispersion of the non-aqueous phase and the aqueous phase.

[0216] A first crosslinking unit or a first crosslinking matrix for the structure of the capsule shell or the capsule wall is formed by the catalytic crosslinking between the functional groups of at least one polysaccharide and / or at least one protein of the above-described layer and the functional groups of the first crosslinking agent.

[0217] The formation of the first crosslinking unit in the process according to the invention is based on an addition polymerization reaction between the polysaccharide and the first crosslinking agent and / or between the protein and the first crosslinking agent. Thereby, the hydroxyl group of the polysaccharide reacts with the isocyanate group of the first crosslinking agent to form polyurethane, and the amino group of the protein reacts with the isocyanate group of the first crosslinking agent to form polyurea. In addition to polyurethane and polyurea, soluble or insoluble composites of proteins and polysaccharides ​​The body is also formed during the first crosslinking step (v) and constitutes the capsule wall matrix or the capsule shell.

[0218] 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 microcapsules. In addition to the number of functional groups, the chain length of the individual capsule wall building blocks also has a great influence on the mechanical properties, i.e., the stability of the microcapsules: for example, a large number of hydroxyl groups of starch enable the formation of particularly prominent spatial crosslinking; longer-chain capsule wall building blocks, such as polyisocyanates, also result in the formation of more stable capsule walls. By the numerous hydroxyl groups of starch, the formation of particularly prominent spatial crosslinking becomes possible; longer-chain capsule wall building blocks, such as polyisocyanates, also result in the formation of more stable capsule walls.

[0219] The formation of the first crosslinked matrix or the first crosslinked unit causes the core material, i.e., the emulsified or dispersed oil droplets containing the encapsulated active ingredient, to be surrounded at the interface by the outer crosslinked matrix or crosslinked unit, thus generating a capsule wall and making the diffusion of the encapsulated active ingredient more difficult.

[0220] The addition of at least one catalyst to the emulsion or dispersion promotes the crosslinking reaction between the polysaccharide and / or the protein and the crosslinking agent, and preferably catalyzes the reaction for the formation of the first crosslinked matrix or the first crosslinked unit.

[0221] The catalyst added in the process according to the invention is preferably 1,4-diazabicyclo[2.2.2] octane (DABCO), also known as triethylenediamine (TEDA), and is a bicyclic tertiary amine. DABCO is generally used in the production of polyurethane plastics . ​It is used as a catalyst. A tertiary amine having a free electron pair promotes the reaction between the isocyanate group of the first crosslinking agent and the hydroxyl group of the polysaccharide.

[0222] K.C. Frisch & L.P. Rumao, Catalysis in Isocy anate Reactions, Polymer Reviews, 1970, 5: 1, 103 - 149, DOI: 10.1080 / 15583727008085365 As described in, in addition to DABCO, for example, catalysts based on bismuth or tin, such as catalysts based on bismuth (II) salts or bismuth (III) salts, are also used to catalyze the first crosslinking, and the disclosure thereof in this regard is incorporated herein in its entirety.

[0223] According to the present invention, a combination of DABCO and one of the above catalysts is preferred. Such a mixture results in a doubling of reactivity, as described in K.C. Frisch & L.P. Rumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5:1, 103 - 149, DOI: 10.1080 / 15583727008085365, and the disclosure thereof in this regard is incorporated herein in its entirety. 0, 5:1, 103 - 149, DOI: 10.1080 / 155837270080 85365, and the disclosure in this regard is incorporated herein in its entirety.

[0224] DABCO and the above catalysts preferably catalyze the polyurethane reaction between at least one polymerizable polyisocyanate having two or more isocyanate groups and a diol or polyol in the process according to the present invention.

[0225] The amount of catalyst added to the external aqueous phase is in the range of 0.001 to 1 wt .%, preferably in the range of 0.02 to 0.75 wt.%, particularly preferably in the range of 0.05 to 0.5 wt.%. However, if the polymerization is slow, the catalyst can also be increased.

[0226] The catalyst is added to the emulsion or dispersion with stirring, for example as a solid or in the form of an aqueous solution, preferably in water. The catalyst is present in the aqueous solution at a concentration of 0.5 to 2 mol / l, preferably 1 m ol / l.

[0227] The catalyst is added at a stirring speed of 500 rpm to 2000 rpm, preferably 1000 rpm to 1500 rpm, at a temperature in the range of 20°C to 30°C, preferably at a temperature of 22°C to 26°C.

[0228] Even more preferably, the process step (v) of the first crosslinking by the catalyst is carried out by gradually heating the emulsion or dispersion to a temperature in the range of 60°C 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 present invention is carried out for a duration of about 30 minutes to 90 minutes, preferably for a duration of 40 minutes to 70 minutes, most preferably for a duration of 60 minutes.

[0229] After the first crosslinking and formation of the capsule shell or capsule wall, the capsules prepared according to the process of the present invention are present as crude microcapsules in the form of an aqueous dispersion or slurry.

[0230] After crosslinking, the microcapsules in the slurry still have a flexible shell, but ​​​​​​​​​It does not have special stability and thus easily breaks open. For this purpose, the cells are cured. The curing in process step (vi) is preferably carried out by gradually raising the microcapsule slurry to a temperature of at least 60 °C, preferably in the range of 60 °C to 65 °C, up to the maximum boiling point of the microcapsule slurry. Usually, the curing is carried out for at least 3 hours, preferably 4 hours, most preferably 5 hours. Alternatively, for example, in the case of quail egg protein-based microcapsules, the microcapsules are cured at a temperature of 70 °C for 1 hour, followed by raising the temperature preferably to 80 °C (within about 30 minutes) and preferably curing at 80 °C for a further 1 hour.

[0231] It is further advantageous to add a substance to the microcapsule slurry for curing. For this purpose, tannin-type natural plant tanning agents are used, which, from a chemical point of view, are especially proanthocyanidins found in tropical and subtropical dicotyledonous plants, shrubs, and leaves. Terpenes generally have a molecular weight in the range of 500 - 3000 KDa. A preferred example of a suitable tannin is corigallin. For curing, an aqueous preparation of tannin is added to the aqueous dispersion containing the crude microcapsules. Typically, tannin is added in an amount of about 0.1 - about 2 wt.%, preferably about 0.5 - about 1.5 wt.% based on the microcapsules.

