Method for producing particles

Abstract

The invention relates to a method for producing microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material, the method comprising i. Providing a water-immiscible liquid containing the organic active compound to be encapsulated and at least one first shell-forming compound (SFC1); ii. Emulsifying the water-immiscible liquid obtained in step i. In an aqueous medium to obtain an oil-in-water (o / w) emulsion of the water-immiscible liquid in the aqueous medium; iii. Adding at least one second shell-forming compound (SFC2) to the aqueous medium or to the emulsion obtained in step ii. Prior to or during performing step ii., thereby obtaining an aqueous suspension of the microparticles; wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, in particular 1, 2 or 3 first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic anhydride groups, per molecule, and the other shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, per molecule, in particular 1, 2 or 3 second reactive groups (RG2) selected from the group consisting of hydroxyl, thiol and primary amino groups, the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) having only one reactive group and the other shell-forming compound having 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, in particular 1, 2 or 3 reactive groups. The invention also relates to microparticles obtainable by this process and to the use thereof.

Description

[0001] The present invention relates to a method for producing microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material formed by an in situ encapsulation process using a combination of two different reactive shell forming compounds, wherein the reactive functional groups of the different shell forming compounds have complementary reactivities such that they react with each other by forming covalent bonds. Microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material are also claimed, wherein the wall material is a urea compound or an amide compound obtained by a combination of two different reactive shell forming materials.

[0002] Microcapsules have various uses, such as carriers for active substances (such as crop protection agents, medicaments, fragrances, aromas) and also for reactive substances or catalysts for industrial applications. They typically contain a polymer material which encapsulates the material to be encapsulated. The advantages of this type of formulation are in particular:

[0003] - Protect reactive substances from environmental influences;

[0004] - safe and practical handling of toxic or unstable active substances;

[0005] - controlled release of active substances;

[0006] - prevent premature mixing of substances;

[0007] - Treat the liquid active substance as a solid and repeatedly.

[0008] An overview of processes for microencapsulation of active substances can be found in H. Mollet, A. Grubenmann, "Formulation Technology", Chapter 6.4 (Microencapsulation), pp. 234-246, Wiley VCH Verlag GmbH, Weinheim 2001 and in the literature cited therein.

[0009] In many agricultural and cosmetic products, it is desirable for aroma chemicals and agrochemical actives to be released slowly over time. For example, in the case of perfume materials, the more volatile perfume raw materials are responsible for the "fresh feeling" experienced by the consumer. In the case of agrochemicals, it is often desirable to achieve a long-lasting effect, reduce volatility and / or reduce negative environmental impacts or acute toxic effects through controlled release of the corresponding actives. Therefore, it is desirable for these materials to be released in a slow, controlled manner.

[0010] A common method for the controlled release of the corresponding active substance is microencapsulation. Typically, these microcapsules contain a hydrophobic liquid core containing the corresponding active substance surrounded by a synthetic polymer shell. Such polymers can be, for example, polyurethanes, polyureas, polyamides, polyesters, polycarbonates, urea / formaldehyde resins, melamine / formaldehyde resins, polystyrenes, or acrylate polymers. Microparticles are typically prepared by interfacial polymerization of the corresponding monomers or oligomers (which form a polymer shell in an oil-in-water (o / w) emulsion of the corresponding hydrophobic liquid).

[0011] Processes for encapsulating organic liquids containing aroma chemicals by urea / formaldehyde resins or melamine formaldehyde resins have been described, for example, in WO 2008 / 066773 and WO 2009 / 090169 and the references cited therein.

[0012] Methods for encapsulating organic liquids containing agrochemicals by in situ formation of polyureas or polyurethanes have been described, for example, in US 5,705,174, US 5,910,314, WO 94 / 13139, WO 2015 / 165834 and WO 2018 / 130588.

[0013] The synthetic polymers of the microcapsules remain in the environment as microplastics and are therefore not ecologically harmless (see, for example, CMRochmann, "The global odyssee of plastic pollution," Science 368 (2020) pp. 1184-1185). The use of synthetic polymer microcapsules is therefore increasingly subject to ecological concerns on the part of consumers and regulators. It is therefore necessary to provide delivery forms for organic active substances that can be produced without or with a reduced amount of non-degradable plastic material.

[0014] WO 2018 / 065481 and WO 2019 / 193094 disclose methods for preparing microparticles loaded with organic compounds (such as aroma chemicals). The method includes producing porous microparticles made of thermoplastic biodegradable polyester materials, and suspending the microparticles in liquid aroma chemicals or solutions of aroma chemicals. The porous microparticles are produced by providing a w / o-emulsion of a polyester material dissolved in a solvent immiscible with water as a continuous phase and an aqueous solution of a pore-forming agent as a discontinuous phase, emulsifying the w / o-emulsion in water to obtain a water-in-oil-in-water (w / o / w) emulsion and removing the organic solvent by evaporation. In order to achieve controlled release, the microparticles loaded with aroma chemicals must be enclosed or sealed, which is achieved by heating the loaded microparticles over an extended period of time, which may cause degradation of the active substance and undesirable aggregation or even destruction of the loaded microparticles. In addition, the release characteristics are not always satisfactory. In addition, several steps must be performed.

[0015] The above-mentioned production method for the microparticles loaded with aroma chemicals still requires or contains polymeric materials, which may eventually not be completely degraded or degraded over a very long period of time, and therefore may contribute to the microplastics in the environment. In addition, their production is tedious and requires extended heating of the loaded microparticles (which may be harmful to microparticles and / or aroma chemicals) or the presence of a coating or matrix. In addition, production usually requires a large amount of chlorinated hydrocarbon solvents. In addition, the preparation of such particles is carried out in a separate step, one step is to prepare hollow microparticles, followed by loading the desired substance and extending the heating to prevent the substance from leaving prematurely. Therefore, an alternative method is needed to simplify the production process.

[0016] RJ Bergeron et al., Bioorganic & Medicinal chemistry, Vol. 5, 11 (1997), pp. 2049-2061 and O. Phanstiel et al., Chem Mater. 2001, 13, 264-272 have reported that organic diamide diacids self-assemble in an aqueous phase to form hollow microparticles. Self-assembly is achieved by lowering the pH of an alkaline aqueous solution of the diacid. This method results in a suspension of microparticles enclosed in an aqueous phase. Therefore, it is not suitable for encapsulating organic active substances, particularly organic active substances that are small in size or insoluble in water.

[0017] SR Wilson-Withfordd et al., ACS Appl. Mater. Interfaces 2021, 13, 4, 5887–5894 describe the preparation of microcapsules by crystallization of diurethane compounds such as decane-1,10-bis(cyclohexylcarbamate) (DBCC). To this end, DBCC is prepared by reacting cyclohexyl isocyanate with 1,10-decanediol in dry chloroform in the presence of a tin catalyst, wherein DBCC is formed within three hours. The DBCC is then dissolved in a 9:1 mixture of dichloromethane / decane at a concentration of 0.1% by weight. The solution is then injected into the aqueous phase and, after evaporation of the dichloromethane, an aqueous suspension of microcapsules containing decane in the capsule shell formed by the crystallized DBCC is formed. The process is lengthy and requires large amounts of chlorinated hydrocarbons, which must be evaporated.

[0018] It is therefore an object of the present invention to provide a simple and straightforward process for preparing microparticles loaded with at least one organic chemical, which process does not require the presence of a polymer matrix or coating. The microparticles will have a relatively low surface porosity, resulting in slow release properties. The loaded microparticles are producible in a simple process and with high yields, but without significant aggregation or even destruction of the loaded microparticles.

[0019] It has been found that, surprisingly, these and further objects are achieved by the process described below and the organic chemical-filled microparticles obtainable therefrom.

[0020] The present invention therefore relates to a process for producing microparticles comprising at least one organic active compound enclosed by a shell of organic wall material, the process comprising

[0021] i. providing a water-immiscible liquid containing an organic active compound to be encapsulated and at least one first shell-forming compound (SFC1);

[0022] ii. emulsifying the water-immiscible liquid obtained in step i. in an aqueous medium to obtain an oil-in-water (o / w) emulsion of a water-immiscible liquid in an aqueous medium;

[0023] iii. adding at least one second shell-forming compound (SFC2) to the aqueous medium before or during step ii. or adding it to the emulsion obtained in step ii., thereby obtaining an aqueous suspension of the microparticles;

[0024] wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has per molecule 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic anhydride groups, and the other shell-forming compound has per molecule 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 second reactive groups (RG2) selected from hydroxyl groups, thiol groups and primary amino groups,

[0025] The first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group, and the other shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups.

[0026] Thus, microparticles are obtained, wherein the shell of the organic wall material is formed by the reaction of the at least one first shell-forming compound (SFC1) with the at least one second shell-forming compound (SFC2). In other words, the wall material of the microparticles obtainable by the process according to the invention consists essentially of the reaction product of the at least one first shell-forming compound (SFC1) with the at least one second shell-forming compound (SFC2). In this context, the term "essentially" is clearly to be understood as meaning that the portion of the organic wall material formed by the reaction of the first shell-forming compound with the second shell-forming compound accounts for at least 90% by weight, based on the total weight of organic matter in the wall material.

[0027] The microparticles obtainable by the process are novel and have particularly advantageous properties when the wall material is formed from a urea compound or an amide compound or a thiocarbamate compound or a thiourea compound. Such a wall material is formed in step iii) if the functional group RG2 is a primary amino group or a thiol group. If the wall material is formed from an available urea compound, microparticles obtainable by the process are particularly preferably considered if the functional group (RG1) is an isocyanate group and the functional group (RG2) is a primary amino group.

[0028] Therefore, the present invention also relates to microparticles comprising at least one organic compound encapsulated by a shell of an organic wall material formed by reaction of a first shell-forming compound (SFC1) with a second shell-forming compound (SFC2),

[0029] wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has per molecule 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic anhydride groups, and the other shell-forming compound has per molecule 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 second reactive groups (RG2) selected from primary amino groups and thiol groups,

[0030] The first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group, and the other shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups.

[0031] The present invention relates in particular to microparticles comprising at least one organic compound encapsulated by a shell of an organic wall material formed by reaction of at least one first shell-forming compound (SFC1) with at least one second shell-forming compound (SFC2), obtainable by the process of the present invention,

[0032] wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has per molecule 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic anhydride groups, and the other shell-forming compound has per molecule 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 second reactive groups (RG2) which are primary amino groups or thiol groups,

[0033] The first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group, whereas the other shell-forming compound has 2, 3, 4, 5 or 6, in particular 2, 3 or 4, especially 2 or 3 reactive groups.

[0034] The present invention is associated with many advantages:

[0035] - The process of the invention produces microparticles loaded with organic active compounds which allow a controlled release of the organic active compound, ie by burst release caused by mechanical pressure, by diffusion or by degradation of a biodegradable membrane, which results in a slow release effect desired for certain applications.

[0036] The wall material of the microparticles obtainable by this process is a non-polymeric material of low and defined molecular weight, since at least one of the shell-forming materials has only one reactive functional group and therefore no polymeric material is formed in the process.

[0037] - The process of the present invention is much simpler, straightforward and less problematic than comparable processes, requiring separate steps of producing hollow particles, subsequently filling the microparticles with aroma chemicals and finally sealing the porous surface of the pores, for example by applying heat or a coating.

[0038] - In particular, the process of the invention does not require volatile organic solvents, in particular halogenated hydrocarbon solvents for encapsulating organic active compounds. In particular, no evaporation step is required to induce shell formation via self-assembly. Therefore, the process is easier to carry out and does not pose health risks, does not require additional solvent recycling and limits waste management.

[0039] - By the process of the present invention, the surface porosity of microparticles loaded with organic active compounds is greatly reduced without significant destruction or aggregation of the loaded microparticles due to prolonged exposure to heat.

[0040] Due to the reduced surface porosity of the loaded microparticles, they can be stored over extended periods of time without any significant loss of organic active compounds, which is particularly important in the case of sensitive and / or volatile organic active substances.

[0041] The present invention also relates to the use of microparticles containing encapsulated aroma chemicals as described herein as additives for imparting fragrance or flavor to products, for example selected from perfumes, washing and cleaning products, cosmetic products, personal care products, hygiene articles, foods, food supplements, fragrance dispensers and perfumes.

[0042] The present invention also relates to the use of microparticles as described herein for the controlled release of organic active compounds. In particular, the present invention relates to the use of microparticles as described herein containing encapsulated aroma chemicals or agrochemicals for the controlled release of aroma chemicals or agrochemicals, respectively.

[0043] Here and throughout the present application, the terms "organic active compound", "organic active substance" and "active compound" are used synonymously. These terms are understood by the person skilled in the art to mean organic chemical compounds which trigger physiological effects in organisms and plants, and substances which cause chemical effects or catalyze chemical reactions in inanimate nature. Examples of active substances are aroma chemicals for use in the construction sector, organic crop protection agents, organic pharmaceuticals, organic cosmetic active substances and organic active substances, known as construction chemicals, in particular catalysts for products in the construction sector, such as crosslinking or polymerization catalysts. The term "organic active substance" also includes "metal organic active substances".

[0044] The term "volatile organic active substances" refers to organic or organometallic chemical compounds having a boiling temperature or evaporation temperature of at most 250°C at 101.3 kPa and / or a vapor pressure of at least 50 Pa at 20°C.

[0045] Here and in the following, the term "water-immiscible" refers to a material whose solubility in deionized water at 20° C. and 1 bar is at most 5 g / L, in particular at most 1 g / L. Under the conditions given here, the solubility of a water-immiscible material in deionized water may be zero, i.e. below the detection limit.

[0046] The term liquid refers to a material which is in the liquid state under ambient conditions, i.e. a non-solid and non-gaseous material. In the context of the present invention, the liquid material preferably has a dynamic viscosity at 20° C. in the range of 0.2 to 2000 mPas, in particular in the range of 0.5 to 1000 mPas. Here and throughout the present specification, ambient conditions refer to temperatures in the range of 20° C.-25° C. and atmospheric pressure, i.e. about 1 bar.

[0047] The term "low molecular weight organic active compound" refers to an organic or organometallic chemically active compound with a defined molecular weight Mn, which is usually below 1000 Daltons and typically in the range of from 80 Daltons to <1000 Daltons and in particular in the range of from 100 to 500 Daltons. The molecular weight can be determined by mass spectrometry.

[0048] The term "sensitive active substance" refers to an organic active compound that is unstable to the conditions of its environment and is damaged or degraded, for example, due to the pH of its environment or by oxidation.

[0049] In the context of the shell forming compounds (SFC1) and (SFC2), the skilled person will clearly understand that the term "isocyanate group" means a functional group of the formula -N=C=O. The term "isothiocyanate group" means a functional group of the formula -N=C=S. The term "carbonyl halide group" means a group of the formula -C(=O)-X, wherein X refers to a halogen, in particular chlorine or bromine, which may also be referred to as a carboxylic acid halide group. The term carboxylic anhydride group means a group of the formula -C(=O)-OC(=O)-R, wherein R refers to hydrogen or a hydrocarbon group preferably having from 1 to 6 carbon atoms, such as a C1-C6 alkyl or phenyl group. The term "primary amino group" is clearly understood to mean a functional group of the formula -NH2. The term "hydroxyl group" is clearly understood to mean a functional group of the formula -OH. The term "thiol group" is clearly understood to mean a functional group of the formula -SH. The aforementioned functional groups are respectively bound to carbon atoms of the shell forming compounds (SFC1) and (SFC2).

[0050] Unless otherwise specified, the term "room temperature" indicates a temperature of 22°C.

[0051] According to the present invention, the shell-forming compound (SFC1) has a reactive group (RG1), i.e. a group selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups, carboxylic anhydride groups, or a reactive group (RG2), i.e. a hydroxyl group and / or a primary amino group and / or a thiol group, wherein RG2 is preferably a primary amino group or a combination of a primary amino group and a hydroxyl group, particularly preferably a primary amino group.

[0052] Thus, if the shell-forming compound (SFC1) has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG1) per molecule, the shell-forming compound (SFC2) must have 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG2) per molecule, provided that the shell-forming compound (SFC1) has only one reactive group (RG1) per molecule or the shell-forming compound (SFC2) has only one reactive group (RG2) per molecule and the other shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 complementary reactive groups per molecule. Likewise, if the shell-forming compound (SFC1) has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG2) per molecule, the shell-forming compound (SFC2) must have 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG1) per molecule, provided that the shell-forming compound (SFC1) has only one reactive group (RG2) or the shell-forming compound (SFC2) has only one reactive group (RG1) per molecule and the other shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, especially 1, 2 or 3 complementary reactive groups per molecule.

[0053] Thus, the reactive groups present in the shell forming compound (SFC2) have complementary reactivity with the reactive groups present in the shell forming compound (SFC1). Complementary reactivity means that the reactive groups (RG1) and (RG2) are capable of reacting with each other by forming a covalent bond between the reactive centers of the reactive groups (RG1) and (RG2). Thus, in step iii), the first shell forming compound (SFC1) contained in the emulsified water-immiscible liquid reacts at the surface of the droplets of the o / w emulsion with the second shell forming compound (SFC2) present in the aqueous phase of the o / w emulsion. Thus, a wall material is formed at the surface of the droplets of the water-immiscible liquid, which wall material forms the shell of the microcapsule and thus encapsulates the droplets of the water-immiscible liquid containing the organic active compound.

[0054] It is immediately clear that the method of the present invention requires

[0055] (a) the first shell forming compound (SFC1) contained in the water-immiscible liquid containing the organic active compound to be encapsulated has exactly 1 reactive group (RG1) or (RG2) per molecule if the second shell forming compound (SCF2) added in step iii) has 1, 2, 3, 4, 5 or 6 reactive groups having a reactivity complementary to the reactivity of the reactive groups of the first shell forming compound (SFC1) - group (a) of the embodiments below;

[0056] or

[0057] (b) If the first shell-forming compound (SCF1) contained in the water-immiscible liquid containing the organic active compound to be encapsulated has 1, 2, 3, 4, 5 or 6 reactive groups having a reactivity complementary to the reactivity of the reactive groups of the second shell-forming compound (SFC2), the second shell-forming compound (SFC2) added in step iii has exactly 1 reactive group (RG1) or (RG2) per molecule - group (b) of the embodiments below.

[0058] It is also evident that in group (a) of embodiments, the water-immiscible liquid containing the organic active compound to be encapsulated does not contain substantially any shell-forming compound having more than one reactive group (RG1) or (RG2) per molecule, whereas in group (b) of embodiments, substantially no shell-forming compound having more than one reactive group (RG1) or (RG2) per molecule is added. In particular, in group (a) of embodiments, the water-immiscible liquid containing the organic active compound to be encapsulated does not contain more than 10% by weight, in particular not more than 5% by weight, of shell-forming compounds having more than one reactive group (RG1) or (RG2) per molecule, based on the total amount of shell-forming compounds contained in the water-immiscible liquid. In other words, in group (a) of embodiments, the relative amount of shell-forming compounds (SCF1) having exactly one reactive group (RG1) or (RG2), based on the total amount of shell-forming compounds contained in the water-immiscible liquid, is at least 90% by weight, in particular at least 95% by weight. Similarly, in group (b) of embodiments, the relative amount of shell-forming compounds (SFC2) having exactly one reactive group (RG1) or (RG2), based on the total amount of shell-forming compounds added in step iii. of the process according to the invention, is at least 90% by weight, in particular at least 95% by weight or 100% by weight. Thus, in group (b) of embodiments, the relative amount of shell-forming compounds having more than one reactive group (RG1) or (RG2), based on the total amount of shell-forming compounds added in step iii., is at most 10% by weight, in particular at most 5% by weight.