[0232] In an alternative variant of the process according to the invention, in order to optimize the crosslinking of the capsule wall matrix, further protein and / or further polysaccharide is, if It can be added to the microcapsule slurry in step (vi).

[0233] Further protein and / or further polysaccharide are selected from the group of proteins and / or polysaccharides already defined in detail above for process step (ii). The same definitions and preferred embodiments and / or preferred combinations regarding the protein and / or polysaccharide are fully effective also for the further protein and / or further polysaccharide.

[0234] The further protein and / or further polysaccharide may be the same as or different from the protein and / or polysaccharide of process step (ii). Preferably, the further protein and / or further polysaccharide is different from the protein and / or polysaccharide of process step (ii).

[0235] The addition of further protein and / or further polysaccharide results in further crosslinking with the first crosslinking agent and contributes to the formation of a particularly dense and stable network of capsule wall building blocks.

[0236] After the curing step (vi) of the process according to the invention, the step of cooling the microcapsule slurry to room temperature and, optionally, a second crosslinking step of the capsule wall building blocks by adding a second crosslinking agent follow.

[0237] As the second crosslinking agent for the second crosslinking step, the process according to the invention uses transglutaminase, already described in relation to the first crosslinking agent and further crosslinking agents. ​​​​​​​​​​​​Peroxidase, a secondary plant compound, a polyphenol, especially tannin, gallic acid , ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol group at least one crosslinking agent selected from the group consisting of secondary plant compounds selected, and the above-mentioned two or more mixtures of the crosslinking agents are used. The same definition and preferred embodiments as for the first and further crosslinking agents are also fully effective for the second crosslinking agent.

[0238] Among the above-mentioned further crosslinking agents, particularly preferred are cinnamaldehyde, tannin and gallic acid.

[0239] In a preferred variant of the process according to the invention, the second crosslinking agent is different from the first and further crosslinking agents in process step (i).

[0240] The content of the second crosslinking agent ranges from 0.1 to 5 wt.%, preferably from 0.15 to 2.5 wt.%, based on the total weight of the non-aqueous phase. Most preferably, the second crosslinking agent is used in the internal non-aqueous phase in the range of 0.5 to 1 wt.% based on the total weight of the non-aqueous phase.

[0241] The second crosslinking agent is added to the emulsion or dispersion while stirring, for example as a solid, or in the form of an aqueous solution.

[0242] The second crosslinking agent is present in the aqueous solution at a concentration of 0.01 to 2 mol / l, preferably at a concentration of 0.1 to 1.5 mol / l, most preferably at a concentration of 0.5 to 1.0 mol / l. The solution has a pH value of 7 to 14, preferably a pH value of 12.

[0243] Even more preferably, the second crosslinking in process step (vii) is an emulsion The solution or dispersion is heated to a temperature in the range of 20°C to 50°C, preferably in the range of 30 to 40°C. The second step in the process according to the invention is carried out by gradually heating the mixture to a temperature of 100° C. The crosslinking is carried out for a duration of about 20 minutes to 10 hours, preferably for a duration of 30 minutes to 8 hours. .

[0244] The first crosslinking and / or proton exchange in process step (v) of the process according to the invention To optimize the second crosslinking in process step (vii), optionally The pH value of the solution or dispersion should be adjusted to a value higher or lower than the isoelectric point of the protein used. At pH values ​​below the isoelectric point, the net electrostatic charge of the protein is positive; Above the electric point, the net charge of the protein becomes negative.

[0245] Preferably, in order to obtain a positive charge on the protein, the pH value is between pH 2.0 and pH 4.0. and most preferably in the range of pH 2.5 to pH 3.5. To obtain a negative charge on the protein, the pH value is adjusted to pH 3.0 or lower. A pH value in the range of 8.0 to pH 12.0, and even more preferably pH 9.0 to pH 10. 0, most preferably to a pH value of 9.5.

[0246] For this purpose, organic acids, such as formic acid or acetic acid, or bases, such as sodium hydroxide, A sodium solution is added to the emulsion or dispersion to adjust the pH value to within the range specified above.

[0247] Carrying out the first and / or second crosslinking at pH values ​​above or below the isoelectric point , the charge of the protein is altered, and thus electrostatic interactions have a positive effect on capsule formation. There is an advantage that it can be achieved. In addition, such modification of proteins has a positive impact on their emulsifying ability.

[0248] During the first and second cross-linking steps, the stirring force is reduced to, for example, a stirring speed of about 800 - 1200 rpm so that the microcapsules being formed are not broken immediately again.

[0249] An important criterion for the usefulness of microcapsules is the weight ratio of the core material to the capsule wall material. On the one hand, as high a proportion of the core material as possible is desired so that the capsules can have the highest possible utility value. On the other hand, in order to ensure the stability of the capsules, it is necessary for the capsules to still have a sufficient proportion of the capsule wall material.

[0250] According to the present invention, it has been found that it is particularly advantageous to design the microcapsules such that the microcapsules have a weight ratio of the core material to the capsule wall material of 50:50 to 90:10, preferably 70:3 0 to 80:20.

[0251] After complete curing, the microcapsules prepared according to the method of the present invention exist as an aqueous dispersion, also called a microcapsule dispersion or a microcapsule slurry. In this form, the microcapsules are already on the market in principle.

[0252] To prevent separation or creaming of such a suspension and thus achieve high storage stability, it has been proven that it is advantageous for the suspension to have a viscosity of 12 - 1500 mPas. To obtain the desired viscosity of the suspension, it is preferable to use a thickener.

[0253] ​​​​​​​​ As the thickener, preferably xanthan gum, diutan gum, carboxymethyl cellulose (CMC), microcrystalline cellulose (MCC) or guar gum is used.

[0254] To improve the shelf life, one or more preservatives are microencapsulated and added to the slurry as needed, or the microcapsule slurry is dried.

[0255] As the preservative, preferably 1,2 - hexanediol, 1,2 - octanediol, phenoxyethanol - based products, products from the mixture of 1,2 - benzisothiazolin - 3 - one (2.5%) and 2 - methyl - 4 - isothiazolin - 3 - one (2.5%) etc. are used.

[0256] Alternatively, for storage purposes, the microcapsule slurry is preferably dried.