[0059] It is also immediately clear that the process of the invention will also work if the shell forming compound (SFC1) is a mixture of different shell forming compounds (SFC1) with the same reactivity and / or if the shell forming compound (SFC2) is a mixture of different shell forming compounds (SFC2) with the same reactivity. It is also clear from the foregoing that the shell forming compounds (SFC1) and (SFC2) must not have reactive groups other than the reactive groups (RG1) and (RG2).

[0060] Depending on the selected combination of the complementary reactive groups of the shell forming compounds (SFC1) and (SFC2), the organic wall material or shell material is

[0061] - urea compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, urea groups, especially 2 or 3 urea groups (ie -NH-C(=O)-NH- groups),

[0062] - carbamate compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, carbamate groups, especially 2 or 3 carbamate groups (ie -NH-C(=O)-O- groups),

[0063] - thiocarbamate compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, thiocarbamate groups, especially 2 or 3 thiocarbamate groups (ie -NH-C(=O)-S- groups),

[0064] - thiourea compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, thiourea groups, especially 2 or 3 thiourea groups (ie -NH-C(=S)-NH- groups),

[0065] - Amide compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, carboxamide groups, especially 2 or 3 carboxamide groups (ie -C(=O)-NH- groups).

[0066] With regard to the stability of the shell, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are preferably selected so that the organic wall material or shell material is formed by a urea compound, a thiourea compound, a carbamate compound, a thiocarbamate compound or a carboxamide compound. In particular, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected so that the organic wall material or shell material is formed by a urea compound, a thiourea compound, a carbamate compound, a thiocarbamate compound or a carboxamide compound having 2, 3 or 4, preferably 2 or 3, in particular 2, groups selected from urea groups, thiourea groups, carbamate groups, thiocarbamate groups and carboxamide groups.

[0067] More preferably, the complementary reactive groups of the shell forming compounds (SFC1) and (SFC2) are selected such that the organic wall material or shell material is formed by a urea compound or a carbamate compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3, in particular 2, groups selected from urea groups and carbamate groups. Most preferably, the complementary reactive groups of the shell forming compounds (SFC1) and (SFC2) are selected such that the organic wall material or shell material is formed by a urea compound, in particular by a urea compound having 2, 3 or 4, preferably 2 or 3, in particular 2, urea groups.

[0068] In these cases, the process is preferably carried out such that the first shell-forming compound (SFC1) has one reactive group (RG1) which is an isocyanate group and the second shell-forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3 and especially 2 primary amino or hydroxyl groups, whereby microparticles are obtained in which the wall material or the shell material, respectively, is formed from compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, urea or carbamate groups, preferably 2 or 3 urea or carbamate groups and especially 2 urea or carbamate groups.

[0069] For the production of microparticles in which the organic wall material is formed from a compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4 carboxamide groups, preferably 2 or 3 carboxamide groups, especially 2 carboxamide groups, the process is preferably carried out such that the first shell-forming compound (SFC1) has one reactive group (RG1) which is a carbonyl halide group or a carboxylic anhydride group, in particular a phosgene group, and the second shell-forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3, in particular 2 primary amino groups, whereby microparticles are obtained in which the organic wall material or the shell material, respectively, is formed from a compound having 2, 3 or 4, in particular 2 or 3 carboxamide groups.

[0070] In another preferred group of embodiments, the complementary reactive groups of the shell forming compounds (SFC1) and (SFC2) are selected such that the organic wall material or the shell material, respectively, is formed from a thiourea compound, in particular from a thiourea compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3 and especially 2 thiourea groups, respectively. In these cases, the process is preferably carried out such that the first shell forming compound (SFC1) has one reactive group (RG1) which is an isothiocyanate group and the second shell forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3 and especially 2 primary amino groups, whereby microparticles are obtained wherein the organic wall material or the shell material, respectively, is formed from a compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4 thiourea groups, preferably 2 or 3 thiourea groups and especially 2 thiourea groups.

[0071] In yet another preferred group of embodiments, the complementary reactive groups of the shell forming compounds (SFC1) and (SFC2) are selected such that the organic wall material or the shell material, respectively, is formed from a thiocarbamate compound, in particular from a thiocarbamate compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3, and especially 2 thiocarbamate groups, respectively. In these cases, the process is preferably carried out such that the first shell forming compound (SFC1) has one reactive group (RG1) which is an isocyanate group, and the second shell forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3 and especially 2 thiol groups, whereby microparticles are obtained wherein the organic wall material or the shell material, respectively, is formed from a compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3, or 4 thiocarbamate groups, preferably 2 or 3 thiocarbamate groups and especially 2 thiocarbamate groups.

[0072] In particular, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected such that the organic wall material or shell material is formed from a urea compound having two urea groups. In this case, the process is preferably carried out by using a shell-forming compound (SFC1) having one reactive group (RG1) which is an isocyanate group, and a second shell-forming compound (SFC2) having two reactive groups (RG2) which are primary amino groups.

[0073] The shell-forming compounds (SFC1) and (SFC2) are generally low molecular weight compounds, which typically have a molecular weight of not more than 1000 g / mol, for example in the range of 60 to 500 g / mol, in particular in the range of 80 to 400 g / mol. Since the number of reactive sites of the respective shell-forming compounds (SFC1) and (SFC2) is limited to a maximum of 6 and the at least one of the shell-forming compounds (SFC1) and (SFC2) each has only one reactive group, the resulting wall material is formed by compounds having a maximum molecular weight of 2000 g / mol and typically up to 1600 g / mol, particularly preferably in the range of 200 to 1600 g / mol, in particular in the range of 200 to 1200 g / mol. Here, the term "maximum" molecular weight refers to the molecular weight of not more than 90% by weight of the molecules forming the organic wall material. The maximum molecular weight of the organic wall material can be determined by established methods of high performance liquid chromatography coupled to mass spectrometry (HPLC-MS).

[0074] For the efficiency of the encapsulation process, it is advantageous if the first shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, preferably 1, 2 or 3, more preferably 1 or 2, and especially 1 first reactive group (RG1). In this case, the second shell-forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, preferably 1, 2 or 3, more preferably 1 or 2, and especially 2 second reactive groups (RG2) per molecule, provided that the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group and the other shell-forming compound has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, preferably 1, 2 or 3, more preferably 2 or 3, and especially 2 complementary reactive groups. In particular, the reactive groups (RG1) are isocyanate groups.

[0075] For the efficiency of the encapsulation process, it is particularly advantageous if the first shell-forming compound (SFC1) has 1 first reactive group (RG1) per molecule and the second shell-forming compound (SFC2) has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, more particularly 2 or 3, especially 2 second reactive groups (RG2) per molecule. In this case, the first reactive group (RG1) is in particular an isocyanate group.

[0076] It is also advantageous if the first shell-forming compound (SFC1) has 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, more particularly 2 or 3, in particular 2, first reactive groups (RG1) per molecule and the second shell-forming compound (SFC2) has 1 second reactive group (RG2) per molecule. In this case, the first reactive group (RG1) is in particular an isocyanate group.

[0077] Preferably, the combination of shell forming compounds (SFC1) and (SFC2) is selected in such a way that urethane, urea or amide groups are formed from the reaction of shell forming compound (SFC1) with shell forming compound (SFC2).

[0078] Thus, a specific group (1) of embodiments relates to the process according to the invention, wherein the first reactive group (RG1) is an isocyanate group and the second reactive group (RG2) is a hydroxyl group or, in particular, a primary amino group, while another group (2) of embodiments relates to the process according to the invention, wherein the first reactive group (RG1) is a carbonyl halide or carboxylic anhydride group and the second reactive group (RG2) is a primary amino group.

[0079] A further special group (3) of embodiments relates to the process according to the invention, wherein the first reactive group (RG1) is an isothiocyanate group and the second reactive group (RG2) is a hydroxyl group or, in particular, a primary amino group.

[0080] Suitable combinations are given in the following Table 1, wherein RG indicates the type of reactive groups present in the shell forming compounds (SFC1) and (SFC2), respectively, and n indicates the number of reactive groups (RG) present in the shell forming compounds (SFC1) and (SFC2), respectively. The skilled person will immediately understand that rows 1 to 8 of Table 1 relate to group (1) of embodiments, while the combinations given in rows 9 to 12 of Table 1 relate to group (2) of embodiments, and the combinations given in rows 13 to 18 of Table 1 relate to group (3) of embodiments.

[0081] Table 1:

[0082]

[0083] Among the combinations given in Table 1, the combinations given in rows 1 to 4 and in rows 9 to 10 come into consideration with particular preference, and the combinations in rows 1 and 3 come into consideration with particular preference.

[0084] Suitable shell-forming compounds having a reactive group (RG1) include, but are not limited to

[0085] - monoisocyanates from the group of aliphatic monoisocyanates, cycloaliphatic monoisocyanates, aromatic monoisocyanates and araliphatic monoisocyanates;

[0086] - diisocyanates from the group of aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates and araliphatic diisocyanates;

[0087] - triisocyanates from the group of aliphatic triisocyanates, cycloaliphatic triisocyanates, aromatic triisocyanates and araliphatic triisocyanates;

[0088] - monoacid chlorides from the group of aliphatic monoacid chlorides, cycloaliphatic monoacid chlorides, aromatic monoacid chlorides and araliphatic monoacid chlorides;

[0089] - diacid chlorides from the group of aliphatic diacid chlorides, cycloaliphatic diacid chlorides, aromatic diacid chlorides and araliphatic diacid chlorides;

[0090] - monoisocyanates of the group of aliphatic monoisocyanates, cycloaliphatic monoisocyanates, aromatic monoisocyanates and araliphatic monoisocyanates;

[0091] - diisocyanates from the group of aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates and araliphatic diisocyanates; and

[0092] - triisothiocyanates from the group of aliphatic triisothiocyanates, alicyclic triisothiocyanates, aromatic triisothiocyanates and araliphatic triisothiocyanates.

[0093] In the above shell-forming compounds having reactive groups (RG1), isocyanate groups, isothiocyanate groups and carbonyl chloride groups are usually bound to carbon atoms of aliphatic, alicyclic, aromatic or araliphatic groups having from 2 to 20 carbon atoms, wherein 1, 2 or 3 non-adjacent CH2 groups in the aliphatic and alicyclic groups may be replaced by oxygen atoms or N-methyl groups, and wherein in the aliphatic, alicyclic, aromatic or araliphatic groups, 1, 2 or 3 non-adjacent CH2 groups may be replaced by N. Such groups include C1-C4 alkyl groups optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups. 20 Alkyl, C5-C 20 Cycloalkyl, aryl optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups, such as phenyl group, phenylalkylphenyl group optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups, and diphenyl ether group optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups.

[0094] Here and throughout the specification, the prefix C used in conjunction with a compound or molecular moiety n -C m Each indicates a range of possible carbon number that a molecular moiety or compound can have. n"Alkyl" means a straight-chain or branched saturated hydrocarbon group having from 1 to n carbon atoms. n / C m "Alkyl" means a mixture of two alkyl groups, one having n carbon atoms and the other having m carbon atoms.

[0095] For example, the term C1-C 20 Alkyl refers to a group having a straight chain or branched saturated hydrocarbon group of from 1 to 20 carbon atoms, while the term C1-C4 alkyl refers to a group having a straight chain or branched saturated hydrocarbon group of from 1 to 4 carbon atoms, and C5-C 20 Alkyl represents a group of a straight or branched saturated hydrocarbon group having from 5 to 20 carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2, 2-Trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, their isomers, in particular mixtures of isomers, such as "isononyl", "isodecyl". Examples of C1-C4-alkyl are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0096] As used herein, the term "C5-C 20 "-Cycloalkyl" refers to a saturated monocyclic or polycyclic, especially monocyclic, bicyclic or tricyclic (alicyclic) radical which is unsubstituted or substituted by 1, 2, 3 or 4 C1-C4 alkyl radicals, wherein the C5-C 20 The total number of carbon atoms of the -cycloalkyl group is from 5 to 20, and wherein the total number of ring-forming atoms is preferably in the range of 3 to 16.20 Examples of -cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, norbornyl (= bicyclo[2.2.1]heptyl) and isobornyl (= 1,7,7-trimethylbicyclo[2.2.1]heptyl). 20 -cycloalkyl" in which 1, 2 or 3 non-adjacent ring-forming CH2 groups may be replaced by oxygen atoms, while the remainder of the ring-forming atoms are carbon atoms. These groups are also known as C3-C 20 -heterocycloalkyl, and wherein C3-C 20 The total number of carbon atoms in the -heterocycloalkyl group is in the range of 3 to 20. Examples of such groups include, but are not limited to, oxolan-2-yl, oxolan-3-yl, oxan-2-yl, oxan-3-yl, oxan-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 2-methyl-1,3-dioxolan-4-yl, 2,2-dimethyl-1,3-dioxolan-4-yl, 1,4-dioxan-2-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 2-methyl-1,3-dioxan-4-yl, 2-methyl-1,3-dioxan-5-yl, 2,2-dimethyl-1,3-dioxan-4-yl, 2,2-dimethyl-1,3-dioxan-5-yl, 2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-2-yl, 2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3-yl and 2,5-dioxabicyclo[2,2,1]heptan-7-yl.

[0097] Aryl refers to phenyl, naphthyl and biphenyl which are optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups,

[0098] Aromatic aliphatic groups, also indicated as arylalkyl, refer to phenyl and naphthyl groups optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups carrying further alkylene groups. Examples of arylalkyl groups include benzyl, phenethyl, phenylalkylphenyl groups and diphenylether groups, wherein the phenyl rings in these 4 mentioned groups are optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups.

[0099] Examples of suitable monoisocyanates include C1-C 20 Alkyl esters, such as methyl isocyanate, ethyl isocyanate, butyl isocyanate, amyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, C5-C 20 Cycloalkyl esters such as cyclohexyl isocyanate, cycloheptyl isocyanate, and aryl isocyanates such as phenyl isocyanate and toluene isocyanate.

[0100] Examples of suitable diisocyanates include C2-C 20 Alkylene diisocyanates, such as hexamethylene diisocyanate, tetramethylene diisocyanate, 1,8-diisocyanatooctanoate, 1,10-diisocyanatodecane, C2-C 20 Cycloalkylene diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, aryl diisocyanates such as 2,4- and 2,6-tolylene diisocyanate and isomeric mixtures thereof, and aryl alkyl diisocyanates such as 2,4'- and 4,4'-diphenylmethane diisocyanate and mixtures thereof.

[0101] Examples of suitable triisocyanates include the biureths and isocyanurates of the above-mentioned diisocyanates.

[0102] Examples of suitable monoacyl chlorides include C1-C 20 Alkanyl chlorides, such as acetyl chloride, propionyl chloride, butyryl chloride, pentanoic acid chloride, hexanoic acid chloride, heptanoic acid chloride, octanoic acid chloride, nonanoic acid chloride, decanoic acid chloride, C5-C 20 Cycloalkanecarboxylic acid chlorides such as cyclohexanoic acid chloride and aromatic carboxylic acid chlorides such as benzoyl chloride.

[0103] Examples of suitable diacyl chlorides include succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride, suberic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, brassic acid dichloride, cyclohexanedicarboxylic acid dichloride, phthalic acid dichloride, and isophthalic acid dichloride.

[0104] Suitable shell-forming compounds having a reactive group (RG2) include, but are not limited to

[0105] - a primary monoamine selected from the group consisting of aliphatic monoamines, alicyclic monoamines and aromatic monoamines,

[0106] - a primary diamino compound selected from the group consisting of aliphatic diamines, alicyclic diamines and aromatic diamines;

[0107] - primary triamino compounds selected from the group consisting of aliphatic triamines, alicyclic triamines and aromatic triamines;

[0108] - a primary tetraamino compound selected from the group consisting of aliphatic tetraamines, alicyclic tetraamines and aromatic tetraamines;

[0109] - a monoalcohol selected from the group consisting of an aliphatic monoalcohol, an alicyclic monoalcohol and an aromatic monoalcohol;

[0110] - diols selected from the group consisting of aliphatic diols, cycloaliphatic diols, aromatic diols and araliphatic diols;

[0111] - triols selected from the group consisting of aliphatic triols, cycloaliphatic triols, aromatic triols and araliphatic triols;

[0112] - a tetraol selected from the group consisting of aliphatic tetraols, alicyclic tetraols, aromatic tetraols and araliphatic tetraols

[0113] - monothiols selected from the group consisting of aliphatic monothiols, alicyclic monothiols and aromatic monothiols;

[0114] - a dithiol selected from the group consisting of aliphatic dithiols, cycloaliphatic dithiols, aromatic dithiols and araliphatic dithiols;

[0115] - a trithiol selected from the group consisting of aliphatic trithiol, alicyclic trithiol, aromatic trithiol and araliphatic trithiol; and

[0116] - Tetrathiol selected from the group consisting of aliphatic tetrathiol, alicyclic tetrathiol, aromatic tetrathiol and araliphatic tetrathiol.

[0117] In the above-mentioned shell-forming compounds having a reactive group (RG2) as a primary amino group, the thiol group and the hydroxyl group are usually bound to a carbon atom of an aliphatic, alicyclic or aromatic group having from 2 to 20 carbon atoms, wherein 1, 2 or 3 non-adjacent CH2 groups in the aliphatic and alicyclic groups may be replaced by oxygen atoms, and wherein 1, 2 or 3 non-adjacent CH2 groups in the aliphatic, alicyclic or aromatic groups may be replaced by N. Such groups include C1-C4 alkyl groups optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups. 20 Alkyl, C5-C 20 Cycloalkyl, C6-C4 optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups 20 Bicycloalkyl, aryl optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups, such as phenyl group, phenylalkylphenyl group optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups, and diphenyl ether group optionally substituted by 1, 2, 3 or 4 C1-C4 alkyl groups and 1,3,5-triazine group.

[0118] Examples of suitable monoamines include C1-C 20 Alkylamines, such as methylamine, ethylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, C5-C 20 Cycloalkylamines such as cyclohexylamine and cycloheptylamine, and arylamines such as aniline, benzylamine, phenethylamine and toluidine.

[0119] Examples of suitable diamines include diamino C2-C 20Alkanes, such as diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, N-methyl-N-(3-aminopropyl)-1,3-diaminopropane, 3-oxa-1,5-diaminopentane, 3,6-dioxa-1,8-diaminooctane, 4,7-dioxa-1,10-diaminooctane, C5-C6-diaminopropane; 20 Cycloalkanes, such as 1,2-, 1,3- and 1,4-diaminocyclohexane and isophoronediamine, and arylamines, such as o-, m- and p-diaminobenzene and the diaminotoluene isomers.