[0257] Regarding the drying of the microcapsule slurry, processes such as freeze - drying are considered, but reference is made to, for example, spray - drying in a fluidized bed. Thereby, to support the drying process and protect the capsules during this process, additional polysaccharide, preferably dextrin, especially maltodextrin, is added to the suspension at a temperature of about 20 to about 50 °C, preferably about 40 °C. It has been proven advantageous that thereby the amount of polysaccharide used is about 50 to about 150 wt.%, preferably about 80 to about 120 wt. % based on the capsule mass in the dispersion. % can be.

[0258] Spray - drying itself can be carried out continuously or batch - wise in a conventional spray plant, and the inlet temperature is about 170 to about 200 °C, preferably about 180 - 185 °C, and the outlet temperature is about 70 ~about 80 °C, preferably about 72 - 78 °C.

[0259] As shown in the following embodiments, large molecules are introduced into the network of the capsule shell by catalytic crosslinking of polysaccharides and / or proteins with a first crosslinking agent and optionally a second crosslinking agent, thereby increasing the amount of natural components in the capsule shell or the microcapsule slurry, and thus increasing the biodegradability of the capsule shell. The process according to the invention further features that, as main components, proteins, polysaccharides and polyisocyanates are polymerized and / or crosslinked via a specifically catalyzed mechanism, thus enabling the preparation of biocompatible polymer-based biodegradable microcapsules. Different from the microcapsules of the prior art in which polyisocyanates constitute most of the capsule shell material, in this case it is the opposite. Polyisocyanates no longer function as the main material of the microcapsules according to the invention, but solely function as crosslinking agents for amino acids and the other components mentioned above. Thus, by the process according to the invention, it is possible to replace part of the polyisocyanates with biodegradable wall materials such as proteins and / or polysaccharides, thus reducing the polyisocyanate content without causing loss or reduction of positive secondary properties such as the functionality and high stability of the microcapsules, such as olfactory properties, i.e., the ability to retain the active ingredient. Thus, the microcapsules can be prepared by the process according to the invention, which on the one hand has excellent functionality and at the same time is easily biodegradable.

[0260]

[0261]

[0262] Surprisingly, as shown in the following embodiments, using the process according to the invention, without causing loss or decrease in the stability of the obtained microcapsules, while maintaining the same amount of the encapsulated active ingredient, microcapsules can be prepared with up to 25%, preferably up to 50%, even more preferably up to 75% reduced amount of the starting material isocyanate, or by other microcapsule starting materials of the latest prior art. This has been found. It has been found that microcapsules can be prepared with up to 25%, preferably up to 50%, even more preferably up to 75% reduced amount of the starting material isocyanate, or by other microcapsule starting materials of the latest prior art, without causing loss or decrease in the stability of the obtained microcapsules while maintaining the same amount of the encapsulated active ingredient. while maintaining the same amount of the encapsulated active ingredient, up to 25%, preferably up to 50%, even more preferably up to 75% reduced amount of the starting material isocyanate, or by other microcapsule starting materials of the latest prior art while maintaining the same amount of the encapsulated active ingredient, up to 25%, preferably up to 50%, even more preferably up to 75% reduced amount of the starting material isocyanate, or by other microcapsule starting materials of the latest prior art while maintaining the same amount of the encapsulated active ingredient, up to 25%, preferably up to 50%, even more preferably up to 75% reduced amount of the starting material isocyanate, or by other microcapsule starting materials of the latest prior art has been found.

[0263] In a second aspect, the present invention relates to microcapsules or microcapsule slurries prepared according to the process of the present invention. In a second aspect, the present invention relates to microcapsules or microcapsule slurries prepared according to the process of the present invention.

[0264] Biodegradable protein and / or polysaccharide microcapsules are those that (a) a core containing or consisting of at least one hydrophobic active ingredient; (b) at least one polysaccharide and / or at least one protein and at least one first cross-linking agent cross-linked matrix or unit; and optionally a protective colloid and / or optionally a second cross-linking agent, and a capsule shell comprising or consisting of them at least one polysaccharide and / or at least one protein and at least one first cross-linking agent cross-linked matrix or unit; and optionally a protective colloid and / or optionally a second cross-linking agent, and a capsule shell comprising or consisting of them at least one polysaccharide and / or at least one protein and at least one first cross-linking agent cross-linked matrix or unit; and optionally a protective colloid and / or optionally a second cross-linking agent, and a capsule shell comprising or consisting of them shell characterized by being composed of or containing them.

[0265] The microcapsules according to the present invention contain a core surrounded or encapsulated by a capsule shell or capsule wall. As a core material for preparing the microcapsules according to the present invention, any material suitable for encapsulation into microcapsules can be used. The microcapsules according to the present invention contain a core surrounded or encapsulated by a capsule shell or capsule wall. As a core material for preparing the microcapsules according to the present invention, any material suitable for encapsulation into microcapsules can be used. As a core material for preparing the microcapsules according to the present invention, any material suitable for encapsulation into microcapsules can be used. Preferably, hydrophobic, i.e., water-insoluble or water-immiscible, liquids or solids, and suspensions The turbid liquid is considered to be the material to be encapsulated.

[0266] In the context of this specification, the core material is, as described above, a hydrophobic active ingredient, i.e., , a substance having a specific effect or causing a specific reaction, such as the above-mentioned drug, pesticide, cosmetic active ingredient, food active ingredient, etc. The term "hydrophobic active ingredient" means that the active ingredient to be encapsulated is in the internal non-aqueous phase during the preparation of the microcapsules and does not mix with the external aqueous phase.

[0267] Polymerization and / or crosslinking of the functional groups of proteins and / or polysaccharides by polyisocyanates results in an alternating and dense, and thus stable, crosslinked matrix or stable capsule wall of crosslinked units based on polyureas and polyurethanes, as well as soluble or insoluble complexes of proteins and polysaccharides.

[0268] In a preferred embodiment, the capsule shell comprises or consists of a crosslinked matrix or crosslinked units from the polymerization and / or crosslinking of at least one protein by a first and optionally a second crosslinking agent, and / or a crosslinked matrix or crosslinked units from the polymerization and / or crosslinking of at least one polysaccharide by a first and optionally a second crosslinking agent.

[0269] The crosslinked matrix or crosslinked units from the polymerization and / or crosslinking of at least one protein by a first and optionally a second crosslinking agent is mainly a polyurea-based network, and the crosslinked matrix or crosslinked units from the polymerization of at least one polysaccharide by a The crosslinked matrix or crosslinked unit from the crosslinking or crosslinking is mainly a polyurethane-based network and a soluble or insoluble complex of protein and polysaccharide.