[0120] Examples of suitable triamines include N,N-bis(3-aminopropyl)-1,3-diaminopropane, N,N-bis(2-aminoethyl)-1,3-diaminopropane and 2,4,6-triamino-s-triazine.

[0121] Examples of suitable tetramines include N,N,N',N'-tetrakis(3-aminopropyl)-1,3-diaminopropane, N,N,N',N'-tetrakis-(2-aminoethyl)-1,3-diaminopropane and tetraaminobenzene.

[0122] Examples of suitable monoalcohols include C1-C 20 Alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, 2-hexanol, n-heptanol, n-octanol, isooctyl alcohol, 2-ethylhexan-1-ol, n-nonanol, isononanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propylene glycol monomethyl ether, 1,3-propylene glycol monoethyl ether, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclodecanol, phenol and benzyl alcohol.

[0123] Examples of suitable diols include C2-C 20 Alkanediols, such as 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tripropylene glycol, cycloaliphatic diols, such as 1,2-, 1,3- and 1,4-cyclohexanediol, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, aromatic diols, such as resorcinol, and araliphatic diols, such as p-hydroxybenzyl alcohol and 1,2-, 1,3- and 1,4-bis(hydroxymethyl)benzene.

[0124] Examples of suitable triols include C3-C 20 Alkantriols, such as glycerol, 2,2-bis(hydroxymethyl)-1-ethanol, 2,2-bis(hydroxymethyl)-1-propanol, 2,2-bis(hydroxymethyl)-1-butanol, triethanolamine, tripropanolamine.

[0125] Examples of suitable tetraols include C3-C 20 Alkanetols, such as pentaerythritol, N,N,N',N'-tetrakis-(2-hydroxyethyl)-1,2-diaminoethane, N,N,N',N'-tetrakis-(2-hydroxyethyl)-1,3-diaminopropane, N,N,N',N'-tetrakis-(2-hydroxyethyl)-1,4-diaminobutane, N,N,N',N'-tetrakis-(2-hydroxyethyl)-1,5-diaminopentane, N,N,N',N'-tetrakis-(2-hydroxyethyl)-1,6- diaminohexane, N,N,N',N'-tetrakis-(2-hydroxypropyl)-1,2-diaminoethane, N,N,N',N'-tetrakis-(2-hydroxypropyl)-1,3-diaminopropane, N,N,N',N'-tetrakis-(2-hydroxypropyl)-1,4-diaminobutane, N,N,N',N'-tetrakis-(2-hydroxypropyl)-1,5-diaminopentane and N,N,N',N'-tetrakis-(2-hydroxypropyl)-1,6-diaminohexane.

[0126] Examples of suitable monothiols include C1-C 20 Alkanethiols such as thiomethanol, thioethanol, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, 2-thiobutanol, isobutyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, n-hexyl mercaptan, 2-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, isooctyl mercaptan and thiophenol.

[0127] Examples of suitable dithiols include C2-C 20 Alkanedithiols, such as 1,2-ethaneedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexandedithiol, alicyclic dithiols, such as 1,2-, 1,3- and 1,4-cyclohexanededithiol, aromatic dithiols, such as benzenedithiol and biphenyl-4,4-dithiol.

[0128] In a preferred group (a.1) of embodiments, the first shell forming compound (SFC1) is selected from the group consisting of monoisocyanates, i.e. compounds having exactly 1 isocyanate group (NCO) per molecule, including aliphatic monoisocyanates, cycloaliphatic monoisocyanates and aromatic monoisocyanates, and wherein the second shell forming compound (SFC2) is selected from the group consisting of aliphatic diamines, aliphatic triamines, aliphatic tetraamines, aliphatic pentamines, aliphatic hexamines, cycloaliphatic diamines, alicyclic triamines, alicyclic tetraamines, alicyclic pentamines, alicyclic hexamines, aromatic diamines, aromatic triamines, aromatic tetraamines, aromatic pentamines and aromatic hexamines. In this very preferred group of embodiments, the second shell-forming compound (SFC2) is in particular selected from the group consisting of aliphatic diamines, aliphatic triamines, cycloaliphatic diamines, cycloaliphatic triamines, aromatic diamines and aromatic triamines, particular preference being given to aliphatic diamines, aliphatic triamines and aromatic triamines, such as melamine (2,4,6-triamino-s-triazine).

[0129] In a particularly preferred group (a.11) of embodiments, the first shell-forming compound (SFC1) is selected from the group consisting of aliphatic monoisocyanates, alicyclic monoisocyanates and aromatic monoisocyanates, and wherein the second shell-forming compound (SFC2) is selected from the group consisting of aliphatic diamines. In this very preferred group of embodiments, the second shell-forming compound (SFC2) is in particular selected from the group consisting of diamino C4-C 16 Alkanes, such as 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane.

[0130] In a further preferred group (b.1) of embodiments, the first shell-forming compound (SFC1) is selected from the group consisting of isocyanates having at least 2 NCO groups per molecule, in particular 2, 3 or 4 NCO groups per molecule, and wherein the second shell-forming compound (SFC2) is selected from the group consisting of aliphatic monoamines, alicyclic monoamines and aromatic monoamines. In this preferred group (b.1) of embodiments, the isocyanate having at least 2 NCO groups can in particular be an aliphatic, aromatic or alicyclic diisocyanate, in particular a C2-C 20 Alkylene diisocyanates, such as hexamethylene diisocyanate, tetramethylene diisocyanate, 1,8-diisocyanatooctanoate, 1,10-diisocyanatodecane, C2-C 20Cycloalkylene diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, aryl diisocyanates such as 2,4- and 2,6-tolylene diisocyanate and isomeric mixtures thereof, and aryl alkyl diisocyanates such as 2,4'- and 4,4'-diphenylmethane diisocyanate and mixtures thereof.

[0131] The relative amounts of shell forming materials (SFC1) and (SFC2) are preferably selected so that the molar ratio of reactive groups (RG1) to (RG2) present in the shell forming materials (SFC1) and (SFC2) is close to the desired stoichiometry. However, reactive groups (RG1) may be used in a certain excess or deficiency. Preferably, the molar ratio of the total amount of reactive groups (RG1) to the total amount of reactive groups (RG2) is in the range of 1.0:2.0 to 2.0:1.0, in particular in the range of 1.0:1.6 to 1.6:1.0, and especially in the range of 1.0:1.3 to 1.3:1.0.

[0132] The total amount of shell forming compounds (SFC1) and (SFC2) is preferably selected such that the weight ratio of the total amount of shell forming compounds (SFC1) and (SFC2) to the water-immiscible liquid is in the range of 1:1 to 1:50, in particular in the range of 1:1 to 1:25 and especially in the range of 1:1 to 1:10. Thus, the total amount of shell material in the final microcapsule is typically in the range of 2 to 50% by weight, in particular in the range of 4 to 40% by weight and especially in the range of 5 to 40% by weight, based on the total weight of the final microcapsule, i.e. based on the total weight of the water-immiscible liquid and the shell material resulting from the reaction of the shell forming compound (SFC1) with the shell forming compound (SFC2).

[0133] In the process according to the invention, the organic active compound to be encapsulated and the first shell-forming compound (SFC1) are present in a water-immiscible liquid. Here and in the following, the term "water-immiscible liquid" refers to a liquid whose solubility in deionized water at 20° C. and 1 bar is at most 5 g / L, in particular at most 1 g / L. Under the conditions given here, the miscibility of the water-immiscible liquid with deionized water may be zero, i.e. below the detection limit.

[0134] The organic active compound to be encapsulated and the first shell forming compound (SFC1) may form a water-immiscible liquid, i.e. the organic active compound to be encapsulated and the first shell forming compound (SFC1) constitute more than 99% by weight of the total weight of the water-immiscible liquid. Alternatively, the organic active compound may be present dissolved or dispersed in a water-immiscible organic solvent, in particular if the organic active compound is not liquid at 25° C. and 1 bar. Preferably, the organic active compound to be encapsulated and the first shell forming compound (SFC1) are mutually soluble in each other, or they are solutions in a water-immiscible organic solvent.

[0135] The term "water-immiscible organic solvent" refers to an organic solvent whose solubility in deionized water at 20° C. and 1 bar is at most 5 g / L, in particular at most 1 g / L. Under the conditions given here, the miscibility of the water-immiscible organic solvent with deionized water may be 0, i.e. below the detection limit.

[0136] In particular, the water-immiscible liquid is a solution of the organic compound to be encapsulated and the first shell-forming compound (SFC1) and optionally one or more organic water-immiscible solvents.

[0137] Suitable water-immiscible organic solvents are, in particular, hydrocarbons, such as aliphatic and cycloaliphatic organic solvents and aromatic solvents and mixtures thereof, C2-C 20 -monocarboxylic acid or dicarboxylic acid with C1-C 10 Esters of alkanols having a total of at least 6 carbon atoms, such as butyl acetate, hexyl acetate, isononyl acetate, isopropyl myristate, C6-C 10 Alcohols, fatty acid amides having a total of at least 8 carbon atoms, such as dimethylhexanamide and dimethyloctanamide, and mixtures of the foregoing organic solvents.

[0138] Preferably, the organic solvent has a boiling point of at least 100°C at 1 bar, for example in the range of 100°C to 350°C.

[0139] The organic active compound may be essentially any active compound which is liquid at 20° C. and 1 bar or which can be dissolved or dispersed in a water-immiscible organic solvent. In particular, the organic active substance is non-polar and has a high affinity for water-immiscible liquids. In particular, the organic active substance has an octanol-water partition coefficient K at 20° C. of greater than 0, in particular of at least 1.5. ow =C o / C w .

[0140] In a particular group of embodiments, the organic active compound is liquid at 22°C and 1 bar, or is a mixture of two or more organic active compounds that are liquid at 22°C and 1 bar.

[0141] In another particular group of embodiments, the organic active substance is a solid at 22° C. and 1 bar, or a mixture of two or more organic active compounds that are solid at 22° C. and 1 bar. In this case, the organic active compound or the mixture of these two or more organic active compounds is provided as a solution in a water-immiscible compound.

[0142] The organic active compound may be a single compound or a mixture of compounds, for example a mixture of 2, 3 or more active compounds.

[0143] The organic active compound is usually a low molecular weight organic active compound or a mixture of low molecular weight organic active compounds.

[0144] The organic active compound typically has no reactive groups reactive toward reactive groups (RG1) and (RG2).

[0145] The organic active compounds may be selected from agrochemicals, aromachemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds, such as polymerization catalysts, dyes and UV filters.

[0146] In a preferred group of embodiments, the organic active substance is an aroma chemical, especially an aroma chemical that is liquid at 22°C and 1 bar, or a mixture of two or more aroma chemicals that are liquid at 22°C and 1 bar. Preferred aroma chemicals are hydrophobic and have a solubility in deionized water of not more than 100 mg / L, especially at 25°C. In another preferred group of embodiments, the organic active substance is an aroma chemical that is solid at 22°C and 1 bar, or a mixture of two or more aroma chemicals that are solid at 22°C and 1 bar. In this case, the aroma chemical or the mixture of these two or more aroma chemicals is provided as a solution in a water-immiscible compound.

[0147] The term "aroma chemicals" is understood by a person skilled in the art to mean organic compounds that can be used as "odorants" and / or "flavoring agents". In the context of the present invention, "odorants" are understood to mean natural or synthetic substances with an inherent odor. In the context of the present invention, "flavoring agents" are understood to mean natural or synthetic substances with an inherent flavor. In the context of the present invention, "odor" or "olfactory perception" is the interpretation of sensory stimuli sent from chemical receptors in the nose or other olfactory organs to the brain of an organism. Odors may be the result of the perception of odorants by the nose that occurs during inhalation. In this case, the air acts as an odor carrier.

[0148] Preferred aroma chemicals for loading microparticles are selected, for example, from the following compounds:

[0149] α-Hexylcinnamaldehyde, 2-phenoxyisobutyric acid ethyl ester (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis isomer content of greater than 60% by weight) (Hedione 9 、Hedione HC 9 )、4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]benzopyran (Galaxolide 3 ), Tetrahydrolinalool (3,7-dimethyloctan-3-ol), Ethyl linalool, Benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propanal (Lilial 2 ), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate and / or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate (Herbaflorat 1 ), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styryl acetate (ethyl 1-phenyl acetate), octahydro-2,3,8,8-tetramethyl-2-naphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso ESuper 3 ), hexyl salicylate, 4-tert-butyl cyclohexyl acetate (Oryclone 1 ), 2-tert-butyl cyclohexyl acetate (Agrumex HC 1 ), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-butene-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpineol acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene glycol brazilate, (E)- and / or (Z)-3-methylcyclopentadecan-5-enone (Muscenone 9 ), 15-pentadeca-11-enolate and / or 15-pentadeca-12-enolate (Globalide 1 ), 15-cyclopentadecanol (Macrolide 1 )、1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethanone (Tonalide 10 ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol 9)、2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-butene-1-ol (Sandolene 1 ), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2-cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral 1 )、2,4,4,7-Tetramethyloct-6-en-3-one (Claritone 1 )、2,6-dimethyl-5-heptene-1-aldehyde (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butyraldehyde (Florhydral 2 ), 2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional 3 )、3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon 1 ), tetrahydro-2-isobutyl-4-methyl-2H-pyran (Dihydrorosenon 4 ),

[0150] 1,4-Bis(ethoxymethyl)cyclohexane(Vertofruct 4 ), L-isopulegol (1R, 2S, 5R)-2-isopropenyl-5-methylcyclohexanol, pyranyl acetate (2-isobutyl-4-methyltetrahydropyran-4-yl acetate), nerol ((Z)-2,6-dimethyl-2,6-octadien-8-ol), neryl acetate, 7-methyl-2H-1,5-benzodioxine -3(4H)-Keto 19515 ), 3,3,5-trimethyl cyclohexyl acetate (preferably having a cis isomer content of 70% by weight) or more and 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 ), tetrahydro-4-methyl-2-(2-methylpropenyl)-2H-pyran (rose oxide), 4-methyl-2-(2-methylpropyl)oxane or 4-methyl-2-(2-methylpropyl)-2H-pyran (Dihydrorosan 4 ), amyl acetate (=3-methylbut-2-enyl acetate), isoamyl acetate, dihydromyrcenol (2,6-dimethyloct-7-en-2-ol) and methylheptenone (6-methylhept-5-en-2-one) and mixtures thereof, as well as mixtures thereof with one or more other fragrances.

[0151] In the context of the present invention, it is therefore preferred to combine the abovementioned fragrances or odorants with the mixtures according to the invention.

[0152] Where product names are specified above, these refer to the following sources:

[0153] 1 A trade name of Symrise GmbH of Germany;

[0154] 2 A trade name of Givaudan AG of Switzerland;

[0155] 3 A trade name of the International Flavors & Fragrances Inc. of the United States;

[0156] 4 A trade name of BASF SE;

[0157] 5 A trade name of Danisco Seillans SA of France;

[0158] 9 A trade name of Firmenich SA of Switzerland;

[0159] 10 A trade name of PFW Aroma Chemicals BV of the Netherlands.

[0160] More particularly, the advantages of the invention are manifested in the case of an aromachemical selected from volatile fragrances and aroma mixtures comprising at least one volatile fragrance. Volatile fragrances are understood to mean fragrances having a high vapor pressure at room temperature. A fragrance is considered to be a volatile fragrance, in particular when it has the following properties: if a drop of the volatile fragrance is applied to a paper strip and allowed to evaporate under ambient conditions at room temperature (22° C.), its odor is no longer perceptible to an experienced perfumer 2 hours after application. Volatile fragrances include in particular the following compounds: rose oxide (tetrahydro-4-methyl-2-(2-methylpropenyl)-2H-pyran), 4-methyl-2-(2-methylpropyl)oxane or 4-methyl-2-(2-methylpropyl)-2H-pyran Pentenyl acetate (=3-methylbut-2-enyl acetate), isopentyl acetate, dihydromyrcenol (2,6-dimethyloct-7-en-2-ol) and methylheptenone (6-methylhept-5-en-2-one). If an aroma mixture comprising at least one volatile aroma is used for the loading, the proportion of the volatile aroma is generally at least 1% by weight, in particular at least 5% by weight, for example 1 to 99% by weight, in particular 5 to 95% by weight, based on the total weight of the aromachemical mixture used for the loading.

[0161] Further odorants or aroma chemicals with which the odorants mentioned can be combined to give odorant compositions can be found in S. Arctander, Perfume and Flavor Chemicals, Volumes I and II, Montclair, New Jersey, 1969, author's edition or in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th edition, Wiley-VCH, Weinheim 2001. In particular, the following may be mentioned:

[0162] Extracts from natural raw materials, such as essential oils, condensed resins, absolutes, resins, balms, tinctures, for example amber tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; moss absolute; laurel oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; buchu leaf oil; kalua oil; juniper oil; calamus oil; camphor oil; cananga oil; cardamom oil; quinoa oil; cinnamon oil; Acacia absolute; castoreum absolute; cedar leaf oil; cedarwood oil; labdanum oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill oil; dill seed oil; eau de toilette absolute; oakmoss absolute; elemi oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; anise oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; guarana balsam; guarana balsam oil; helichrysum absolute Oil; Helichrysum Oil; Ginger Oil; Orris Root Absolute; Orris Root Oil; Jasmine Absolute; Calamus Oil; Blue Camellia Oil; Roman Camellia Oil; Carrot Seed Oil; Carrot Oil; Pine Needle Oil; Spearmint Oil; Kumei Oil; Lavender Oil; Lavender Absolute; Lavender Resin; Lavender Absolute; Lavender Oil; Lavender Absolute; Lavender Oil; Lemongrass Oil; Lovage Oil; Lime Oil Distilled; Lime Oil Pressed; Linalool Oil; Litsea Cubeba Oil; Bay Leaf Oil; Myristica Fragrance Oil; Mayonnaise Oil orchid oil; orange oil; cinnamon bark oil; mimosa absolute; musk seed oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; frankincense absolute; frankincense oil; red myrrh oil; neroli absolute; orange oil; oregano oil; palmarosa oil; patchouli oil; perilla oil; Peru balsam oil; parsley leaf oil; parsley seed oil; orange leaf oil; mint oil; pepper oil; allspice oil; pine oil; poley oil oil); rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; lavender oil; anise oil; styrax oil; marigold oil; fir oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; brewer's yeast oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil; and fractions thereof or components isolated therefrom.

[0163] Individual odorants are for example those from the group of

[0164] - hydrocarbons, for example 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; citronellene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0165] aliphatic alcohols, for example hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 1-octen-3-ol; a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;

[0166] - aliphatic aldehydes and their acetals, for example hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal Aldehydes; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyl acetaldehyde; (E / Z)-1-(1-methoxypropoxy)-3-hexene; aliphatic ketones and their oximes, for example 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;

[0167] - aliphatic sulfur compounds, such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;

[0168] - aliphatic nitriles, for example 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0169] - esters of aliphatic carboxylic acids, for example (E)- and (Z)-3-hexenylcarboxylate; ethyl acetoacetate; isopentyl 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; isopentyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenylisobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylvalerate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; (E / Z)-ethyl 2,4-decadienoate;

[0170] 2-octynoic acid methyl ester; 2-nonynoic acid methyl ester; 2-isopentyloxyacetic acid allyl ester; 3,7-dimethyl-2,6-octadienoic acid methyl ester; 4-methyl-2-pentyl crotonate;

[0171] acyclic terpene alcohols, for example geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoate esters;

[0172] acyclic terpene aldehydes and ketones, for example geranyl aldehyde; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and also the dimethyl and diethyl acetals of geranyl aldehyde, neral, 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, for example menthol; isopulegol; α-terpineol; terpineol-4; menthane-8-ol; menthane-1-ol; menthane-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambroxanol; vetivol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoate esters;

[0173] - Cyclic terpene aldehydes and ketones, for example menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; aniseed ketone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascone; β-damascone; β-damascone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexene)-1-yl)-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl-2-nitro-1-yl -1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-naphthone-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megatrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedarwood oil (methyl cedar ketone);

[0174] - cyclic alcohols, for example 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0175] - cycloaliphatic alcohols, for example α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5 -(2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

[0176] - cyclic and alicyclic ethers, for example eucalyptol; methyl cedarwood ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; 1,4-bis(ethoxymethyl)cyclohexane; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0177] - cyclic ketones and macrocyclic ketones, for example 4-tert-butylcyclohexanone;

[0178] 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; cis-3-methylpent-2-en-1-ylcyclopent-2-en-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecanone; 3-methyl-5-cyclopentadecanone; 3-methylcyclopentadecanone; 4-( 1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; cyclohexadec-5-en-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 7-cyclohexadecene-1-one; (7 / 8)-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0179] - cycloaliphatic aldehydes, for example 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal;

[0180] 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0181] - cycloaliphatic ketones, for example 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone;

[0182] 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-naphthylmethyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone;

[0183] - esters of cyclic alcohols, for example 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; acetate 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl ester; 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-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate;

[0184] - esters of cycloaliphatic alcohols, for example 1-cyclohexylethyl crotonate;

[0185] - esters of cycloaliphatic carboxylic acids, for example allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate;

[0186] - arylaliphatic alcohols, for example benzyl alcohol; 1-phenylethanol,

[0187] 2-phenylethanol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0188] - Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate;

[0189] 2-Phenylethyl acetate; 2-Phenylethyl propionate; 2-Phenylethyl isobutyrate;

[0190] 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;

[0191] - aromatic aliphatic ethers, for example 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated atroaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

[0192] - aromatic and araliphatic aldehydes, for example benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroataldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde;

[0193] 2-Methyl-3-(4-methoxyphenyl)propanal; 2-Methyl-3-(4-methylenedioxyphenyl)propanal;

[0194] - aromatic and araliphatic ketones, for example acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone;

[0195] 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthyl acetonide;

[0196] - aromatic and araliphatic carboxylic acids and their esters, for example benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate;

[0197] - nitrogen-containing aromatic compounds, for example 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenylvaleronitrile; methyl anthranilate; methyl N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0198] -phenols, phenyl ethers and phenyl esters, for example estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate;

[0199] 2-Methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;

[0200] - heterocyclic compounds, for example 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0201] - lactones, for example 1,4-octanolactone; 3-methyl-1,4-octanolactone;

[0202] 1,4-nonalactone; 1,4-decanolide; 8-decene-1,4-lactone; 1,4-undecalactone;

[0203] 1,4-Dodecanolactone; 1,5-Decanolactone; 1,5-Dodecanolactone; 4-Methyl-1,4-Decanolactone; 1,15-Pentadecanolactone; cis- and trans-11-Pentadecane-1,15-lactone; cis- and trans-12-Pentadecane-1,15-lactone; 1,16-Hexadecanolactone; 9-Hexadecene-1,16-lactone;

[0204] 10-Oxa-1,16-hexadecanolide; 11-Oxa-1,16-hexadecanolide; 12-Oxa-1,16-hexadecanolide; 1,12-dodecanoic acid ethylene ester; 1,13-tridecanedioic acid ethylene ester; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

[0205] Furthermore, suitable aroma chemicals are macrocyclic carboxaldehyde compounds as described in WO 2016 / 050836.

[0206] L-menthol and / or DL-menthol,

[0207] A mixture of L-menthone, L-menthyl acetate or L-isopulegol, which is highly sought after as an analogue or substitute for what is known as dementholized oil (DMO). A mixture of these mint-flavored components is preferably used in a ratio of 20%-40% by weight of L-menthol or DL-menthol, 20%-40% by weight of L-menthone and 0-20% by weight of L-menthyl acetate, or in a ratio of 20%-40% by weight, 20%-40% by weight of L-menthone and 0-20% by weight of L-isopulegol.

[0208] The above-mentioned fragrances and fragrance mixtures can be used as such or in solvents which are not fragrances themselves. Typical solvents for fragrances are especially those which have a boiling point above 150° C. at standard pressure and do not dissolve the wall material, for example glycols such as propylene glycol and dipropylene glycol, C8-C 22 Fatty acids C1-C 10 -alkyl esters such as isopropyl myristate, di-C6-C 10 - alkyl ethers, for example dioctyl ether ( OE), di-C1-C1-OE of an aliphatic, aromatic or alicyclic dicarboxylic acid or tricarboxylic acid 10 -alkyl esters, for example dialkyl phthalates such as dimethyl phthalate and diethyl phthalate and mixtures thereof, dialkyl hexahydrophthalates such as dimethyl cyclohexane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate and diisononyl 1,2-cyclohexanedicarboxylate, and dialkyl adipates such as dibutyl adipate (e.g. B), C8-C 22 Fatty acid triglycerides, for example vegetable oils or cosmetic oils such as capryl / capryl triglycerides (for example the commercial products BASF SE 318), dimethyl sulfoxide and white oil.

[0209] In other groups of embodiments, the low molecular weight organic active substance is an active pharmaceutical ingredient, referred to as API. Active pharmaceutical ingredients are typically active therapeutic ingredients, active diagnostic ingredients and active preventive ingredients, and corresponding combinations of active ingredients. Active pharmaceutical ingredients can be in an amorphous state, a crystalline state or a mixture thereof. Active pharmaceutical ingredients can be labeled with detectable labels such as fluorescent labels, radioactive labels or enzymatic or chromatographic detectable species and used together with the label as a mixture for the load of microparticles.

[0210] The API may have an aqueous solubility in deionized water of greater than 10 mg / mL at 25° C. Active pharmaceutical ingredients with low aqueous solubility may also be used as active substances, for example those having an aqueous solubility in deionized water of less than 10 mg / mL at 25° C. In any case, the API should have a partition coefficient relative to the water-immiscible liquid and the aqueous phase of at least 1.0, in particular at least 2.0.

[0211] Preferred active therapeutic, diagnostic and prophylactic ingredients are those APIs suitable for parenteral administration. Representative examples of suitable APIs are the following classes and examples of APIs and alternative forms of these APIs, such as alternative salt forms, free acid forms, free base forms and hydrates:

[0212] Analgesics / antipyretics; antiasthmatics; antibiotics; antidepressants; antidiabetics; anti-inflammatory / inflammation inhibitors; antihypertensives; inflammation inhibitors; antineoplastics; antianxiety drugs; immunosuppressants; antimigraine drugs; tranquilizers / hypnotics; antianginal drugs (antitanginal drug); antipsychotics; antimanics; antiarrhythmic drugs; antiarthritics; antigout drugs; anticoagulants; thrombolytics; antifibrinolytics; hemorheology drugs; antiplatelet drugs / platelet aggregation inhibitors; anticonvulsants; antiparkinsonian drugs; antihistamines / antipruritics; drugs used for calcium regulation; antibacterial drugs; antiviral drugs; antimicrobial drugs; anti-infective drugs; bronchodilators; corticosteroids; steroids and hormones; hypoglycemic drugs; hypolipidemic drugs; proteins; nucleic acids; drugs that can be used to stimulate erythropoiesis; antiulcer drugs / antireflux drugs; antinausea drugs / antimosis drugs; oil-soluble vitamins and other drugs.

[0213] Suitable active pharmaceutical ingredients are mentioned, for example, in WO 2007 / 070852, in particular on pages 15 to 19. Furthermore, suitable active ingredients and drugs are listed in Martindale: The Extra Pharmacopoeia, 30th edition, The Pharmaceutical Press, London 1993.

[0214] In another group of embodiments, the organic active substance is an agrochemical compound, i.e. an organic compound for crop protection, which is also referred to as an organic crop protection agent. Agrochemicals for encapsulation in microparticles are, for example, pesticides, in particular selected from the group consisting of fungicides, insecticides, nematicides, herbicides, pheromones and also safeners and growth regulators, which can be included as single compounds and also as mixtures of different agrochemical compounds, for example as a mixture of two or more herbicides, a mixture of two or more fungicides, a mixture of two or more insecticides, a mixture of an insecticide and a fungicide, a mixture of one or more herbicides with a safener and a mixture of one or more fungicides with a safener.

[0215] Typically, the agrochemical is liquid or solid at 20° C. and 1 bar and is usually non-volatile. At 20° C., the vapor pressure is typically below 0.1 mbar, especially below 0.01 mbar. Agrochemicals particularly suitable for inclusion in the microcapsules of the present invention are sparingly water-soluble or even insoluble in water, especially at 25° C., having a water solubility in deionized water of not more than 5 g / L and especially not more than 2 g / L.

[0216] Agrochemicals are known to the person skilled in the art, for example from The Pesticide Manual, 17th edition, The British Crop Protection Council, London, 2015. Suitable crop protection agents are listed in particular in WO 2018 / 019629 on pages 10 to 15.

[0217] Examples of suitable insecticides are compounds from the classes of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, bisacodyl, METI acaricides and insecticides from the class of non-classes such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargyl, triclofenac, cypermethrin, DNOC, buprofezin, cyromazine, amitraz, hydrazone, acequinoxaline, pyrimidine, rotenone, or agriculturally acceptable salts and derivatives thereof.

[0218] Examples of suitable fungicides are compounds from the classes of dinitroaniline, allylamine, anilinopyrimidine, antibiotic fungicides, aromatic hydrocarbons, benzenesulfonamide, benzimidazole, benzisothiazole, benzophenone, benzothiadiazole, benzotriazine, benzyl carbamate, carbamate, carboxamide, carboxylic acid diamide, chloronitrile, cyanoacetamide oxime, cyanoimidazole, cyclopropanecarboxamide, dicarboximide, dihydrodioxazine, dinitrophenyl crotonate, dithiocarbamate, dithiolane, ethyl phosphonate, ethylaminothiazolecarboxamide, guanidine, hydroxy(2-amino)pyrimidine, hydroxyanilide, imidazole, imidazolinone, isobenzofuranone, methoxyacrylic acid Esters, methoxycarbamates, morpholine, N-phenylcarbamates, oxazolidinedione, oxime acetate, oxime acetamide, peptidyl pyrimidine nucleoside, phenylacetamide, phenylamide, phenylpyrrole, phenylurea, phosphonate, phosphorothioate, o-carbamoylbenzoic acid, phthalimide, piperazine, piperidine, propionamide, pyridazinone, pyridine, pyridylmethylbenzamide, pyrimidineamine, pyrimidine, pyrimidone, hydrazone, pyrroloquinolinone, quinazolinone, quinoline, quinone, sulfonamide, sulfamoyltriazole, thiazolecarboxamide, thiocarbamate, thiophanate, thiophenecarboxamide, toluamide, triphenyltin compounds, triazines, triazoles and agriculturally acceptable salts and derivatives thereof.

[0219] Examples of suitable herbicides are compounds from the following classes: acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridylium salts, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanedione, dinitroaniline, dinitrophenol, diphenyl ether, glycine, imidazolinone, isoxazole, isoxazolidinone, nitrile, N-phenylphthalimide, oxadiazole, oxazolidinedione, oxyacetamide, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazoline, phenylpyridazine, The invention also includes but is not limited to oxadiazole, phosphinic acid, phosphoroamidate, phosphorodithioate, o-carbamoylbenzoate, pyrazole, pyridazinone, pyridine, picolinic acid, picolinamide, pyrimidinedione, (thio)benzoic acid pyrimidine ester, quinolinecarboxylic acid, semicarbazone, sulfonylaminocarbonyltriazolinone, sulfonylurea, tetrazolinone, thiadiazole, thiocarbamate, triazine, triazone, triazole, triazolinone, triazolocarboxamide, triazolopyrimidine, triketone, uracil, urea and agriculturally acceptable salts and derivatives thereof.

[0220] In a particular subgroup of this group of embodiments, the crop protection agent is a crop protection agent that is liquid at 22° C. and 1 bar, or a mixture of two or more crop protection agents that are liquid at 22° C. and 1 bar. Examples of room temperature liquid active ingredients are dimethenamid, especially its enantiomer dimethenamid-P, clomazone, metolachlor, especially its enantiomer S-metolachlor, alachlor, cyproconazole.

[0221] In a further specific subgroup of this group of embodiments, the crop protection agent is a crop protection agent or a mixture of crop protection agents or a mixture of such active ingredients having a low water solubility and a melting point of not more than 110° C. These include, for example, pyraclostrobin (64° C.), prochloraz (47° C.), metrafenone (100° C.), alphacypermethrin (79° C.) and pendimethalin (58° C.).

[0222] In yet another specific subgroup of this group of embodiments, the crop protection agent is a pheromone or a mixture of pheromones, optionally in combination with one or more attractants.

[0223] Pheromones are well-known chemical compounds used to control undesirable insects. For example, Metcalf, RLUllmann's Encyclopedia of Industrial Chemistry 2000, keyword "insect control", lists suitable examples in Chapter 15.1 (sex pheromone attractants) and Chapter 15.2 (aggregation pheromones), where the pheromones in Table 4 for Lepidoptera are highly suitable.

[0224] Examples of pheromones include volatile alkanols and enols having from 5 to 18 carbon atoms, volatile alkanals and enals having from 5 to 18 carbon atoms, alkanones having from 6 to 18 carbon atoms, 1,7-dioxaspirononane and 3- or 4-hydroxy-1,7-dioxaspiroundecane, benzyl alcohol, Z-(9)-tricosene (trichocene), heneicosene, diacetyl, alcanoic acids having from 5 to 16 carbon atoms, such as octanoic acid, lauric acid, α-pinene, methyl eugenol, ethyl dodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane-carboxylate, mycrenone, cucurbitacin, Mediterranean fruit fly attractant (as Commercially available) and (E,E)-8,10-dodecadien-1-ol (Codmon).

[0225] Further examples of known pheromones are: Z-5-decenyl acetate, dodecyl acetate, Z-7-dodecenyl acetate, E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E-8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate, 11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9,11-dodecadienyl acetate, Z-11-tridecenyl acetate, E-11-tridecenyl acetate, tetradecenyl acetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8- Tetradecenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenyl acetate, Z-10-tetradecenyl acetate, E-10-tetradecenyl acetate, Z-11-tetradecenyl acetate, E-11-tetradecenyl acetate, Z-12-pentadecenyl acetate, E-12-pentadecenyl acetate, hexadecyl acetate, Z-7-hexadecenyl acetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecyl acetate, E,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate, E,E-7,9-dodecadienyl acetate, Z,Z-7,9 -dodecadienyl acetate, E,E-8,10-dodecadienyl acetate, E,Z-9,12-dodecadienyl acetate, E,Z-4,7-tri-decadienyl acetate, 4-methoxy-cinnamaldehyde, [β]-ionone, estragol, eugenol, indole, 8-methyl-2-decyl propionate, E,E-9,11-tetradecadienyl acetate, Z,Z-9,12-tetradecadienyl acetate, Z,Z-7,11-hexadecadienyl acetate, E,Z-7,11-hexadecadienyl acetate, Z,E-7,11-hexadecadienyl acetate, E,E-7,11-hexadecadienyl acetate, Z,E -3,13-octadecadienyl acetate, E,Z-3,13-octadecadienyl acetate, E,E-3,13-octadecadienyl acetate, hexanol, heptanol, octanol, decyl alcohol, Z-6-nonenol, E-6-nonenol, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol, E-9-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol, Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadienol, E,Z-8,1 0-Dodecadienol, Z,Z-8,10-Dodecadienol, Z,E-8,10-Dodecadienol, E,Z-7,9-Dodecadienol, Z,Z-7,9-Dodecadienol, E-5-Tetradecadienol, Z-8-Tetradecadienol, Z-9-Tetradecadienol, E-9-Tetradecadienol, Z-10-Tetradecadienol, Z-11-Tetradecadienol, E-11-Tetradecadienol, Z-11-Hexadecadienol, Z,E-9,11-Tetradecadienol, Z,E-9,12-Tetradecadienol, Z,Z-9,12-Tetradecadienol, Z,Z-10,12-Tetradecadienol, Z,Z-7,11-Hexadecadienol, Z,E-7,11-Hexadecadienol, (E)-14-Methyl-8-Hexadecene-1-ol, (Z)-14-Methyl-8-Hexadecene-1- alcohol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecenal, Z-7-tetradecenal, Z-9-tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal, E,E-8,10-tetradecadienal, Z,E-9,11-tetradecadienal, Z,E-9,12-tetradecadienal, hexadecenal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal, Z-12-hexadecenal, Z-13- Hexadecene aldehyde, (Z)-14-methyl-8-hexadecene aldehyde, (E)-14-methyl-8-hexadecene aldehyde, Z,Z-7,11-hexadecadienal, Z,E-7,11-hexadecadienal, Z,E-9,11-hexadecadienal, E,E-10,12-hexadecadienal, E,Z-10,12-hexadecadienal, Z,E-10,12-hexadecadienal, Z,Z-10,12-hexadecadienal, Z,Z-11,13-hexadecadienal, octadecene aldehyde, Z-11-octadecene aldehyde, E-13-octadecene aldehyde, Z-13-octadecene aldehyde, Z-5-decenyl-3-methylbutyrate, nonadecane oxide (disparlure ): (+) cis-7,8-epoxy-2-methyloctadecane, seudenol: 3-methyl-2-cyclohexene-1-ol, sulcatol: 6-methyl-5-heptene-2-ol, ipsenol: 2-methyl-6-methylene-7-octen-4-ol, ipsdienol: 2-methyl-6-methylene-2,7-octen-4-ol, ene mixture I: cis-2-isopropenyl-1-methylcyclobutane-ethanol, ene mixture II: Z-3,3-dimethyl-1-cyclohexane-ethanol, ene mixture III: Z-3,3-dimethyl-1-cyclohexane-acetaldehyde, ene mixture IV: E-3,3-Dimethyl-1-cyclohexaneacetaldehyde, cis-2-verbenol: cis-4,6,6-trimethylbicyclo[3,1,1]hept-3-en-2-ol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, [α]-pinene: 2,6,6-trimethylbicyclo[3,1,1]heptene-2-ene, [α]-caryophyllene: 4,11,11-trimethyl-8-methylene-bicyclo[7,2,0]undecane, Z-9-tricosane Carbenes, ([α]-polymorphine, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane, methyl eugenol: 1,2-dimethoxy-4-(2-propenyl)phenol, trimethyldioxatricyclononane (lineatin): 3,3,7-trimethyl-2,9-dioxatricyclo[3,3,1,0]nonane, chalcogran: 2-ethyl-1,6-dioxaspiro[4,4]nonane, southern pine beetle aggregation pheromone (frontalin): 1,5-dimethyl-6,8-dioxabicyclo[ 3,2,1] octane, endo-brevicomin: endo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1] octane, exo-brevicomin: exo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1] octane, (Z)-5-(1-decenyl)dihydro-2-(3H)-furanone, farnesol: 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol, nerolidol: 3,7-11-trimethyl-1,6 ,10-dodecatrien-3-ol, 3-methyl, 6-(1-methylvinyl)-9-decen-1-ol acetate, (Z)-3-methyl-6-(1-methylvinyl)-3,9-decadien-1-ol acetate, (E)-3,9-methyl-6-(1-methyl-vinyl)-5,8-decadien-1-ol acetate, 3-methylene-7-methyl-octen-1-ol propionate, (Z)-3,7-dimethyl-2,7-octadien-1-ol propionate and (Z)-3,9-dimethyl-6-(1-methyl-vinyl)-3,9-decadien-1-ol propionate. ,

[0226] The preferred pheromone is Z-9-dodecenyl acetate (as 1 is commercially available from BASF SE), (E7,Z9)-dodecadienyl acetate (as 2 is commercially available from BASF SE), (E,E)-8,10-dodecadien-1-ol (as 3 is commercially available from BASF SE) and Z-8-dodecenyl acetate.