[0270] The respective disclosures of M.F. Sonnenschein, Introduction to Polyurethane Chemistry, Polyurethanes: Science, Technology, Markets, and Trends, 1st Edition, 2015, John Wiley & Sons, pages 105-126, are incorporated herein in their entirety. In addition to the above polyurea formation and / or polyurethane formation, polyisocyanates, such as urea, allophanate, biuret, uretonimine, etc., due to their reactivity, by-products are formed during the aforementioned crosslinking step. These by-products are each part of the capsule shell or the capsule wall. chein, Introduction to Polyurethane Chemi stry, Polyurethanes: Science, Technology, Ma rkets, and Trends, 1st Edition, 2015, John Wiley & So ns, as described on pages 105-126, in addition to the above polyurea formation and / or polyurethane formation, polyisocyanates, such as urea, allophanate, biuret, uretonimine, etc., due to their reactivity, by-products are formed during the aforementioned crosslinking step. These by-products are each part of the capsule shell or the capsule wall. In addition to the above polyurea formation and / or polyurethane formation, polyisocyanates, such as urea, allophanate, biuret, uretonimine, etc., due to their reactivity, by-products are formed during the aforementioned crosslinking step. These by-products are each part of the capsule shell or the capsule wall. retidione, carbodiimide, uretonimine, etc., by-products are formed during the aforementioned crosslinking step. These by-products are each part of the capsule shell or the capsule wall. retidione, carbodiimide, uretonimine, etc., by-products are formed during the aforementioned crosslinking step. These by-products are each part of the capsule shell or the capsule wall. retidione, carbodiimide, uretonimine, etc., by-products are formed during the aforementioned crosslinking step. These by-products are each part of the capsule shell or the capsule wall.

[0271] By constructing the capsule wall based on several individually defined alternating crosslinked matrices or crosslinked units, particularly stable microcapsules with excellent sensory performance can be prepared, and at the same time, the shell components can be significantly reduced. By constructing the capsule wall based on several individually defined alternating crosslinked matrices or crosslinked units, particularly stable microcapsules with excellent sensory performance can be prepared, and at the same time, the shell components can be significantly reduced. By constructing the capsule wall based on several individually defined alternating crosslinked matrices or crosslinked units, particularly stable microcapsules with excellent sensory performance can be prepared, and at the same time, the shell components can be significantly reduced.

[0272] In addition to the main components listed above, the capsule shell may optionally contain a protective colloid and / or an additional crosslinking agent as required. In addition to the main components listed above, the capsule shell may optionally contain a protective colloid and / or an additional crosslinking agent as required.

[0273] In a preferred variant according to the second aspect, the microcapsules according to the invention are in the form of a dispersion or slurry in which the microcapsules are dispersed in an external aqueous phase. The dispersion or slurry In a preferred variant according to the second aspect, the microcapsules according to the invention are in the form of a dispersion or slurry in which the microcapsules are dispersed in an external aqueous phase. The dispersion or slurry - The weight percentage of the microcapsules therein is about 20 to 60 wt.%, particularly about 25 to 50 wt.%, more preferably about 30 to 35 wt.%.

[0274] The microcapsules prepared according to the process of the present invention can be characterized by their d (0.5) value of the particle size distribution: 50% of the capsules are larger than this value and 50% of the capsules are smaller than this value.

[0275] To determine the particle size distribution, microcapsules according to the present invention having different compositions were dispersed in water as part of a dynamic process and then the particle size was determined by laser diffraction. Depending on the size of the capsules, the refraction of the laser beam is different, so this can be converted into size. For this purpose, Mie theory was used. For particle measurement, a MALVE RN Mastersizer 3000 was used. The corresponding calculations are based on Mie theory.

[0276] The microcapsules according to the present invention are characterized by having a particle size distribution with a d(0.5) value of 18 to 50 μm, preferably 22 to 30 μm of d(0.5) value.

[0277] The corresponding particle size distribution of the microcapsules according to the present invention is shown in FIGS. 1a to 1d: FIG. 1a: SymcapB: 20% isocyanate content; whey protein / pectin and maltodextrin; microcapsules according to the present invention; FIG. 1b: SymcapB: 20% isocyanate content. Milk protein and maltodex trin, additional crosslinking agent tannin. Microcapsules according to the present invention; FIG. 1c: SymcapB: 30% isocyanate content; milk protein, L-glutamine , L-lysine, maltodextrin; microcapsules according to the present invention; Figure 1d: Symcap B: 20% isocyanate content; gelatin and maltodextrin ; microcapsules according to the present invention; Figure 1e: Comparison of particle size distributions: microcapsules according to the latest prior art, i.e., Symc ap G2.1: 100% isocyanate, polyvinyl alcohol and guanidine carbonate; microcapsules according to the present invention, i.e., Symcap B: 20% isocyanate, milk protein, tannin.

[0278] Direct comparison of the microcapsules shows that the process according to the present invention can achieve microcapsules having the same particle size distribution as the microcapsules of the latest prior art.

[0279] Surprisingly, as shown in FIGS. 2 and 3, despite the decrease in the polyisocyanate content in the microcapsule wall, the proteins and / or polysaccharide microcapsules prepared according to the process of the present invention exhibit stability comparable to that of the microcapsules of the latest prior art and a content of essential oil that does not leak unintentionally. As shown in FIGS. 2 and 3, the microcapsules according to the present invention prepared using an additional second crosslinking agent exhibit stability comparable to that of the microcapsules of the latest prior art, if not better, and thus exhibit a lower content of free oil, which may be due to a more efficient encapsulation of odoriferous substances in particular. In particular, the use of an additional crosslinking agent, especially together with the decrease in the isocyanate content, results in a stability comparable to that of the microcapsules of the latest prior art, if not better, and thus a lower content of free oil, which may be due to a more efficient encapsulation of odoriferous substances in particular.

[0280] In particular, the use of a further crosslinking agent, especially together with the decrease in the isocyanate content, results in a stability comparable to that of the microcapsules of the latest prior art, if not better, and thus a lower content of free oil, which may be due to a more efficient encapsulation of odoriferous substances in particular. ​​​​​​​​A significant qualitative improvement is achieved, thus reducing the percentage of sesame oil that leaks (see Figures 2 and Samples 7 and 8, Samples 3 and 4, 5 and 6 of 3).