[0227] Particularly preferred pheromones include (E,E)-8,10-dodecadien-1-ol, which is also known as codlemone or codlure and is commercially available (e.g. as HERBAL® from Suterra LLC, USA). CM-F, from Pacific Biocontrol Corp.USA Plus; from BASF 3). Codmon can be used in pure form, in technical qualities or mixed with other pheromones.

[0228] The above pheromones may be combined with one or more attractants. An attractant is a non-pesticidal material that can act in one or more of the following ways: a) to attract insects to approach the composition or the material treated with the composition; b) to attract insects to contact the composition or the material treated with the composition; c) to attract insects to ingest the composition or the material treated with the composition; and d) to attract insects to return to the composition or the material treated with the composition. Suitable attractants include non-food attractants and food attractants, also known as feeding stimulants.

[0229] Suitable non-food attractants are typically volatile materials. Volatile attractants serve as bait and their type will depend on the harmful organisms to be controlled in a known manner. Non-food attractants include flavoring agents such as natural or synthetic sources. Suitable flavoring agents include meat flavoring agents, yeast flavoring agents, seafood flavoring agents, milk flavoring agents, butter flavoring agents, cheese flavoring agents, onion flavoring agents and fruit flavoring agents, such as the flavoring agents of apples, apricots, bananas, blackberries, cherries, red currants, gooseberries, grapes, grapefruits, raspberries and strawberries.

[0230] Suitable food attractants include:

[0231] Proteins, including animal and vegetable proteins, for example in the form of meat meal, fish meal, fish extract, seafood, seafood extract, or blood meal, insect parts, cricket meal, yeast extract, egg yolk, protein hydrolysates, yeast autolysates, gluten hydrolysates, etc.;

[0232] Carbohydrates and hydrogenated carbohydrates, in particular mono- and disaccharides, such as glucose, arabinose, fructose, mannose, sucrose, lactose, galactose, maltose, maltotriose, maltotetraose, maltopentose or mixtures thereof, such as molasses, corn syrup, maple syrup, invert sugar and honey; polysaccharides, including starches, such as potato starch, corn starch and starch-based materials, such as cereal flours (e.g. wheat flour, corn flour, malt flour, rice flour, rice bran), pectin and glycerol, hydrogenated mono- and oligosaccharides (sugar alcohols), such as xylitol, sorbitol, mannitol, isomaltolose, trehalose and maltitol and maltitol-containing syrups;

[0233] Preferred attractants are ethyl 3-methylbutyrate, methyl salicylate, amyl acetate, limonene or fruit extracts (e.g., apple extract made from dried and extracted apples, containing fructose, glucose, sorbitol, and apple flavor). Mixtures of attractants are also suitable.

[0234] In a further group of embodiments, the organic active substances are organic active substances or active mixtures suitable for cosmetic applications in addition to the abovementioned fragrances.Preferred cosmetic active substances for the loading of the microparticles are especially active plant ingredients and plant extracts.

[0235] Examples of cosmetic active substances are skin and hair pigmentation agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial active ingredients, light filter active ingredients, repellent active ingredients, hyperemic substances, keratolytic and keratinogenic substances, antidandruff active ingredients, anti-inflammatory agents, keratinizing substances, antioxidant active ingredients and active ingredients which act as free radical scavengers, skin moisturizing or humectant substances, relubricating active ingredients, deodorizing active ingredients, sebostatic active ingredients, plant extracts, antierythematous or antiallergic active ingredients and mixtures thereof.

[0236] Artificial tanning active substances suitable for tanning the skin in the absence of natural or artificial UV rays are, for example, dihydroxyacetone, alloxan and walnut shell extracts. Suitable keratin hardening substances are usually active ingredients also used in antiperspirants, such as potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc. Antimicrobial active ingredients are used to destroy microorganisms and / or inhibit their growth, and are therefore used as preservatives and also as deodorizing substances that reduce the formation or intensity of body odor. These include, for example, conventional preservatives known to those skilled in the art, such as parabens, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for example, zinc ricinoleate, triclosan, undecylenic acid alkyl alcohol amides, triethyl citrate, chlorhexidine, etc. Suitable light filter active ingredients are substances that absorb UV rays in the UV-B and / or UV-A regions. Suitable UV filters are those mentioned above. Also suitable are para-aminobenzoic acid esters, cinnamic acid esters, benzophenone and camphor derivatives, as well as UV-ray blocking pigments such as titanium dioxide, talc and zinc oxide. Suitable repellent active ingredients are compounds that can repel or drive certain animals, especially insects, away from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide, etc. Suitable hyperemic substances that stimulate blood flow through the skin are, for example, essential oils such as dwarf pine, lavender, rosemary, juniper, roasted chestnut extract, birch leaf extract, hay seed extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratin dissolving and keratin hyperplasia substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable anti-dandruff active ingredients are, for example, sulfur, sulfur polyethylene glycol dehydrated sorbitan monooleate, sulfur ricinol polyethoxylate, hydroxypyrithione zinc, hydroxypyrithione aluminum, etc. Suitable anti-inflammatory agents for combating skin irritation are, for example, allantoin, bisabolol, dragosantol, chamomile extract, panthenol and the like.

[0237] Further cosmetic active substances are aspalatin, glycyrrhizin, caffeine, proanthocyanidins, hesperidin, rutin, luteolin, polyphenols, oleuropein, theobromine, bioflavonoids and polyphenols.

[0238] Examples of plant extracts are also acai berry extract (Euterpe oleracea), acerola extract (Malpighia glabra), wild horsetail extract (Equisetum arvense), agarius extract (Agarius blazei murill), aloe vera extract (Aloe vera, Aloe Barbadensis), apple extract (Malus), artichoke leaf extract (Cynara scolymus), artichoke flower extract (Cynara edulis), arnica extract (Arnica Montana), oyster extract (Ostrea edulis), valerian root extract (Valeriana officinalis), bearberry leaf extract (Arctostaphylos uva-ursi), bamboo extract (Bambus vulgaris), bitter melon extract (Momordica charantia), bitter orange extract (Citrus aurantium), nettle leaf extract (Urtica dioica), nettle root extract (Urtica dioica), kale extract (Brassica oleracea), watercress extract (Rorippa nasturtium), Coleus forskohlii, Capsicum frutescens, Gotu Kola, Cinchona, Vaccinium vitis-daea, Curcuma longa, Tunera diffusa, Pitaya, Echinacea, Placenta wheat extract, Leotopodium alpinum, Hedera helix, Tribulus terrestris, Garcinia cambogia, Ginkgo biloba, Panax ginseng, Punica granatum, Citrus paradisi, Griffonia suffruticosa seed extract simplicifolia), green tea extract (Camellia sinensis), guarana extract (Paullinia cupana), cucumber extract (Cucumis sativus), dog rose extract (Rosacanina), blueberry extract (Vaccinium myrtillus), hibiscus extract (Malvacea), mallow extract, honey extract, hops extract (Humulus), ginger extract (Zingiber officinale), Iceland moss extract (Cetraria islandica), jojoba extract (Simmondsia chinensis), St. John's wort extract (Hypericum perforatum), coffee concentrate, cocoa bean extract (Theobroma cacao), cactus flower extract, chamomile flower extract (Matricaria recutita, Matricaria chamomila), carrot extract (Daucus carota), kiwi fruit extract (Aperygidae), kudzu extract (Pueraria lobata), coconut milk extract, pumpkin seed extract (Curcurbita pepo), cornflower extract (Centaurea cyanus), lotus extract, dandelion extract (Taraxacum officinale), maca extract (Lepidium peruvianum), magnolia extract, mango extract, milk thistle extract (Silybum marianum), Calendula officiennalis, Yerba mate extract (Hex paraguariensis), Rugcus aculeatus, Algae extract, Vaccinium macrocarpon, Moringa extract, Malva moschata extract, Evening primrose oil extract (Azadirachta indica), Urticaceae, Olive leaf extract (Olea europea), Orange extract (Hesperidin), Orchid extract, Papaya extract (Carica papaya), Peppermint extract, Geissospermum extract, Bitter orange extract (Citrus aurantioum), Bilberry extract (Vaccinium vitas-ideea), African cherry extract (Prunus africana), Sugar beet extract, Polygonum cuspidatum extract, Rooibos extract (Aspalasthus Linnearis), Rose Flower Extract, Horse Chestnut Extract (Aesculushippocastanum), Rosemary Extract (RosemarinusOfficinalis), Red Clover Extract (Trifoliumplatense), Red Wine Extract (Vitis vinifera), Saw Palmetto Extract (Serenoa repens), Lettuce Extract (Lactuca sativa), Sandalwood Extract (Santalum rubrum), Sage Extract (Salviaofficinalis), Horsetail Extract (Equisetum), Yarrow Extract (Achillea millefolium), Black Pepper Extract (Piper nigrum), Black Tea Extract, Water Lily Extract (Nymphaea), White Willow Bark Extract (Salix Alba), Licorice Extract (Glycyrrhiza), Devil's Claw Extract (Harpagophytum procumbens), Thyme Extract (Thymus vulgaris), Tomato Extract (Lycopersicum esculentum), Grape Seed Extract (Vitisvinifera), Grape Skin Extract (Vitis vinifera), Watercress (Rorippa amphibia), Willow Bark Extract (Salix alba), Wormwood Extract (Artemisia absinthium), white tea extract, yam extract (Dioscorea opposita), yohimbe extract (Pausinystalia yohimbe), witch hazel extract (Hamamelis), cinnamon extract (Cinnamomum cassia Presl), lemon extract (Citrus), and onion extract (Allium cepa).

[0239] In a further group of embodiments, the low molecular weight organic active substance is a vitamin, in particular a lipophilic vitamin, such as vitamin A, vitamin D, vitamin E or vitamin K or a combination thereof.

[0240] In other groups of embodiments, low molecular weight organic active substances are organic effect compounds. Effect compounds are organic active substances that do not belong to agricultural chemicals, aromatic chemicals, vitamins, AIPs and cosmetic active substances. The group of effect compounds is typically not allowed to be used in agriculture, for application to humans, for cosmetics or dietary purposes. They include but are not limited to compounds for building chemistry, particularly catalysts, but also dyes, UV stabilizers, polymerization inhibitors, oxidation stabilizers, etc. Preferred active substances for being encapsulated in microparticles for use in building chemistry are especially polymerization catalysts.

[0241] Available polymerization catalysts include those suitable for curing reactive resins, especially addition resins, condensation resins or oxidation-curing resins. For this purpose, polymerization catalysts are catalysts for free radical polymerization, polycondensation and / or polyaddition. Suitable catalysts for free radical polymerization include peroxide splitting agents in particular, and catalysts known as driers or siccatives by coating technology for oxidative drying oils and alkyd resins. Suitable polycondensation catalysts are catalysts for silicone condensation and crosslinking. The polyaddition catalyst used can be, for example, a catalyst for curing epoxy resins. In addition, the polyaddition catalyst used can be, for example, a urethanization catalyst conventionally used in polyurethane chemistry. These are compounds that accelerate the reaction of the reactive hydrogen atoms of isocyanate-reactive components with organic polyisocyanates.

[0242] Useful polymerization catalysts include, inter alia, tertiary amines, phosphines and organic metal salts.

[0243] Tertiary amines which can be used as polymerization catalysts, in particular for polyaddition, are, for example, triethylamine, tributylamine, N,N-dimethylcyclohexylamine (DMCHA), N-methyldicyclohexylamine, N,N-dimethylbenzylamine (BDMA), N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, 2,2'-dimorpholinodiethyl ether (DMDEE), N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexamethylenediamine, -1,6-diamine, N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA), N,N,N',N",N"-pentamethyldipropylenetriamine (PMDPTA), N,N,N-tris(3-dimethylaminopropyl)amine, bis(2-dimethylaminoethyl)ether (BDMAEE), bis(dimethylaminopropyl)urea, 2,4,6-tris(dimethylaminomethyl)phenol and its salts with 2-ethylhexanoic acid and its isomers, 1,4-dimethylpiperazine (DMP),

[0244] N-methylimidazole, 1,2-dimethylimidazole, 1-methyl-4-(2-dimethylaminoethyl)piperazine, 1-azabicyclo[3.3.0]octane, 1,4-diazabicyclo[2.2.2]octane (DABCO),

[0245] 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-7-ene (DBN).

[0246] Additional useful polymerization catalysts, especially for polyaddition, include tris(dialkylamino)-s-hexahydrotriazines, especially 1,3,5-tris(3-[dimethylamino]propyl)hexahydrotriazine.

[0247] Phosphines which can be used as polymerization catalysts, in particular for polyaddition, are preferably tertiary phosphines, such as triphenylphosphine or methyldiphenylphosphine.

[0248] Organic metal salts useful as polymerization catalysts preferably have the general formula

[0249] L m M n+ n A -

[0250] in

[0251] The ligand L is an organic group or organic compound selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl and acyl, the ligand L has 1 to 20 carbon atoms, and the m ligands L are the same or different,

[0252] m is 0, 1, 2, 3, 4, 5, or 6,

[0253] M is for metal,

[0254] n is 1, 2, 3, or 4, and

[0255] Anion A - It is a carboxylate ion, an alkoxylate ion or an enolate ion.

[0256] The metal M is preferably selected from lithium, potassium, cesium, magnesium, calcium, strontium, barium, boron, aluminum, indium, tin, lead, bismuth, cerium, cobalt, iron, copper, lanthanum, manganese, mercury, scandium, titanium, zinc and zirconium; more particularly selected from lithium, potassium, cesium, tin, bismuth, titanium, zinc and zirconium.

[0257] The ligand L is preferably an alkyl group having 1 to 20 carbon atoms. More preferably, L is an alkyl group having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0258] The carboxylate ion preferably has the formula R 1 -COO - , where R 1 is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, and wherein R 1 The radicals have up to 20 carbon atoms, preferably 6 to 20 carbon atoms. Particularly preferred carboxylate ions are selected from the anions of natural and synthetic fatty acids, such as neodecanoate, isooctanoate and laurate, and the anions of resin acids and cycloalkane acids.

[0259] The enolate ion preferably has R 2 CH=CR3 -O - , where R 2 and R 3 are each selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, and wherein R 2 and R 3 The radicals each have up to 20 carbon atoms. Specific examples are ethyl pyruvate, heptyl pyruvate or phenyl pyruvate. The enolate ion is preferably derived from a 1,3-diketone having five to eight carbon atoms. Possible examples include acetylacetonate, the enolate of 2,4-hexanedione, the enolate of 3,5-heptanedione and the enolate of 3,5-octanedione.

[0260] The alkoxide ion preferably has the formula R 4 -O - , where R 4 is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl and acyl, and wherein R 4 The radical has up to 20 carbon atoms.

[0261] In a specific embodiment, the organometallic compound is selected from

[0262] - alkali metal carboxylates, such as lithium ethylhexanoate, lithium neodecanoate, potassium acetate, potassium ethylhexanoate, cesium ethylhexanoate;

[0263] - Alkaline earth metal carboxylates, such as calcium ethylhexanoate, calcium naphthenate, calcium octoate (as Calcium available from OMG Borchers), magnesium stearate, strontium ethylhexanoate, barium ethylhexanoate, barium naphthenate, barium neodecanoate;

[0264] - Aluminium compounds such as aluminium acetylacetonate, aluminium dionate (e.g. Aluminium from King Industries 5218);

[0265] - zinc compounds, for example zinc diacetate (II), zinc ethylhexanoate (II) and zinc octoate (II), zinc neodecanoate, zinc acetylacetonate;

[0266] - tin compounds, such as tin(II) carboxylates, examples being tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, tin(II) neodecanoate, tin(II) isononanoate, tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids, examples being dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate, in particular dibutyltin dilaurate;

[0267] - titanium compounds, such as tetra(2-ethylhexyl)titanate;

[0268] - zirconium compounds such as zirconium ethylhexanoate, zirconium neodecanoate, zirconium acetylacetonate (e.g. from King Industries 4205); Zirconium diacetylacetonate (e.g., from King Industries XC-9213; XC-A 209 and XC-6212); 2,2,6,6-tetramethyl-3,5-heptane acetylacetonate zirconium;

[0269] - bismuth compounds such as bismuth carboxylates, in particular bismuth octanoate, bismuth ethylhexanoate, bismuth neodecanoate or bismuth pivalate (e.g. bismuth bismuth from King Industries 348, XC-B221, XC-C227, XC 8203, XK 651, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals, and those from ShepherdLausanne);

[0270] - manganese salts, such as manganese neodecanoate, manganese naphthenate;

[0271] - cobalt salts, such as cobalt neodecanoate, cobalt ethylhexanoate, cobalt naphthenate;

[0272] - iron salts, such as iron ethylhexanoate;

[0273] - Mercury compounds, such as phenylmercury carboxylates.

[0274] Preferred organometallic compounds are dibutyltin dilaurate, dioctyltin dilaurate, zinc(ll) diacetate, zinc(ll) dioctoate, zirconium acetylacetonate and 2,2,6,6-tetramethyl-3,5-heptanezirconium acetylacetonate, bismuth neodecanoate, bismuth dioctoate and bismuth ethylhexanoate.