[0281] The use of microcapsules in target applications, particularly those prepared using additional crosslinking agents, also shows comparable stability values compared to the latest prior art microcapsules, despite the reduced polyisocyanate content (see Figure 5). The protein and / or polysaccharide microcapsules according to the present invention also show a significant improvement in sensory performance (aroma release) compared to the latest prior art

[0282] capsules, which may be due to the encapsulation of the stable active ingredient and the low loss of the associated active ingredient. The microcapsules according to the present invention show a significantly higher sensory intensity when the aroma is released by opening the capsules by mechanical friction or pressure, as shown in Figure 6. This may be due to the encapsulation of the stable active ingredient and the low loss of the associated active ingredient. As the degree of crosslinking, which depends on the crosslinking agent and its concentration, increases, the stability of the microcapsules also increases, but at the same time the ability to biodegrade the capsule shell decreases. Figure 7 generally shows the correlation between the stability, performance, and biodegradability of the microcapsules as a function of the degree of crosslinking. For example, when the microcapsules are very stable, the number of microcapsules that break open and release the active ingredient by rubbing or applying pressure decreases, resulting in a decrease in performance such as sensory performance. If the microcapsules are too unstable, they may already be broken during use or storage and will not function.

[0283] As the degree of crosslinking, which depends on the crosslinking agent and its concentration, increases, the stability of the microcapsules also increases, but at the same time the ability to biodegrade the capsule shell decreases. Figure 7 generally shows the correlation between the stability, performance, and biodegradability of the microcapsules as a function of the degree of crosslinking. For example, when the microcapsules are very stable, the number of microcapsules that break open and release the active ingredient by rubbing or applying pressure decreases, resulting in a decrease in performance such as sensory performance. If the microcapsules are too unstable, they may already be broken during use or storage and will not function. This may be due to the encapsulation of the stable active ingredient and the low loss of the associated active ingredient. The microcapsules according to the present invention show a significantly higher sensory intensity when the aroma is released by opening the capsules by mechanical friction or pressure, as shown in Figure 6.

[0284] In the protein-based and / or polysaccharide-based microcapsules according to the present invention, the following implementation As shown in the form, compared with the polyurea / polyurethane microcapsules of the latest prior art The polyisocyanate content is reduced by up to 75% without causing loss or reduction in the stability of the microcapsules to be encapsulated or the amount of active ingredient used. In contrast to the microcapsules of the latest prior art, isocyanate no longer functions as the main material of the capsule shell or capsule wall, but only as a cross-linking agent for the protein and / or polysaccharide of the capsule shell. Therefore, the absolute polyisocyanate content of the microcapsules described herein corresponds to only 1.5% of all microcapsules. On the one hand, the lower polyisocyanate content in the capsule shell or capsule wall, and on the other hand, the use of proteins and / or polysaccharides as capsule wall building blocks, make the microcapsules according to the present invention more biodegradable than the capsules of the latest prior art. The microcapsules according to the present invention exhibit significantly excellent biodegradability, as shown in the following examples. Biodegradability refers to the ability of an organic material to decompose into water, carbon dioxide (CO2), and biomass after a predetermined time under defined conditions of temperature, oxygen, and moisture in the presence of microorganisms or fungi. According to OECD 301F, when more than 60% of the wall material is decomposed after 28 days, the microcapsules are considered to be easily biodegradable.

[0285] On the one hand, the lower polyisocyanate content in the capsule shell or capsule wall, and on the other hand, the use of proteins and / or polysaccharides as capsule wall building blocks, make the microcapsules according to the present invention more biodegradable than the capsules of the latest prior art. On the one hand, the lower polyisocyanate content in the capsule shell or capsule wall, and on the other hand, the use of proteins and / or polysaccharides as capsule wall building blocks, make the microcapsules according to the present invention more biodegradable than the capsules of the latest prior art. On the one hand, the lower polyisocyanate content in the capsule shell or capsule wall, and on the other hand, the use of proteins and / or polysaccharides as capsule wall building blocks, make the microcapsules according to the present invention more biodegradable than the capsules of the latest prior art. The microcapsules according to the present invention are, as shown in the following examples, exhibiting significantly excellent biodegradability.

[0286] Biodegradability refers to the ability of an organic material to decompose into water, carbon dioxide (CO2), and biomass after a predetermined time under defined conditions of temperature, oxygen, and moisture in the presence of microorganisms or fungi. Under defined conditions of temperature, oxygen, and moisture in the presence of microorganisms or fungi, after a predetermined time, the ability of an organic material to decompose into water, carbon dioxide (CO2), and biomass. is decomposed into water, carbon dioxide (CO2), and biomass.

[0287] According to OECD 301F, when more than 60% of the wall material is decomposed after 28 days, the microcapsules are considered to be easily biodegradable. are considered to be easily biodegradable.

[0288] The microcapsules according to the present invention have ≧ 10% biodegradability according to OECD 301F after 28 days, preferably ≧ 50% biodegradability, more preferably ≧ 70% biodegradability, and most preferably ≧ 90% biodegradability. By combining the starting components, it is possible to obtain microcapsules according to the present invention having sufficient stability (mechanical and diffusion stability during use), high sensory performance, and at the same time excellent biodegradability. At the same time, by the composition of the starting components, the degree of crosslinking can be kept low, thereby significantly improving the biodegradability of the microcapsules.

[0289] Therefore, the previously effective correlation between sensory performance, high crosslinkability, and biodegradability may be disrupted. The biodegradability, excellent stability and excellent release ability of the microcapsules, as well as the possibility of encapsulating a wide range of hydrophobic active ingredients using the microcapsules according to the present invention, enable the protein-based and polysaccharide-based microcapsules according to the present invention to be used for a wide range of applications for flavoring and aromatization. Furthermore, the microcapsules according to the present invention are universal capsules that can be used to encapsulate a wide range of aromatic or fragrant substances, aldehydes, carboxylic acids, or aromatic or fragrant substances having an ester functional group according to the latest prior art without any restrictions on individual active ingredients. Due to their advantageous properties, particularly the stability and targeted release of the active ingredients, and their biodegradability, the microcapsules according to the present invention are suitable for a wide range of applications, particularly in household products, textiles,

[0290]

[0291]

[0292] ​​​​​​​​​​Style care products, laundry detergents, fabric softeners, cleaners, fragrance boosters, fragrance lotions, and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceuticals, or printing coatings for paper, etc., are suitable for use.

[0293] Accordingly, in another aspect, the present invention relates to household products, textile care products, laundry detergents, fabric softeners, cleaners, fragrance boosters, fragrance lotions, and liquid or solid fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceuticals, or printing coatings for paper, for the preparation of biodegradable proteins and / or polysaccharide microcapsules according to the present invention, or for the use of a dispersion of biodegradable proteins and / or polysaccharide microcapsules according to the present invention. The microcapsules according to the present invention are particularly suitable for encapsulating hydrophobic aromatic substances or scented substances, which can be used in various household and textile care products.

[0294] Finally, the present invention relates to household products, textile care products, laundry detergents, fabric softeners, cleaners, fragrance boosters, fragrance lotions, and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceuticals, or printing coatings for paper, etc., containing biodegradable proteins and / or polysaccharide microcapsules according to the present invention, or a dispersion of biodegradable proteins and / or polysaccharide microcapsules according

[0295] The proportion of microcapsules in the aforementioned products is 0.05 to 15 wt.%, preferably 0.2 to 5 wt.%, based on the total weight of the product.

[0296] Examples of Embodiments The biodegradable protein and / or polysaccharide microcapsules according to the present invention and their advantageous properties will be described in more detail with reference to the following examples.

Examples

[0297] The free oil content of the microcapsules according to the present invention compared with the microcapsules SYMCAP® G2.1 and SYMC AP® G3 according to the latest prior art

[0298] The following stability data refers to tests at 4 0 °C in commercial formulations such as fragrance boosters or softeners.

[0299] In the following examples, the microcapsules according to the latest prior art were selected as those based solely on a polyurea network for their capsule walls. The polyisocyanate used was a mixture of hexamethylene diisocyanate and 4,4'-methylenediphenylene di isocyanate in a ratio of 80:20. Polyvinyl alcohol was used as the protective colloid, and guanidine carbonate was used for crosslinking. Generally, no catalyst was used in the preparation of these capsules, and the synthesis was carried out at a pH value of 9.

[0300] The microcapsules according to the present invention were prepared with two different proteins. One was gelatin, and the other was made of milk protein additionally added with the amino acids L-glutamine and L-lysine. The polysaccharide used in both cases was maltodextrin DE8-10. As the polyisocyanate, a mixture of hexamethylene diisocyanate and 4,4'-methylenediphenylene di isocyanate in a ratio of 80:20 was used. DABCO was used as the catalyst. Cinnamaldehyde was used as an additional crosslinking agent.​

[0301] The content of sesame oil in all samples was 35% of the obtained microcapsule slurry, and sesame oil was mixed with vegetable oil at a ratio of 1:1.

[0302] Measure the amount of free oil in isopropanol, that is, mix a specified amount of microcapsule slurry with isopropanol, stir for 30 seconds, and collect a sample therefrom. The collected sample is measured by GC-MS. The results indicate respectively how much of the encapsulated oil has migrated into isopropanol or is not fully encapsulated. Therefore, the free oil content provides an indication of whether the process itself is functioning, that is, whether the sesame oil is fully encapsulated and / or whether the capsule shell is stable enough to prevent the sesame oil from leaking into isopropanol. In this context, a value of less than 1% is considered to indicate successful encapsulation and a stable capsule shell. The free oil content of the microcapsules according to the present invention was compared with the free oil contents of the microcapsules SYMCAP® G2.1 (100%) and SYMCAP® G3

[0303] according to the latest prior art, at 75%. The microcapsules according to the latest prior art, that is, Sample 1: SYMCAP® G2.1: Isocyanate content: 100%; Crosslinked with polyvinyl alcohol and guanidine carbonate.

[0304] Sample 2: SYMCAP® G3: Isocyanate content: 75%; Crosslinked with polyvinyl alcohol and guanidine carbonate. Crosslinked with polyvinyl alcohol and guanidine carbonate. Sample 2: SYMCAP® G3: Isocyanate content: 75%; Crosslinked with polyvinyl alcohol and guanidine carbonate.

[0305] Microcapsules according to the present invention: Sample 3: SYMCAP B: Isocyanate content 50%; Gelatin and maltodex trin Sample 4: SYMCAP B: Isocyanate content 50%; Gelatin and maltodex trin; Additional crosslinking agent gallic acid; Sample 5: SYMCAP B: Isocyanate content 30%; Gelatin and maltodex trin Sample 6: SYMCAP B: Isocyanate content 30%; Gelatin and maltodex trin; Additional crosslinking agent cinnamaldehyde; Sample 7: SYMCAP B: Isocyanate content 50%; Milk protein + L-gluta mine + L-lysine and maltodextrin; Sample 8: SYMCAP B: Isocyanate content 50%; Milk protein + L-gluta mine + L-lysine and maltodextrin; Additional crosslinking agent cinnamaldehyde; Sample 9: SYMCAP B: Isocyanate content 30%; Milk protein + L-gluta mine + L-lysine and maltodextrin; Sample 10: SYMCAP B: Isocyanate content 30%; Milk protein + L-gluta mine + L-lysine and maltodextrin; Additional crosslinking agent cinnamaldehyde;

[0306] Since good results have already been obtained with an isocyanate content of 50%, the isocyanate content was further reduced and attempts were made to achieve results comparable to those of the latest prior art microcapsules by a second crosslinking.

[0307]

Table 1

[0308] ​The results are shown in Figs. 2 and 3.

[0309] As can be seen from the above results, the micro capsules according to the present invention with a reduced isocyanate content have a free oil portion that is almost comparable to that of the latest prior art microcapsules. By crosslinking with an additional crosslinking agent, the stability of the microcapsule wall can be further enhanced and the free oil content can be further reduced.

[0310] All three microcapsule samples according to the present invention have a free oil content of less than 1%, which is an indicator of successful encapsulation and a stable capsule shell.

Example

[0311] The free oil content of the microcapsules according to the present invention with and without an additional crosslinking agent (transglutaminase (TG))

[0312] The microcapsules were prepared with three different proteins. First, gelatin was used, second, milk protein was used, and further, milk protein mixed with the amino acids L-glutamine and L-lysine was used. The polysaccharide used in both cases was maltodextrin DE8 -10. DABCO was used as a catalyst. The microcapsule samples were prepared with and without using another crosslinking agent; as an additional crosslinking agent, trans glutaminase (TG) was used.

[0313] The free oil content was determined as described in Example 1.