[0275] In the first step i. of the process of the invention, a water-immiscible liquid is prepared by mixing at least one organic active substance, a shell-forming compound (SFC1) and, if necessary, one or more organic solvents. Preferably, the water-immiscible liquid is a solution of the organic active substance, the shell-forming compound (SFC1) and optionally one or more organic solvents. In order to achieve dissolution of the components, the mixture may be agitated and / or stirred. Typically, the temperature for providing the water-immiscible liquid is not critical and is typically in the range of 5° C. to 80° C.

[0276] The concentration of the organic active compound to be encapsulated in the water-immiscible liquid can vary and is typically in the range of 1% to 99% by weight, in particular in the range of 10% to 98.5% by weight, in particular in the range of 20% to 98% by weight, based on the total weight of the water-immiscible liquid. The concentration of the shell-forming compound (SFC1) in the water-immiscible liquid is typically in the range of 1% to 50% by weight, in particular in the range of 1.5% to 25% by weight and in particular in the range of 2% to 15% by weight, based on the total weight of the water-immiscible liquid. Preferably, the total amount of shell-forming compound (SFC1) and the organic active compound to be encapsulated is at least 10% by weight, in particular at least 20% by weight or at least 50% by weight, based on the total weight of the water-immiscible liquid. Typically, the remainder is, if necessary, a water-immiscible organic solvent.

[0277] In a second step ii., the water-immiscible liquid obtained in step i. is emulsified in an aqueous medium. Thus, an oil-in-water emulsion of a water-immiscible liquid, also referred to below as an o / w emulsion, is formed, which contains at least one organic active substance and a shell-forming compound (SFC1). In this o / w emulsion, the water-immiscible liquid forms the dispersed phase, while the aqueous phase is the continuous phase.

[0278] The aqueous phase generally contains at least one dispersant in order to stabilize the droplets of the o / w emulsion during its production in step ii. and also during the reaction of the shell-forming compounds (SFC1) and (SFC2) in step iii.

[0279] Dispersants suitable for stabilizing o / w emulsions are common knowledge and are mentioned, for example, in EP 2794085 and EP 3007815, the teachings of which are expressly incorporated by reference. Typical dispersants include polysaccharides, polyvinyl alcohols, polymers with sulfonate groups, polymers with carboxylate groups, polyvinyl pyrrolidone, copolymers of vinyl pyrrolidone and inorganic Pickering stabilizers.

[0280] Suitable dispersants are typically water-soluble organic polymers. Inorganic Pickering systems such as colloidal silica and colloidal clay minerals can also be used as dispersants for this purpose. Pickering stabilizers (also called Pickering systems) can be used as such or in combination with water-soluble organic polymers.

[0281] Dispersants from the group of polysaccharides include, for example, cellulose derivatives such as hydroxyethylcellulose, methylhydroxyethylcellulose, methylcellulose and carboxymethylcellulose, methylhydroxypropylcellulose, lignin sulfonates and also mixtures thereof.

[0282] Preferred dispersants include at least one of partially or completely hydrolyzed polyvinyl acetate (polyvinyl alcohol) and methylhydroxy (C1-C4) alkyl cellulose and mixtures thereof. Preferred dispersants also include a Pickering system, in particular a combination of a Pickering system with one or more of the above-mentioned organic polymer dispersants, preferably partially or completely hydrolyzed polyvinyl acetate (polyvinyl alcohol) and also methylhydroxy (C1-C4) alkyl cellulose and mixtures thereof.

[0283] Among the organic water-soluble polymers, particularly preferably partially hydrolyzed polyvinyl acetate, also referred to as partially hydrolyzed polyvinyl alcohol (PVA), wherein in particular a degree of hydrolysis of 70% to 99.9%, in particular 75% to 99%, more particularly 80% to 95% is considered. In addition, PVA copolymers are also suitable, as described in WO 2015 / 165836. PVA can in particular be a carboxyl-modified anionic PVA. Such a carboxyl-modified PVA preferably has a carboxyl ratio of 1 to 6 mol%. In particular, a carboxyl-modified PVA is used as a dispersant, and a 4% by weight aqueous solution thereof preferably has a viscosity in the range of 20.0 to 30.0 mPa*s at 20°C. In the group of partially hydrolyzed polyvinyl alcohols, particularly preferably those having a degree of hydrolysis of 70% to 99.9%, in particular 75% to 99%, more particularly 80% to 95% and especially 85% to 95% are considered. Particularly preferred dispersants are carboxyl-modified anionic PVAs having 1 to 6 mol% of carboxyl groups based on the amount of repeating units and a degree of hydrolysis in the range of 75% to 99%, particularly 80% to 95% and especially 85% to 95%. Among these, preferred are those whose 4% by weight aqueous solution has a viscosity of 20.0 to 30.0 mPa*s at 20°C.

[0284] Among the organic water-soluble polymers, methylhydroxy(C1-C4)alkylcelluloses are also particularly preferably considered. Methylhydroxy(C1-C4)alkylcelluloses are understood to mean methylhydroxy(C1-C4)alkylcelluloses of various degrees of methylation and also degrees of alkoxylation. Preferred methylhydroxy(C1-C4)alkylcelluloses have an average degree of substitution DS of 1.1 to 2.5 and a molar degree of substitution MS of 0.03 to 0.9. Suitable methylhydroxy(C1-C4)alkylcelluloses are, for example, methylhydroxyethylcellulose or methylhydroxypropylcellulose. A particularly preferred methylhydroxypropylcellulose is methylhydroxypropylcellulose, whose 2% aqueous solution has a viscosity in the range of 90 to 700 mPa·s, in particular in the range of 100 to 600 mPa·s, in particular in the range of 400 to 550 mPa·s, as determined on a dry basis by a Brookfield RVT at 20° C. at 20 rpm. Particularly preferred is a methylhydroxypropylcellulose whose 2% aqueous solution has a viscosity in the range of 400 to 550 mPa·s, as determined on a dry basis by a Brookfield RVT at 20° C. at 20 rpm. The methylhydroxypropylcellulose is commercially available, for example, as Culminal MHPC 400R from Ashland. Non-limiting examples of commercially available methylhydroxypropylcelluloses having a viscosity in the above range are, for example, Culminal MHPC 100, Culminal MHPC 400R, Culminal MHPC 500RF from Ashland.

[0285] Also preferred dispersants are salt polymers with sulfonate groups. Such polymers include homopolymers and copolymers of ethylenically unsaturated sulfonic acids (such as 2-acrylamide-2-methylpropane sulfonic acid) optionally with one or more water-soluble monomers (such as acrylamide or methacrylamide and salts thereof). They also include salts of lignin-based sulfonic acids, also referred to as lignin sulfonates (lignin sulfonate or lignosulfonate). Suitable lignin sulfonates can include, for example, sodium lignin sulfonate, calcium lignin sulfonate, ammonium lignin sulfonate, magnesium lignin sulfonate, potassium lignin sulfonate or sulfomethylated lignin sulfonates. The above-mentioned salts are particularly sodium salts or ammonium salts of polymers with sulfonate groups.

[0286] Particularly suitable lignin-based sulfonic acids have an average molar weight Mw of at least 5,000 Da. Preferably, the average molar weight Mw is in the range of 5,000 Da to 100,000 Da, as determined by gel permeation chromatography according to DIN 55672-3. Preferably, the lignin-based sulfonic acid has a degree of sulfonation of from 1.0 to 2.5 mol / kg of the lignin-based sulfonic acid, wherein the degree of sulfonation of the lignin-based sulfonic acid as applied herein is calculated from the sulfur content of the lignin-based sulfonic acid as determined by atomic emission spectroscopy, from which the content of sulfate (determined according to DIN 38405-D5-2) is subtracted. Preferred lignin-based sulfonic acids are lignin-based sulfonic acid, ethoxylated lignin-sulfonic acid or oxidized lignin. Particularly preferred lignin sulfonates are sulfonated kraft lignin, which is, for example, Ingevity 910 is commercially available. Non-limiting examples of commercially available lignin sulfonates include, for example, Greensperse s7, 85. 88A, 907, 910, o, Hyact, Kraftsperse 25m and Borresperse NA. Greensperse s7, Kraftsperse 25m and 85 (commercially available from Ingevity) and Borresperse NA (commercially available from Borregaard AS) contain sodium lignin sulfonate. 88A, 907, 910, O and Hyact (commercially available from Ingevity) contain sulfonated kraft lignin.

[0287] Among the organic water-soluble polymers, preference is also given to polymers with carboxyl groups. Typically, such polymers are homopolymers or copolymers of monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid. The polymers with carboxyl groups are typically used in their partially or completely neutralized form, wherein the carboxyl groups are converted in the form of anionic carboxylates. Typically, the counterion is selected from sodium and ammonium.

[0288] Another group of preferred dispersants are the inorganic pickering systems, in particular colloidal silica or phyllosilicates.

[0289] In the context of the present invention, the term "colloidal silica", also referred to as colloidal silica dispersion, colloidal nanoparticle silica or colloidal silica sol, refers to a stable dispersion of amorphous particulate silica SiO2 having a particle size in the range of 3 to 200 nm, preferably in the range of 5 to 170 nm, especially in the range of 10 to 150 nm. In this respect, the particle size of the colloidal silica is at least 3 nm, preferably at least 5 nm and even more preferably at least 10 nm. The upper limit is set by the fact that the particles must be able to exist in a stable colloidal silica sol. Therefore, the particle size is at most 200 nm, preferably at most 170 nm and most preferably at most 150 nm, especially at most 100 nm. The particle size of colloidal silica refers to the volume average particle diameter of the silica particles as determined by static light scattering, as described above.

[0290] An example of a suitable colloidal silica sol is a colloidal silica sol having a particle size of 9 nm, which is available, for example, under the trade name 30 / 360 is commercially available from Akzo Nobel. Another example of a suitable colloidal silica sol is a colloidal silica sol having a particle size in the range of 10 to 150 nm, for example as 50 / 80 is commercially available from Akzo Nobel. Another suitable silica sol is 15 / 500, 30 / 220, 40 / 200, CC151 HS, CC301 (Akzo Nobel), 215. 830, 1430, 2034DI and DP5820, DP5480, DP5540, etc. (Nyacol Products), 100 / 30, 10°F. / 30, 100S / 30, 200 / 30, 200F / 30, 300F / 30, VP 4038, VP 4055 (HCStarck / Bayer) or PG 001, PG 002( Aqueous dispersions of, Cabot Corporation (Cabot), Quartron PL-1, Quartron PL-3 (Fuso Chemical Co.), 0830, 1030, 1430(Chemiewerk Bad ).

[0291] In a preferred embodiment, the dispersant comprises a colloidal silica sol having a particle size in the range of 3 to 200 nm, in particular in the range of 5 to 170 nm, in particular in the range of 10 to 150 nm, which is commercially available, for example, as Bindzil 50 / 80 from Akzo Nobel.

[0292] In another preferred embodiment, the dispersant comprises a phyllosilicate, in particular a clay mineral that is swellable in water, such as hectorite, montmorillonite, saponite or in particular a smectite with a high content (in particular sodium montmorillonite, such as Laponite TM ) of phyllosilicate.

[0293] In particular, inorganic pickering systems, such as the above-mentioned colloidal silica and phyllosilicates, are used in combination with organic polymer dispersants, in particular with organic polymer dispersants from the group consisting of polyvinyl alcohols. Thus, particularly dense microparticles are obtained. In this case, the particles of the inorganic pickering system remain at the surface of the microparticles.

[0294] To stabilize the o / w emulsion, a dispersant is added to the aqueous phase. The concentration of the dispersant in the aqueous phase is typically in the range of 0.1% to 10.0% by weight, in particular in the range of 0.2% to 5.0% by weight and in particular in the range of 0.3% to 3.0% by weight, based on the total weight of the aqueous phase.

[0295] Regarding the amount of water-immiscible liquid of step i. to be emulsified, the concentration of the dispersant and the relative amounts of the water-immiscible liquid of step i. and the aqueous phase are preferably selected so that the amount of dispersant is in the range of 0.1 to 10% by weight, in particular in the range of 0.2 to 5% by weight, based on the total weight of the water-immiscible liquid of step i.

[0296] The weight ratio of the water-immiscible liquid prepared in step i. to the aqueous phase is typically in the range from 1:10 to 1.5:1, in particular in the range from 1:5 to 1.1:1 and in particular in the range from 1:2 to 1:1.

[0297] In order to prepare the o / w emulsion in step ii. and for its stabilization, one or more emulsifiers can be used together with the above-mentioned dispersants. Compared with dispersants, emulsifiers typically have a lower molecular weight of usually no more than 500 g / mol (number average). Preferably, emulsifiers with an HLB value of at least 10, especially at least 15 according to Griffin are considered. The HLB value (HLB=hydrophilic-lipophilic balance) according to Griffin (WCGriffin:Classification of surface-active agents by HLB [HLB classification of surfactants]. In: J.Soc.Cosmet.Chem.1,1949, pages 311–326) is a dimensionless number between 0 and 20, which provides information about the water and oil solubility of the compound. Preferably, these are nonionic emulsifiers with an HLB value of at least 10, especially at least 15 according to Griffin. However, anionic and zwitterionic emulsifiers with an HLB value of at least 10, especially at least 15 according to Griffin are also suitable. Such emulsifiers are generally used in an amount of from 0.1% to 10% by weight, especially 0.5% to 5% by weight, based on the total weight of the emulsion prepared in step ii. Typically, one or more emulsifiers may be added to the water-immiscible liquid of step i prior to emulsification or in an aqueous medium.

[0298] Examples of suitable emulsifiers having an HLB value of at least 10 according to Griffin are:

[0299] - ethoxylated sorbitan fatty acid esters, in particular sorbitan mono-, di- and tri-fatty acid esters and mixtures thereof, such as sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan tristearate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate;

[0300] - lactyl esters of fatty acid monoesters of glycerol;

[0301] - lecithin;

[0302] - ethoxylated castor oil, ethoxylated hydrogenated castor oil having a degree of ethoxylation of at least 20, for example from 20 to 60;

[0303] - ethoxylated and / or propoxylated C having a degree of alkoxylation in the range of at least 10 12 -C 22-alkanols, for example stearyl alcohol ethoxylate having a degree of ethoxylation in the range of 10 to 50, stearyl alcohol ethoxylate-co-propoxylate having a degree of alkoxylation in the range of 10 to 50, isotridecyl ethoxylate having a degree of ethoxylation in the range of 10 to 50 and isotridecyl ethoxylate-co-propoxylate having a degree of alkoxylation in the range of 10 to 50;

[0304] - ethoxylated and / or propoxylated C4-C 16 - Alkylphenols, for example nonylphenol ethoxylate having a degree of ethoxylation in the range of 10 to 50 and octylphenol ethoxylate having a degree of ethoxylation in the range of 10 to 50.

[0305] Typically, the aqueous phase is water, which preferably contains a dispersant and optionally an emulsifier. In addition, the aqueous phase may contain a defoamer. The concentration of the defoamer in the aqueous phase is typically less than 2 g / kg, in particular not more than 1 g / kg, based on the total weight of the aqueous phase. The aqueous phase may contain a small amount of an organic solvent miscible with water. The amount of such solvents is usually not more than 10% by weight, in particular not more than 5% by weight or 1% by weight, based on the total weight of the aqueous phase.

[0306] The emulsification of the water-immiscible liquid provided in step i. in an aqueous medium to obtain an o / w emulsion in process step ii. can be achieved by standard procedures for producing emulsions. Typically, the emulsification is achieved by stirring or shearing the mixture of the aqueous phase and the solution obtained in step i. or a combination of the two.

[0307] The aqueous phase containing the dispersant is preferably initially charged to the container and the water-immiscible liquid provided in step i. is metered into the aqueous phase with mixing of the two liquids, for example with stirring or shearing. It is also possible to combine the aqueous phase flow and the solution flow of step i. continuously in a mixing chamber and to remove the o / w-emulsion continuously from the mixing chamber. The mixing chamber can have static or dynamic mixing elements.

[0308] Depending on the energy input into the mixture of the aqueous phase and the water-immiscible liquid provided in step i., the droplet size can be controlled. In addition, the type and amount of dispersant described above influence the size of the emulsion droplets in equilibrium. A suitable amount can be selected by conventional methods. For the purposes of the present invention, it has been found to be beneficial if the final average particle size D[v,0.5] of the microparticles will not exceed 400 μm, in particular 200 μm and especially 100 μm.

[0309] Here and below, all figures for particle size, particle diameter and particle size distribution, including the D[v,0.1], D[v,0.5], D[v,0.9], D[4,3] and D[3,2] values, are based on the particle size distribution determined by static laser scattering of a sample of particulates according to ISO 13320:2009. The abbreviation SLS is also used below to refer to "static laser scattering according to ISO 13320:2009". In this regard, the D[v,0.1] value means that 10% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v,01]. Thus, the D[v,0.5] value means that 50% by volume of the particles of the measured sample have a particle size below the value reported as D[v,0.5], and the D[v,0.9] value means that 90% by volume of the particles of the measured sample have a particle size below the value reported as D[v,0.9]. The D[4,3] value is a volume-weighted average determined by means of SLS, which is also called the De Brouckere average and corresponds to the mass average of the particles of the present invention. The D[3,2] value is a surface-weighted average determined by means of SLS, which is also called the Sauter mean diameter (SMD).

[0310] Although stirring will generally produce droplets with an average droplet size D[v,0.5] of at most or below 400 μm, in particular at most 200 μm and in particular at most 100 μm, for example in the range of 0.5 to 400 μm, in particular 1 to 200 μm, in particular 1 to 100 μm, this is achieved with the aid of a device for generating a high shear field. Sufficient shear energy can also be introduced by vigorous stirring so that an average droplet size with a D[v,0.5] value in the range from 0.5 to 400 μm, preferably 1 to 200 μm and in particular 1 to 100 μm is obtained. If a higher shear energy input is desired, the use of a device for generating a high shear field can be advantageous.

[0311] By adjusting the droplet size and droplet size distribution of the o / w emulsion, the particle size and particle size distribution of the final microparticles containing the organic active compound can be adjusted. In other words, a small average particle size of the microparticles is achieved by providing an o / w emulsion with a small average droplet size, and similarly, a narrow droplet size distribution of the o / w emulsion will result in a narrow particle size distribution of the obtained microparticles loaded with the organic active compound.

[0312] Suitable agitator types include propeller agitators, impeller agitators, pan agitators, paddle agitators, anchor agitators, inclined blade agitators, cross-beam agitators, spiral agitators, screw agitators, and the like.

[0313] The suitable device for shearing, i.e., for generating a high shear field, is a disperser operated by the rotor-stator principle, i.e., a rotor-stator mixer, such as a gear ring disperser, also referred to as a gear disperser, and other colloid mills and disc mills, high-pressure homogenizers, also referred to as high-pressure mixers and ultrasonic homogenizers. High shear can also be achieved by using a dispersion disk or a cross-blade agitator with one or more stages. High shear can also be achieved by passing the mixture through a microfluidic device. Among the devices for shearing, a disperser operated by the rotor-stator principle for generating a shear field, particularly a gear ring disperser, is preferred. Depending on the machine size and dispersibility, the diameter of the rotor and stator is typically in the range of 1 cm to 40 cm. Depending on the type of structure, the rotational speed of such a disperser is usually in the range of from 500 to 20 000 rpm, particularly from 1000 to 15000 rpm (rev / min). Of course, a machine with a large rotor diameter rotates at the lower end of the speed range, while a machine with a small rotor diameter is usually operated at the upper end of the speed range. The peripheral speed of the rotor is typically in the range of 5 to 50 m / s. The distance between the rotating part and the fixed part of the dispersing tool is usually 0.1 to 3 mm.