[0314] The results are shown in Fig. 4.

Example

[0315] ​​Stability of Microcapsules in Application

[0316] The microcapsules according to the invention and the most recent prior art microcapsules prepared as described above or by a similar method were measured for stability in the target application. The stability test was carried out using a typical softener (finishing agent) incorporating the microcapsule slurry in an amount of 1 wt.%, stored at room temperature and 40 °C respectively. After regular time intervals (aging for 24 hours, 1 week, 2 weeks, 4 weeks), samples were taken therefrom and the stability was measured.

[0317] Microcapsules according to the latest prior art, namely Sample 1: SYMCAP® G2.1: Isocyanate content: 100%; Sample 2: SYMCAP® G3: Isocyanate content: 75%;

[0318] Microcapsules according to the invention: Sample 3: SymcapB: Isocyanate content 50%, pea protein, dextrin. Sample 4: SymcapB: Isocyanate content 50%; gelatin, maltodextrin Sample 5: SymcapB: Isocyanate content 50%, milk protein, amino acids, crosslinking agent transglutaminase, maltodextrin Sample 6: SymcapB: Isocyanate content 30%; maltodextrin Sample 7: SymcapB: Isocyanate content 30%, gelatin, crosslinking agent tannin, maltodextrin

[0319] Measurement: The capsule contents were analyzed by headspace GC / MS (SPME-fiber: PDMS -DVB 65 μm sheath). ​​​​​

[0320] Analysis: Integration of the areas of each perfume compound and calculation of the stability interval ΣGC area of all the encapsulated components of the sample 100% Stability of the capsule = 100% ΣGC area of all the perfume components of the quantitative standard

[0321] The identification of the aromatic components is based on the in-house database as well as the analytical database of commercially available aromatic formulations. Subsequently.

[0322] Thereby, the percentage of the perfume oil remaining in the capsule can be obtained. For example, a result of 98 % means that 2% of the original amount of the perfume oil used is no longer in the capsule.

[0323] The results are shown in Figure 5.

[0324] As can be seen from Figure 5, the use of the additional crosslinking agent shows equivalent stability values in the application, regardless of the decrease in the polyisocyanate content. Regardless of the decrease in the polyisocyanate content.

Example

[0325] Sensory evaluation of the microcapsules according to the present invention For the sensory evaluation, the microcapsules according to the present invention were compared with the microcapsules according to the latest prior art, i.e., the microcapsules prepared as described above:

[0326] Microcapsules according to the latest prior art, i.e., Sample 1: SYMCAP® G2.1: Isocyanate content: 100%;

[0327] Microcapsules according to the present invention: Sample 2: SYMCAP B: 30% isocyanate content; gelatin and maltodextrin; Additional crosslinking agent tannin; Sample 3: SYMCAP B: Isocyanate content 20%; milk protein and maltodextrin Essential oil: Tomcap

[0328] The sensory evaluation was conducted as follows: Each of the above-mentioned microcapsules was added to a softener (perfume Tomcap) at a slurry concentration of 0.4 wt.%, and then washed. For comparison, capsules were filled with 17.5% essential oil (+17.5% vegetable oil = total usage 35%), and when 0.4% of the capsule slurry was injected, the injection amount of pure essential oil in the softener was 0.07% of the essential oil. 30 g of the softener was used for a 2 kg amount of laundry including terry towels. The washing instructions were as follows: The amount of laundry including terry towels (cotton cloth) was put into the washing machine, and the softener was put into the softener compartment. The washing program "Express 20; 900 rpm" was started. Then, the terry towels were dried overnight at room temperature.

[0329]

[0330]

[0331] The results of the sensory evaluation are shown in Table 6.

[0332] The microcapsules according to the invention are in fact superior to the state-of-the-art microcapsules. It has the same, if not stronger, odor, especially with the use of additional crosslinking agents. This results in superior sensory performance.

[0333] The advantage here is due to the stability of the microcapsules according to the invention. A 30% reduction in the isocyanate content based on the capsule shell showed comparable stability. Present.

[0334] Due to the above mentioned advantageous properties, the microcapsules according to the present invention are superior to the microcapsules according to the state of the art. Microcapsules provide consistent quality and therefore sensory stability over time. On the other hand, the microcapsules according to the latest conventional technology are They are less degradable than microcapsules. EXAMPLES

[0335] Biodegradability of the microcapsules according to the present invention

[0336] Biodegradability according to OECD 301F was determined as follows: The inoculum was measured by oxygen consumption (O2 consumption) and Degradability of non-pre-adapted wall materials.

[0337] [Table 2]

[0338] Reducing the amount of isocyanate (crosslinker) increases biodegradability.

Claims

1. A process for the preparation of biodegradable polysaccharide-based microcapsules, comprising the steps of: (i) providing an internal non-aqueous phase comprising at least one first crosslinker and at least one hydrophobic active ingredient, the internal non-aqueous phase comprising 20-80 wt. % of the hydrophobic active ingredient and 0.1-5 wt. % of the first crosslinker; (ii) providing an external aqueous phase comprising at least one polysaccharide and, optionally, at least one protective colloid, wherein the proportion of the at least one polysaccharide in the external aqueous phase ranges from 0.5 to 7.0 wt. %, based on the total weight of the external aqueous phase; (iii) emulsifying or dispersing said internal non-aqueous phase in said external aqueous phase, optionally in the presence of at least one stabilizer and / or at least one emulsifier, to obtain an oil-in-water emulsion or dispersion, wherein the weight ratio of internal non-aqueous phase to external aqueous phase is in the range of 30:70 to 60:40; (iv) optionally adding at least one further polysaccharide; (v) performing a first cross-linking by adding at least one catalyst to obtain a microcapsule slurry; (vi) curing the microcapsule slurry at a temperature of at least 60°C; (vii) cooling; and (viii) optionally separating the microcapsules from the microcapsule slurry and optionally drying the microcapsules or adjusting the viscosity of the microcapsule slurry by adding at least one thickening agent. in that order, wherein said at least one first crosslinking agent is selected from the group consisting of a polyisocyanate having two or more isocyanate groups selected from the group consisting of aliphatic, cycloaliphatic, hydroaromatic, aromatic or heterocyclic polyisocyanates, their substitution products and mixtures of the aforementioned compounds, and a mixture of two or more of the aforementioned first crosslinking agents, in particular said polyisocyanates comprise two aliphatic polyisocyanates or one aliphatic and one aromatic polyisocyanate, in particular said polyisocyanate is a mixture of polyisocyanates of alternating monomeric, oligomeric or polymeric structures having different chain lengths and two or more of the aforementioned first crosslinking agents.