[0314] As mentioned above, the droplet size can be controlled by the shear energy input into the mixture of aqueous phase and solution obtained in step i. The introduced shear energy can be derived directly from the power consumption of the device for generating the shear field, taking into account the heat losses. Thus, the shear energy input into the o / w emulsion is preferably 250 to 25 000 Watt h / m 3 Batch size. Based on the motor current calculation, 500 to 15,000, in particular 800 to 10,000 watts h / m 3 Energy input for batch size.

[0315] In a preferred embodiment, the emulsification is performed so that the emulsion droplets of the o / w emulsion have an average diameter D[v,0.5] of at most or below 400 μm, for example in the range of 0.5 to 400 μm, in particular in the range of 1 to 200 μm and especially in the range of 1 to 100 μm, as determined by means of light scattering. To this end, the emulsification typically comprises mixing the solution of step i. with an aqueous phase and homogenizing the mixture. Homogenization is typically achieved by subjecting the mixture to high shear using a suitable apparatus as described above. Mixing and homogenization can be performed sequentially or simultaneously.

[0316] For example, the solution of step i. and the aqueous phase are mixed under stirring, and the obtained emulsion is then homogenized as described herein, for example by

[0317] - treating the emulsion with a rotor-stator mixer, in particular a gear-rim mixer;

[0318] - applying ultrasound to the emulsion;

[0319] - treating the emulsion with a dispersing disk or cross-blade stirrer having one or more stages;

[0320] - passing the emulsion through a membrane device,

[0321] - passing the emulsion through a high pressure homogenizer;

[0322] or by a combination thereof.

[0323] Mixing and homogenization can also be carried out simultaneously. For example, the aqueous phase flow and the solution flow of step i. are continuously combined in a mixing chamber as a homogenizer, and the o / w-emulsion is continuously removed from the mixing chamber. For this purpose, the above-mentioned homogenizer can be used and is adapted to continuous operation. For this purpose, mainly any of the above-mentioned homogenizers can be used. Membrane equipment and high-pressure homogenizers are preferred.

[0324] The emulsification is usually carried out at a temperature in the range of 5°C to 80°C, in particular in the range of 10°C to 60°C. The temperature of the mixture is preferably selected so that it has a temperature in the range of 10°C to 60°C, in particular in the range of 10°C to 40°C. Typically, the emulsification is carried out at atmospheric pressure or a pressure above atmospheric pressure, for example at a pressure of up to 2 bar. However, a slight vacuum may be applied. Preferably, the vacuum will not be less than 800 mbar.

[0325] In step iii., at least one second shell-forming compound (SFC2) is added to the aqueous medium. The second shell-forming compound (SFC2) can be added to the aqueous medium before or during step ii. Preferably, the second shell-forming compound (SFC2) is added to the emulsion obtained in step ii., i.e. it is added to the emulsion after step ii. has been completed. Thereby, particularly uniform microparticles are obtained.

[0326] Microparticles are obtained by adding a second shell forming compound (SFC2) to the o / w emulsion of step ii., which reacts with the first shell forming compound (SFC1) as explained above, whereby a shell is formed on the surface of the droplets of the water-immiscible liquid present in the emulsion obtained in step ii. of the process.

[0327] Typically, the second shell forming compound (SFC2) may be added as such, or it may also be added as an aqueous solution or emulsion depending on its solubility in water.

[0328] The second shell-forming compound (SFC2) may be added all at once or over a certain period of time, for example over 1 to 60 minutes, in particular over 5 to 30 minutes.

[0329] The temperature during the addition may vary depending on the reactivity of the shell forming compounds (SFC1) and (SFC2) and is typically in the range of 0°C to 60°C, in particular in the range of 5°C to 40°C. Higher temperatures will typically result in a faster reaction, but potentially in a broader size distribution of the resulting microparticles. Particularly preferably, the temperature during the addition will not exceed 30°C.

[0330] After the addition has been completed, the mixture of the o / w emulsion obtained in step ii. and the second shell forming compound (SFC2) may be allowed to react for a further period of time to complete the reaction of the shell forming compounds (SFC1) and (SFC2). This further period of time is also referred to as the post-reaction period. Typically, 24 h will be sufficient to achieve a complete reaction. During the post-reaction period, the temperature of the reaction mixture is typically in the range of 0° C. to 80° C., in particular in the range of 5° C. to 70° C.

[0331] During the addition and during the post-reaction time, the mixture may be agitated or stirred to achieve a more uniform reaction and avoid settling of the particles before the reaction of the shell forming compounds (SFC1) and (SFC2) is complete.

[0332] By the process of the invention an aqueous suspension of microparticles is obtained.As explained above, the microparticles comprise a shell of organic wall material resulting from the reaction of shell forming compounds (SFC1) and (SFC2) and a core containing an organic active compound.

[0333] The microparticles obtainable by the process of the present invention preferably have a median particle size, i.e. a D[v,05] value, in the range of 0.5 to 400 μm, in particular in the range of 0.8 to 200 μm, preferably in the range of 1.0 to 100 μm, more preferably in the range of 1.0 to 50 μm, in particular in the range of 1.0 to 30 μm.

[0334] The microparticles obtainable by the method of the present invention preferably have a Sauter mean diameter, i.e. a D[3,2] value, in the range of 0.3 to 300 μm, in particular in the range of 0.5 to 180 μm, more preferably in the range of 0.8 to 100 μm, more preferably in the range of 1.0 to 100 μm and in particular in the range of 1.0 to 80 μm.

[0335] The microparticles obtainable by the process of the invention are preferably particles of regular shape, in particular spherical particles. The term "regular shape" means that the surface of the particle does not have any large depressions in the wall material or in the height of the wall material. The term "spherical" means that the particle has the shape of an approximate spheroid of rotation and is in particular spherical, wherein, in particular in the particle, the ratio of the longest axis passing through the center of the particle to the shortest axis passing through the center of the particle does not exceed a value of 2 and is in particular in the range from 1:1 to 1.5:1.

[0336] As described above, step iii. produces an aqueous suspension of microparticles. For further applications, an aqueous suspension can be used. However, the microparticles can also be separated from the aqueous suspension obtained in step iii. by conventional techniques. This further step can be carried out by separating the microparticles from the aqueous phase, for example by filtering or by centrifugation, or by evaporating the water of the aqueous suspension, for example in a spray drying device. Regardless of the separation technique used, the microparticles can be dried. "Drying" should be understood to mean that the loaded microparticles contain a residual amount of water of ≤5% by weight, preferably ≤1% by weight, based on the microparticles. Drying can be carried out, for example, in an air stream and / or by applying a vacuum, optionally heated in each case. Depending on the size of the microparticles, this is achieved by means of a convection dryer (such as a spray dryer, a fluidized bed and a cyclone dryer), a contact dryer (such as a disc dryer, a paddle dryer, a contact belt dryer), a vacuum drying cabinet or a radiation dryer (such as an infrared rotary tube dryer and a microwave mixing dryer). After the supported polymer particles have been separated from the aqueous suspension, any residual water present can also be removed by rinsing with ethanol or acetone and / or blowing the particles dry with an inert gas such as air, nitrogen or argon. Optionally, pre-dried and / or preheated inert gases can also be used for this purpose. The supported polymer particles can also preferably be washed with an aqueous propylene glycol solution, for example as a 10% by weight solution, and optionally dried thereafter.

[0337] Surprisingly, the organoleptic properties were not significantly affected by microencapsulation. In other words, the organoleptic properties of the loaded microcapsules corresponded to the organoleptic properties of the unencapsulated aroma chemicals to a large extent and did not change significantly over time.

[0338] The invention further provides a composition of microparticles obtainable by the process of the invention. The composition of the invention preferably contains a total amount of active organic chemicals of 1 to 98% by weight, in particular 5 to 96% by weight, especially 10 to 90% by weight, based on the total weight of the microparticles. The ingredients of the microparticles, i.e. the ingredients of the composition other than the solvent, are essentially the organic active substance, the wall material formed by the reaction of the shell-forming compounds (SFC1) and (SFC2) and any auxiliary agents (such as dispersants) used in the production of the microparticles and not removed. The composition of the invention can be in the form of a suspension or a powder, preferably a suspension being considered.

[0339] The invention further provides a product comprising the composition according to the invention.Preferred products come into consideration which comprise the composition according to the invention in a proportion of 0.01% to 80% by weight, based on the total weight of the product.

[0340] The properties of the product are naturally guided by the properties of the organic active substances. In the case of aroma chemicals, this may be a product typically comprising, for example, a perfume, a washing product, a cleaning product, a cosmetic product, a personal care product, a hygiene article, a food, a food supplement or a fragrance dispenser.

[0341] In the case of an agrochemical, it is typically an agrochemical formulation containing at least one agrochemical in the form of microparticles obtainable by the process of the invention, optionally one or more additional agrochemicals and suitable formulation adjuvants. Suitable agrochemical formulations include capsule suspensions and solid formulations, such as powders or granules.

[0342] In the case of a pharmaceutically active substance, this is typically a pharmaceutical formulation containing at least one pharmaceutically active substance in the form of microparticles obtainable by the process of the invention, optionally one or more further pharmaceutically active substances and suitable formulation auxiliaries.

[0343] The present invention further provides the use of the composition according to the invention in the above-mentioned products. Preferably, the use of the composition according to the invention in a product selected from the group consisting of perfumes, washing products, cleaning products, cosmetic products, personal care products, hygiene products, foods, food supplements, fragrance dispensers and perfumes is contemplated.

[0344] The compositions of the invention comprising perfume as aroma chemical can be used in the production of perfumed articles.The olfactory properties and also the physical properties and the non-toxicity of the compositions of the invention emphasize their particular suitability for the end uses mentioned.

[0345] The use of the composition has been found to be particularly advantageous in combination with the top notes of the composition, for example in perfume compositions containing dihydrorosan, rose oxide or other volatile fragrances such as isoamyl acetate, amyl acetate or methyl heptenone. In this case, the release of the important, much sought-after top notes is effectively delayed. The fragrance or aroma composition is accordingly metered in the necessary amount at the appropriate point. In the described mint compositions of L-menthol, DL-menthol, L-menthone and L-menthyl acetate, in addition to the aromatic effect, a cooling effect is additionally exerted in a targeted manner, for example in chewing gums, confectionery, cosmetic products and industrial applications, such as in textiles or superabsorbents. A further advantage is the high material compatibility of the composition according to the invention, even with reactive or relatively unstable components such as aldehydes, esters, pyrans / ethers, which may also exhibit secondary reactions on the surface.

[0346] The positive character facilitates the use of the compositions according to the invention, particularly preferably in perfume products, personal care products, hygiene articles, textile detergents and in cleaning products for solid surfaces.

[0347] The perfumed article is selected, for example, from perfume products, personal care products, hygiene products, textile detergents and cleaning products for solid surfaces. Preferred perfumed articles according to the invention are also selected from:

[0348] - perfume products chosen from perfume extracts, eau de parfums, eau de toilette, eau de colognes, eau de solide, extrait parfum, air fresheners in liquid form, in gel form or in a form applied to a solid carrier, aerosol sprays, scented cleansers and scented oils;

[0349] - personal care products selected from aftershaves, preshave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, self-tanning creams and lotions, hair care products, such as hair sprays, hair gels, hair setting lotions, hair conditioners, shampoos, permanent and semi-permanent hair colorants, hair setting compositions such as cold perms and hair smoothing compositions, hair tonics, hair creams and milks, deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, decorative cosmetic products, such as eye shadows, nail polishes, foundations, lipsticks, mascaras, toothpaste, dental floss;

[0350] - hygiene products selected from the group consisting of candles, lamp oils, incense sticks, propellants, rust removers, scented freshening wipes, underarm pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, handkerchiefs, dishwashing detergents, deodorants;

[0351] - cleaning products for solid surfaces chosen from perfumed acidic, alkaline and neutral cleaning products, such as floor cleaners, window cleaners, dishwashing detergents, bath and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes such as furniture polishes, floor waxes, shoe polishes, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, limescale removers, grill and oven cleaners, algae and moss removers, mildew removers, facade cleaners;

[0352] - a textile detergent selected from the group consisting of liquid detergents, powder detergents, laundry pretreaters (such as bleaches, soaking agents and stain removers), fabric softeners, detergent soaps, detergent tablets.

[0353] In a further aspect, the compositions of the invention are suitable for use in surfactant-containing perfumed preparations. This is because, in particular for the perfumery of surfactant-containing formulations such as cleaning products (particularly dishwashing compositions and multi-purpose cleaners) - odorants and / or odorant compositions having a rose top note and a pronounced naturalness are often sought.

[0354] In a further aspect, the composition of the present invention may be used as a product for providing (a) hair or (b) textile fibers with an attractive odor note.

[0355] Therefore, the compositions of the present invention have good suitability for use in surfactant-containing perfumed articles.

[0356] It is preferred if the perfumed preparation is one of the following:

[0357] - acidic, alkaline and neutral cleaning products, in particular selected from the group consisting of: all-purpose cleaners, floor cleaners, window cleaners, dishwashing detergents, bath and sanitary cleaners, scouring milks, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid detergents, powder detergents, laundry pretreatments such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants,

[0358] - air fresheners in liquid form, in gel form or in the form of an application to a solid carrier or as an aerosol spray,

[0359] a wax or polish, in particular selected from the group consisting of furniture polish, floor wax and shoe polish, or

[0360] - Personal care products, in particular chosen from the group consisting of shower gels and shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, such as, for example, skin creams and emulsions, face creams and emulsions, sunscreen creams and emulsions, after-sun creams and emulsions, hand creams and emulsions, foot creams and emulsions, depilatory creams and emulsions, aftershave creams and emulsions, self-tanning creams and emulsions, hair care products, such as, for example, hair sprays, hair gels, hair setting emulsions, hair conditioners, permanent and semi-permanent hair colorants, hair setting compositions such as cold perms and hair smoothing compositions, hair tonics, hair creams and milks, deodorants and antiperspirants, such as, for example, underarm sprays, roll-ons, deodorant sticks, deodorant balms, decorative cosmetic products.

[0361] Odorants Conventional ingredients with which the odorant composition of the invention is to be used according to the invention or with which it can be combined are common general knowledge and are described, for example, in WO 2016 / 050836, the teaching of which is hereby expressly incorporated by reference.

[0362] Likewise preferred is the use of the compositions according to the invention for the controlled release of active substances such as crop protection agents and pharmaceutical agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0363] Figure 1a and 1b are micrographs at 2 different magnifications of microparticles prepared by the protocol of Example 2. The micrographs were taken by scanning electron microscopy (SEM) as described below.

[0364] Examples

[0365] Material:

[0366] - Cyclohexane : exo-(±)-1-methyl-2-(2-methylbenzyloxy)-4-isopropyl-7-oxa-bicyclo[2.2.1]heptane;

[0367] - Defoamer 1 : Silicon SRE-PFL (Wacker Chemie AG);

[0368] -Defoamer 2: 1-octanol

[0369] - Hexyl Salicylate : 2-Hydroxybenzoic acid hexyl ester;

[0370] - Laponite :Synthetic phyllosilicate ( BYK-Chemie GmbH;

[0371] - Nile Red: 9-(Diethylamino)-5H-benzo[a]phenoxazin-5-one used as a lipophilic dye for fluorescence microscopy;

[0372] - PVA 1 : Polyvinyl alcohol, 88% hydrolyzed, M W : 13,000 to 23,000;

[0373] - PVA2 : Polyvinyl alcohol, 88% hydrolyzed, M W :Approximately 31,000( 4-88, Kuraray Corporation;

[0374] - PVP : Polyvinylpyrrolidone K 90 from BASF SE

[0375] - Water: double distilled water, unless otherwise specified;

[0376] Characterization of prepared microparticles

[0377] method

[0378] Microscopy and Particle Size Distribution

[0379] Scanning electron microscopy (SEM) was used to observe the morphology of the finished capsules. For this purpose, the obtained microparticle slurry was diluted with water (1:20 w / w) and coated onto a glass slide using a Polos spin 150i (2000 RPM, for 20 s) spin coater. The capsules were then sputter coated with a 5 nm thick platinum layer. The SEM images were recorded using a desktop Hitachi TM3030 microscope.

[0380] The particle size distribution of the capsules was measured by laser diffraction using a Malvern Mastersizer 2000 according to ISO 13320 EN: 2020-01. The data were processed according to the Mie-Theory by software using the "Generic Model" provided by Malvern Instruments. The important parameters are d n -value, d 10 d 50 and d 90 value, and D[3,2] value, which is the Sauter mean diameter. 50 Values ​​are based on the mean median of volume d 50 Particle size diameter, which is also referred to as D[v,50].

[0381] Measuring the release rate of active substances from microparticles

[0382] In order to determine the release rate, the following release scheme is followed. The microparticle slurry of 50mg obtained after the synthesis is added in a cylindrical dialysis tubing (diameter: 1cm, length: 2cm, molecular weight cut-off: 14kDa) together with 36% (v / v) 1-propanol aqueous solution of 2mL. The bag is dripped in 100mL of 36% (v / v) 1-propanol, and the whole solution is gently stirred (about 100RPM) on a magnetic stirrer at room temperature. External medium is circulated continuously through a calibrated UV-visible spectrophotometer (Cecil Instruments, Cambridge, Britain), and the concentration of the salicylic acid hexyl ester in the medium is recorded over time from the capsule. In order to calculate the percentage of oil release from the capsule, the microparticle slurry of 50mg is ultrasonically treated in 100mL 1-propanol for 1 hour, and then stirred overnight on an orbital oscillator. Use identical spectrophotometer, record the concentration of the salicylic acid hexyl ester extracted into the 1-propanol. This represents the maximum concentration of hexyl salicylate present in the slurry. Using this value as the denominator, the percentage of hexyl salicylate released from the capsules was calculated.

[0383] As a control experiment, in order to realize the resistance to release provided by the microcapsule shell, the same experiment was repeated by adding pure hexyl salicylate to the dialysis tubing instead of capsules, and the leakage rate of the unencapsulated oil was recorded for comparison.

[0384] Microparticle preparation

[0385] Example 1:

[0386] To prepare the aqueous phase, 1.2 g of Laponite was dispersed in 140 g of water in a 250 mL beaker using an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine. The dispersion was stirred at 1000 rpm for 20 min until a clear aqueous solution was obtained. Then, 2.59 g of a 3.5 wt % aqueous solution of sodium chloride, 7.5 g of a 10 wt % aqueous solution of PVA 1 and 2 drops of defoamer 2 were added, and the entire solution was placed in an ultrasonic bath for 5 min.

[0387] An oil phase was prepared by mixing 21.25 g of hexyl salicylate with 3.75 g of cyclohexyl isocyanate and 2 mg of Nile red dye.

[0388] The aqueous phase is transferred to a jacketed reactor equipped with four baffles placed diametrically opposite to each other. Water is circulated externally in the reactor for temperature control using a water bath (Julabo Me v.2). A temperature of 10°C is maintained throughout. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5min at 8000RPM using silverson L4RT (rotor-stator dispersion tool). After emulsification, silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 1000RPM. Then, using a syringe pump, 2.16g of 1,8-diaminooctane dissolved in 20g of water is added to the emulsion over 60min. After addition, the stirring speed is reduced to 600RPM and maintained for 18h.

[0389] Overall, 198 g of a homogeneous dispersion of spherical and monodisperse microcapsules (D[3,2]=1.5 μm) having an organic crystalline shell were obtained.

[0390] Example 2:

[0391] To prepare the aqueous phase, 1.2 g of Laponite was dispersed in 140 g of water in a 250 mL beaker using an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine. The dispersion was stirred at 1000 rpm for 20 min until a clear aqueous solution was obtained. Then, 2.59 g of a 3.5 wt % aqueous solution of sodium chloride, 7.5 g of a 10 wt % aqueous solution of PVA 1 and 2 drops of defoamer 2 were added, and the entire solution was placed in an ultrasonic bath for 5 min.

[0392] An oil phase was prepared by mixing 21.25 g of cyproconazole with 3.75 g of cyclohexyl isocyanate and 2 mg of Nile red dye.

[0393] The aqueous phase is transferred to a jacketed reactor equipped with four baffles placed diametrically opposite to each other. Water is circulated externally in the reactor for temperature control using a water bath (Julabo Me v.2). The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 8000RPM using a Silverson L4RT (rotor-stator dispersion tool) with a temperature maintained at 10°C. After emulsification, silverson is replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 1000RPM. Then, using a syringe pump, 2.16g of 1,8-diaminooctane dissolved in 20g of water is added to the emulsion over 60min. After addition, the stirring speed is reduced to 600RPM, and the temperature is raised to 20°C. These conditions are maintained for 18h.

[0394] Overall, 198 g of a homogeneous dispersion of spherical and monodisperse microcapsules (D[3,2]=4 μm) having an organic crystalline shell were obtained.

[0395] D[v,10]=2.6μm, D[v,50]=5.7μm, D[v,90]=14.8μm

[0396] Example 3

[0397] To prepare the aqueous phase, 1.2 g of Laponite was dispersed in 140 g of water in a 250 mL beaker using an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine. The dispersion was stirred at 1000 rpm for 20 min until a clear aqueous solution was obtained. Then, 2.59 g of a 3.5 wt % aqueous solution of sodium chloride, 7.5 g of a 10 wt % aqueous solution of PVA1 and 2 drops of defoamer 2 were added, and the entire solution was placed in an ultrasonic bath for 5 min.

[0398] An oil phase was prepared by mixing 18.75 g of hexyl salicylate with 6.25 g of cyclohexyl isocyanate and 2 mg of Nile red dye.

[0399] The aqueous phase is transferred to a jacketed reactor equipped with four baffles placed diametrically opposite to each other. Water is circulated externally in the reactor for temperature control using a water bath (Julabo Me v.2). The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 8000RPM using Silverson L4RT (rotor-stator dispersion tool). During emulsification, a temperature of 10°C is maintained. After emulsification, silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 1000RPM. Then, using a syringe pump, 3.61g of 1,8-diaminooctane dissolved in 20g of water is added to the emulsion at 10°C over 60min. After addition, the stirring speed is reduced to 600RPM, and the temperature is raised to 20°C for 18h.

[0400] Overall, 198 g of a homogeneous dispersion of spherical and monodisperse microcapsules (D[3,2]=2.3 μm) having an organic crystalline shell were obtained.

[0401] Example 4:

[0402] The aqueous phase is prepared as follows. 142.5 g of water are introduced into a beaker. 1.2 g of Laponite are added while stirring using a silent crusher (rotor stator dispersion tool). The powder is dispersed at 7.000 rpm for 10 min. Then, 7.5 g of a 10 wt % aqueous solution of PVA 2 and 2 drops of defoamer 1 are added. The dispersion is placed in an ultrasonic bath (transonic speed 470 / H) for 5 min.

[0403] An oil phase was obtained by mixing 21.25 g of dibutyl adipate and 3.75 g of cyclohexyl isocyanate.

[0404] The emulsion was generated by using a Silverson L5M-A (rotor stator dispersion tool).The oil phase was added to the water phase and homogenized at 10,000 rpm for 7 min.

[0405] The emulsion was then transferred to a glass reactor equipped with an anchor stirrer. The medium was cooled to 10°C with stirring at 300 rpm. When the temperature was reached, a solution consisting of 2.16 g of 1,8-diaminooctane and 20 g of water was added over 60 minutes using a syringe pump. Stirring and temperature were maintained during the addition and for another 4 hours. Afterwards, the bath was removed, the temperature was slowly raised to room temperature, 23°C, and stirring was maintained for another 15 hours.

[0406] Overall, 198 g of a homogeneous dispersion of approximately spherical and monodisperse microcapsules (D[3,2]=11.9 μm) having an organic crystalline shell were obtained.

[0407] Example 5

[0408] The aqueous phase is prepared as follows. 140 g of water is introduced into a beaker. While stirring using a silent crusher (rotor stator dispersion tool), 1.2 g of Laponite is added. The powder is dispersed at 7.000 rpm for 10 min. Then, 2.59 g of a 3.5 wt % aqueous solution of sodium chloride, 7.5 g of a 10 wt % aqueous solution of PVA 2 and 2 drops of defoamer 1 are added. The dispersion is placed in an ultrasonic bath (transonic 470 / H) for 5 min.

[0409] An oil phase was obtained by mixing 21.25 g of dibutyl adipate and 3.75 g of cyclohexyl isocyanate.

[0410] The emulsion was generated by using a Silverson L5M-A (rotor stator dispersion tool).The oil phase was added to the water phase and homogenized at 8,000 rpm for 7 min.

[0411] The emulsion was then transferred to a glass reactor equipped with an anchor stirrer. The medium was cooled to 10°C with stirring at 300 rpm. When the temperature was reached, a solution consisting of 2.16 g of 1,8-diaminooctane and 20 g of water was added over 60 minutes using a syringe pump. Stirring and temperature were maintained during the addition and for another 4 hours. Afterwards, the bath was removed, the temperature was slowly raised to room temperature, 23°C, and stirring was maintained for another 15 hours.

[0412] Overall, 198 g of a homogeneous dispersion of approximately spherical and monodisperse microcapsules (D[3,2]=5.9 μm) having an organic crystalline shell were obtained.

[0413] Example 6:

[0414] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0415] An oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate.

[0416] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000 RPM using Silverson L4RT (rotor-stator dispersion tool). The temperature is maintained at 10 ° C. After emulsification, Silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180 RPM. Then, through 9 min, 1.24 g 1,6-hexanediamine dissolved in 10 g water is added dropwise to the emulsion. After addition, stirring and temperature are maintained for another 18 h.

[0417] Overall, 98 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=9 μm) having an organic crystalline shell were obtained.

[0418] Example 7:

[0419] To prepare the aqueous phase, 3 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0420] An oil phase was prepared by mixing 8 g of hexyl salicylate and 2 g of cyclohexyl isocyanate.

[0421] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12 ° C. After emulsification, Silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180RPM. Then, using a syringe pump, 1.38g 1,8-diaminooctane dissolved in 10g water is added dropwise to the emulsion over 15min. After addition, stirring and temperature are maintained for another 18h.

[0422] Overall, 100 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=6 μm) with an organic crystalline shell were obtained.

[0423] Example 8:

[0424] To prepare the aqueous phase, 3.6 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0425] To prepare the oil phase, 1.47 g of cyclohexyl isocyanate, 0.35 g of phenyl isocyanate and 10.3 g of hexyl salicylate were mixed together.

[0426] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12 ° C. After emulsification, Silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180RPM. Then, using a syringe pump, 1.38g 1,8-diaminooctane dissolved in 10g water is added dropwise to the emulsion over 15min. After addition, stirring and temperature are maintained for another 18h.

[0427] Overall, 108 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=5.8 μm) with an organic crystalline shell were obtained.

[0428] Example 9:

[0429] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA1 were mixed with 80 g of water.

[0430] An oil phase was prepared by mixing 11.33 g of hexyl salicylate, 2 g of cyclohexyl isocyanate and 2 mg of Nile red dye.

[0431] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12 ° C. After emulsification, Silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180RPM. Then, using a syringe pump, 1.35g 1,7-diaminoheptane dissolved in 10g water is added dropwise to the emulsion over 15min. After addition, stirring and temperature are maintained for another 18h.

[0432] Overall, 108 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=5.3 μm) with an organic crystalline shell were obtained.

[0433] Example 10:

[0434] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0435] An oil phase was prepared by mixing 11.33 g of hexyl salicylate, 2 g of cyclohexyl isocyanate and 2 mg of Nile red dye.

[0436] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12 ° C. After emulsification, Silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180RPM. Then, using a syringe pump, 1.48g 1,8-diaminooctane dissolved in 10g water is added dropwise to the emulsion over 15min. After addition, stirring and temperature are maintained for another 18h.

[0437] Overall, 108 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=5.2 μm) with an organic crystalline shell were obtained.

[0438] Example 11

[0439] To prepare the aqueous phase, 1.6 g of PVP were dissolved in 80 g of water.

[0440] An oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate.

[0441] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 20°C. After emulsification, silverson is replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180RPM. Then, through 5min, 1.48g 1,8-diaminooctane dissolved in 10g water is added dropwise to the emulsion. After addition, stirring and temperature are maintained for another 18h.

[0442] Overall, 100 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=4.3 μm) with an organic crystalline shell were obtained.

[0443] Example 12

[0444] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0445] An oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate.

[0446] The aqueous phase is transferred to the jacket reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12 ° C. After emulsification, silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 180RPM. Then, 0.92g 1,8-diaminooctane and 0.16g tris (2-amino-ethyl) amine are mixed together and dissolved in 10g water. Using a syringe pump, through 15min, the amine solution is added dropwise to the emulsion. After addition, stirring and temperature are maintained for another 18h.

[0447] Overall, 105 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=6 μm) with an organic crystalline shell were obtained.

[0448] Example 13

[0449] To prepare the aqueous phase, 0.64 g of Laponite was dispersed in 70 g of water in a 250 mL beaker using an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine. The dispersion was stirred at 1000 rpm for 20 min until a clear aqueous solution was obtained. Then, 4.0 g of a 10 wt % aqueous solution of PVA1 was added, and the entire solution was placed in an ultrasonic bath for 5 min.

[0450] An oil phase was prepared by mixing 11.33 g of hexyl salicylate with 2.0 g of toluene-2,4-diisocyanate.

[0451] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000 RPM using Silverson L4RT (rotor-stator dispersion tool). During emulsification, a temperature of 12 ° C is maintained. After emulsification, silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 400 RPM. Then, using a syringe pump, 2.27 g of cyclohexylamine dissolved in 20 g of water is added to the emulsion at 12 ° C over 15 min. After addition, the temperature is raised to 30 ° C, maintained for 18 h under stirring.

[0452] Overall, 77 g of a homogeneous dispersion of spherical and monodisperse microcapsules (D[3,2]=3.1 μm) having an organic crystalline shell were obtained.

[0453] Example 14

[0454] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0455] An oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of isophorone diisocyanate.

[0456] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12°C. After emulsification, silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 400RPM. Then, 2.27g of cyclohexylamine is dissolved in 10g water. Using a syringe pump, over 15min, the amine solution is added dropwise to the emulsion. After the addition is complete, the temperature is raised to 20°C, and stirring and temperature are maintained for another 18h.

[0457] Overall, 95.2 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=1.7 μm) having an organic crystalline shell were obtained.

[0458] Example 15

[0459] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0460] An oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of sebacoyl chloride.

[0461] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12°C. After emulsification, silverson is replaced by an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 400RPM. Then, 1.65g of cyclohexylamine is dissolved in 10g of water. Using a syringe pump, over 15min, the amine solution is added dropwise to the emulsion. After the addition is complete, the temperature is raised to 20°C, and stirring and temperature are maintained for another 18h.

[0462] Overall, 96 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=9.6 μm) with an organic crystalline shell were obtained.

[0463] Example 16

[0464] To prepare the aqueous phase, 4 g of a 10 wt % aqueous solution of PVA 1 were mixed with 80 g of water.

[0465] An oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate and 0.046 g of 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0466] The aqueous phase is transferred to a jacketed reactor. Water is circulated externally in the reactor using a water bath (Julabo Me v.2) for temperature control. The oil-in-water emulsion is generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 min at 5000RPM using SilversonL4RT (rotor-stator dispersion tool). The temperature is maintained at 12°C. After emulsification, silverson is replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion is stirred at 400RPM. Then, 1.18g of 1.6 hexanediol is dissolved in 10g water. Using a syringe pump, over 15min, the solution is added dropwise to the emulsion. After the addition is complete, the temperature is raised to 20°C, stirring and temperature are maintained for another 18h, and thereafter raised to 50°C and maintained for 2h.

[0467] Overall, 87 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=3.8 μm) with an organic crystalline shell were obtained.

[0468] Release rate

[0469] The slurries obtained in Examples 1 (with laponite) and 10 (without laponite) were examined using the method described above for determining the release rate. In order to achieve the resistance to release provided by the shell of the microparticles, the dissolution and leakage of the unencapsulated hexyl salicylate were also observed in comparison using the same method. It was found that the microparticles of Examples 1 and 10 prepared with PVA 1 or a combination of PVA 1 and Laponite 1 gave almost similar results, since in both cases only less than 20% of the hexyl salicylate was released after about 5 hours, while at this time point about 90% of the unencapsulated hexyl salicylate had already leaked out.

Claims

1. A method for producing microparticles comprising at least one organic active compound enclosed by a shell of organic wall material, the method comprising i. providing a water-immiscible liquid containing the organic active compound to be encapsulated and at least one first shell-forming compound (SFC1); ii. emulsifying the water-immiscible liquid obtained in step i. in an aqueous medium to obtain an oil-in-water emulsion of the water-immiscible liquid in the aqueous medium; iii. adding at least one second shell-forming compound (SFC2) to the aqueous medium before or during step ii. or adding it to the emulsion obtained in step ii., thereby obtaining an aqueous suspension of the microparticles; wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has per molecule 1, 2, 3, 4, 5 or 6 first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic anhydride groups, and the other shell-forming compound has per molecule 1, 2, 3, 4, 5 or 6 second reactive groups (RG2) selected from hydroxyl groups, thiol groups and primary amino groups, Wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group and the other shell-forming compound has 1, 2, 3, 4, 5 or 6 reactive groups.

2. The method of claim 1, wherein: The first shell-forming compound (SFC1) has 1, 2, 3, 4, 5 or 6 first reactive groups (RG1) per molecule and the second shell-forming compound (SFC2) has 1, 2, 3, 4, 5 or 6 second reactive groups (RG2) per molecule, with the proviso that either the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group and the other shell-forming compound has 1, 2, 3, 4, 5 or 6 reactive groups.

3. A method as claimed in any one of the preceding claims, wherein: i. the first reactive group (RG1) is an isocyanate group, and the second reactive group (RG2) is selected from a hydroxyl group, a thiol group and a primary amino group, and wherein RG2 is in particular an amino group or a combination of an amino group and a hydroxyl group; ii. The first reactive group (RG1) is selected from a carbonyl halide group and a carboxylic anhydride group, and the second reactive group (RG2) is a primary amino group.

4. The method of claim 3, wherein: The first shell forming compound (SFC1) is selected from the group consisting of: aliphatic monoisocyanates, alicyclic monoisocyanates and aromatic monoisocyanates, and wherein the second shell forming compound (SFC2) is selected from the group consisting of: aliphatic diamines, aliphatic triamines, aliphatic tetraamines, aliphatic pentamines, aliphatic hexamines, alicyclic diamines, alicyclic triamines, alicyclic tetraamines, alicyclic pentamines, alicyclic hexamines, aromatic diamines, aromatic triamines, aromatic tetraamines, aromatic pentamines and aromatic hexamines.

5. The method of claim 4, wherein: The second shell-forming compound (SFC2) is an aliphatic diamine or a combination of at least an aliphatic diamine and an aliphatic, alicyclic or aromatic triamine.

6. The method according to any one of the preceding claims, having at least one of the following features (a) to (d): (a) the organic active compound to be encapsulated is selected from agrochemicals, aromatic chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds (b) the water-immiscible liquid is a solution of the organic compound to be encapsulated and the first shell-forming compound; (c) the organic active compound to be encapsulated is a liquid immiscible with water at 25° C. and 1 bar; (d) The weight ratio of the shell forming compounds to the water-immiscible liquid is in the range of 1:1 to 1:

50.

7. The method of claim 6, wherein: The organic compound to be encapsulated is an aroma chemical or an agrochemical.

8. A method as claimed in any one of the preceding claims, wherein: The emulsification step ii. is carried out in the presence of at least one dispersant, in particular chosen from the group consisting of polysaccharides, polyvinyl alcohol, polymers carrying sulfonate groups, polymers carrying carboxylate groups, polyvinylpyrrolidone copolymers of vinylpyrrolidone and inorganic Pickering stabilizers.

9. The method of claim 8, wherein: The dispersant contains at least phyllosilicate.

10. A method as claimed in any one of the preceding claims, wherein: Emulsification involves mixing the solution of step i. with water and homogenizing the mixture.

11. Microparticles comprising at least one organic active compound enclosed by a shell of an organic wall material formed by the reaction of at least one first shell-forming compound (SFC1) with at least one second shell-forming compound (SFC2), wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has, per molecule, 1 to 6 first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic anhydride groups, and the other shell-forming compound has, per molecule, 1 to 6 second reactive groups (RG2) selected from primary amino groups and thiol groups, Wherein the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has only one reactive group and the other shell-forming compound has 1, 2, 3, 4, 5 or 6 reactive groups.

12. The microparticle according to claim 11, wherein The first reactive group (RG1) is an isocyanate group or an isothiocyanate group, and the second reactive group (RG2) is a primary amino group.

13. Microparticles according to any one of claims 11 or 12, having an average particle size D[3,2] (Sauter mean diameter) in the range of 0.3 to 300 μm.

14. The microparticle according to any one of claims 11 to 13, wherein The encapsulated organic compound is selected from agrochemicals, aromachemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds.

15. Microparticles according to any one of claims 11 to 14, comprising particles of an inorganic Pickering system.

16. A product comprising microparticles as defined in any one of claims 11 to 15 in a proportion of 0.1% to 80% by weight, based on the total weight of the product.

17. Use of microparticles containing encapsulated aroma chemicals as claimed in any one of claims 11 to 15 as an additive for imparting fragrance or flavor to a product selected from perfumes, washing and cleaning products, cosmetic products, personal care products, hygiene products, foods, food supplements, fragrance dispensers and perfumes.

18. Use of microparticles as claimed in any one of claims 11 to 15 for the controlled release of the organic active compound.

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