2. In step (i) at least one further cross-linking agent is provided or in step (vii) a second cross-linking is carried out by adding at least one second cross-linking agent; 2. The process according to claim 1, further comprising at least one further or at least one second cross-linking agent selected from the group consisting of transglutaminase, peroxidase, secondary plant substances selected from the group consisting of polyphenols, in particular tannins, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of said cross-linking agents.

3. 3. The process according to claim 1 or 2, wherein the at least one hydrophobic active ingredient is selected from the group consisting of fragrances, scents, cooling agents, TRPV1 and TRPV3 modulators, substances producing a pungent taste or a warm or hot sensation on the skin or mucous membranes or substances producing a tingling sensation in the mouth or throat or active ingredients having a pungent, acrid or astringent taste, substances from the group of insecticides, biocides, pesticides, repellents, food additives, cosmetic active ingredients, pharmaceutical active ingredients, agricultural chemicals, dyes, colorants, dye precursors; luminescent paints, optical brighteners, solvents, waxes, silicone oils, lubricants, printing coatings for paper, and mixtures of two or more of the aforementioned active ingredients.

4. The at least one polysaccharide or the at least one further polysaccharide is - indigestible fibres and dietary fibres, in particular insoluble dietary fibres, in particular cellulose, cellulose derivatives, in particular quaternized hydroxyethylcellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), hemicellulose, lichenin, chitin, chitosan, lignin, xanthan, vegetable fibres, in particular cereal fibres, potato fibre, apple fibre, citrus fibre, bamboo fibre, sugar beet extract fibre; oat fibre and soluble dietary fibres, in particular inulin, in particular native inulin, highly soluble inulin, granular inulin, high performance inulin, pectin, alginates, agar, carrageenan, gum arabic, konjac gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, polydextrose and lactulose; starches, in particular starches from wheat, potato, corn, rice, tapioca and oats, chemically, mechanically and / or enzymatically modified starches; and starch derivatives, such as dextrins or maltodextrins, in particular dextrins and maltodextrins from wheat, potato, corn, rice and oats, in particular maltodextrins DE 8-10, DE 17-20, DE 18-20, cyclodextrins, oligosaccharides, in particular oligofructose; and sugar alcohols, in particular sorbitol, mannitol, isomalt, maltitol, maltilol syrup, lactitol, xylitol, erythritol; - gellan; glucose, As well as mixtures of the above polysaccharides 4. The process according to claim 1 or 2, wherein the compound is selected from the group consisting of:

5. The at least one protective colloid is diols, in particular ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, the isomeric butanediols, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and polyols, preferably triols, in particular glycerol and its ethoxylated and propoxylated products, trimethylolpropane and its ethoxylated and propoxylated products, polyvinyl alcohol (PVOH) and its derivatives, in particular ammonium- or sulfonate-functionalized polyvinyl alcohols, polyphenols, preferably 1,3,5-trihydroxybenzene, polysaccharides, in particular glucose, starch or chemically, mechanically and / or enzymatically modified starches, - polyvinylpyrrolidone, vinyl maleate copolymer, sodium lignosulfonate, maleic anhydride / styrene copolymer, ethylene / maleic anhydride copolymer, copolymers of ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitol, sodium dodecyl sulfate, - animal and vegetable polymers, in particular gum arabic (Senegal and Seyal types), proteins, gelatin, olibanum resin, shellac, lignin, chitosan, saponin As well as mixtures of the aforementioned compounds 5. The process according to claim 1 , wherein the protective colloid is selected from the group consisting of:

6. 6. The process according to claim 1, wherein the at least one catalyst is selected from the group consisting of diazobicyclo[2.2.2]octane (DABCO), bismuth catalysts and tin catalysts, and mixtures of two or more of the foregoing catalysts.

7. 7. The process according to claim 1, wherein the first crosslinking is carried out at a temperature between 60°C and 90°C.

8. 8. The process according to claim 1, wherein the hardening of the microcapsules is carried out at a temperature between 60° C. and 90° C. and / or for a duration of at least 3 hours.

9. 9. Biodegradable microcapsules or microcapsule slurry obtainable by the process according to one or more of the preceding claims.

10. (a) a core comprising or consisting of at least one hydrophobic active ingredient; (b) a capsule shell comprising or consisting of a crosslinked matrix or unit of at least one polysaccharide and at least one first crosslinking agent; and, optionally, at least one first protective colloid. A biodegradable microcapsule comprising or consisting of: The at least one first crosslinking agent is selected from the group consisting of aliphatic, cycloaliphatic, hydroaromatic, aromatic or heterocyclic polyisocyanates, their substitution products and mixtures of the aforementioned compounds, polyisocyanates having two or more isocyanate groups, and mixtures of two or more of the aforementioned first crosslinking agents, in particular the polyisocyanates comprise two aliphatic polyisocyanates or one aliphatic and one aromatic polyisocyanate, in particular the polyisocyanates are mixtures of polyisocyanates of alternating monomeric, oligomeric or polymeric structures having different chain lengths and two or more of the aforementioned first crosslinking agents.

11. 11. The biodegradable microcapsule of claim 10, wherein the capsule shell comprises or consists of a crosslinked matrix or crosslinking units from the polymerization and / or crosslinking of at least one polysaccharide by the first and optionally the further crosslinking agents.

12. 12. A microcapsule slurry comprising microcapsules according to any one of claims 9 to 11, optionally in combination with a thickening agent and / or a preservative.

13. 17. Use of the microcapsules according to one or more of claims 9 to 11 or the microcapsule slurry according to claim 9 or claim 12 for the preparation of a household product, a textile care product, a detergent, a fabric softener, a cleaning agent, a fragrance booster or liquid or solid fragrance enhancer, a cosmetic product, a personal care product, a perfume composition, an agricultural product, a pharmaceutical product, or a print coating for paper.

14. 13. A household product, fabric care product, detergent, fabric softener, cleaning agent, fragrance booster, and fragrance enhancer, cosmetic, personal care product, perfume composition, agricultural product, or pharmaceutical product comprising the microcapsules of any one of claims 9 to 11 or the microcapsule slurry of claim 9 or claim 12.

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