Microparticle manufacturing process

Abstract

The present invention provides a process for producing microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material, comprising: i. providing a water-immiscible liquid containing an organic active compound to be encapsulated and at least a 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 before or during step ii. or to the emulsion obtained in step ii., thereby obtaining an aqueous suspension of microparticles; wherein either 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) per molecule selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic acid anhydride groups, and the other shell-forming compound 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) per molecule selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic acid anhydride groups. has 6, in particular 1, 2, 3 or 4, in particular 1, 2 or 3, second reactive groups (RG2) selected from hydroxyl groups, thiol groups and primary amino groups, and 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, in particular 1, 2, 3 or 4, in particular 1, 2 or 3 reactive groups. The present invention also relates to microparticles obtainable by this process and their uses.

Description

[Technical Field]

[0001] The present invention relates to a process 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. Also claimed are microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material, wherein the wall material is a urea or amide compound obtained by combining two different reactive shell-forming materials. [Background technology]

[0002] Microcapsules have a variety of uses, such as carriers for active substances such as crop protection agents, pharmaceuticals, fragrances, aromas, and as carriers for reactive substances or catalysts for industrial applications. They typically comprise a polymeric material that encases the material to be encapsulated. The advantages of this type of formulation are, inter alia: - Protection of reactive active substances from environmental influences; - safe and practical handling of toxic or unstable active substances; - Sustained release of active substances; - Prevention of premature mixing of substances; - Handling of solid and repetitive liquid active substances.

[0003] For an overview of methods for microencapsulation of active substances, see H. Mollet, A. Grubenmann, "Formulation Technology", chapter 6.4 (Microencapsulation), pages 234-246, Wiley VCH Verlag GmbH, Weinheim 2001, and the references cited therein.

[0004] In many agricultural products and cosmetics, it is desirable for aroma chemicals and pesticide actives to be released gradually over time. For example, in the case of perfume materials, the "fresh feeling" experienced by the consumer is due to the more volatile perfume ingredients. In the case of pesticides, it is often desirable to slow the release of the respective active to achieve a sustained effect, reduce volatility, and / or reduce adverse environmental or acute toxic effects. Therefore, it is desirable for these materials to be released slowly in a controlled manner.

[0005] One approach frequently used for the sustained release of each active substance is microencapsulation. Typically, these microcapsules contain a hydrophobic liquid core containing the respective active substance surrounded by a synthetic polymer shell. Such polymers can be, for example, polyurethane, polyurea, polyamide, polyester, polycarbonate, urea / formaldehyde resin, melamine / formaldehyde resin, polystyrene, or acrylate polymer. The microparticles are typically prepared by interfacial polymerization of the respective monomers or oligomers that form the polymer shell in an oil-in-water (o / w) emulsion of the respective hydrophobic liquid.

[0006] Methods for encapsulating organic liquids containing aroma chemicals with urea / formaldehyde resins or melamine formaldehyde resins are described, for example, in WO 2008 / 066773 and WO 2009 / 090169 and the references cited therein.

[0007] Methods for encapsulating organic liquids containing pesticides by in situ formation of polyureas or polyurethanes are described, for example, in U.S. Pat. No. 5,705,174, U.S. Pat. No. 5,910,314, WO 94 / 13139, WO 2015 / 165834 and WO 2018 / 130588.

[0008] The synthetic polymers of the microcapsules persist in the environment as microplastics and are therefore ecologically harmful (see, for example, C.M. Rochmann, "The global odyssee of plastic pollution," Science 368 (2020) pp. 1184-1185). Therefore, the use of synthetic polymer microcapsules is increasingly raising ecological concerns among customers and regulatory authorities. Therefore, there is a need to provide delivery forms of organic active substances that can be produced without or with reduced amounts of non-degradable plastic materials.

[0009] WO 2018 / 065481 and WO 2019 / 193094 disclose processes for preparing microparticles loaded with organic compounds, such as aroma chemicals. The processes include producing porous microparticles made of a thermoplastic biodegradable polyester material and suspending the microparticles in a liquid aroma chemical or a solution of aroma chemicals. The porous microparticles are produced by providing a w / o emulsion of a polyester material dissolved in a water-immiscible solvent 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. To achieve sustained release, the aroma chemical-loaded microparticles must be closed or sealed, which is achieved by heating the loaded microparticles for a long period of time, which may result in degradation of the active substance and undesirable aggregation or even destruction of the loaded microparticles. Furthermore, the release characteristics are not always satisfactory. Furthermore, several steps must be performed.

[0010] The aforementioned methods for producing aromachemical-loaded microparticles still require or contain polymeric materials that may ultimately decompose or degrade incompletely over a very long period of time, thus contributing to microplastics in the environment. Apart from that, their production is laborious, requiring either prolonged heating of the loaded microparticles or the presence of a coating or matrix that may be harmful to the microparticles and / or aromachemicals. Furthermore, production typically requires large amounts of chlorinated hydrocarbon solvents. Also, the preparation of such particles is carried out in separate steps, one of which is the preparation of hollow microparticles, followed by filling with the desired material and prolonged heating to prevent the material from prematurely escaping. Therefore, a separate process is needed to simplify the production process.

[0011] The self-assembly of organic diamide diacids in an aqueous phase to form hollow microparticles has been reported in R.J. Bergeron et al., Bioorganic & Medicinal Chemistry, Vol. 5, 11 (1997), pp. 2049-2061 and O. Phanstiel et al., Chem Mater. 2001, 13, 264-272. Self-assembly is achieved by lowering the pH of an alkaline aqueous solution of the diacid. This process results in a suspension of microparticles that encapsulate the aqueous phase. Therefore, it is not suitable for encapsulating organic active substances, especially those that are poorly soluble or insoluble in water.

[0012] S.R. Wilson-Withford et al., ACS Appl. Mater. Interfaces 2021, 13, 4, 5887-5894, describe the preparation of microcapsules by crystallization of a diurethane component 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, resulting in the formation of DBCC within 3 hours. DBCC is then dissolved in a 9:1 mixture of dichloromethane and decane at a concentration of 0.1 wt%. The solution is then injected into an aqueous phase, and the dichloromethane is evaporated, forming an aqueous suspension of microcapsules containing decane within the capsule shell formed by the crystallized DBCC. This method is tedious and requires large amounts of chlorinated hydrocarbons, which must be evaporated. Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, the object of the present invention is to provide a simple and easy process for preparing microparticles loaded with at least one organic chemical, which does not require the presence of a polymer matrix or coating. The microparticles should have a relatively low surface porosity to induce sustained release. The loaded microparticles can be produced in high yields by a simple process, but without significant aggregation or even destruction of the loaded microparticles. [Means for solving the problem]

[0014] Surprisingly, it has now been found that these and further objects are achieved by the process described below and the organic chemical-loaded microparticles obtainable thereby.

[0015] The present invention therefore provides a process for the production of microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material, comprising: i. providing a water-immiscible liquid containing an organic active compound to be encapsulated and at least a 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 before or during step ii. or to the emulsion obtained in step ii., thereby obtaining an aqueous suspension of microparticles; wherein either 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, in particular 1, 2 or 3, first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic acid 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, in particular 1, 2 or 3, second reactive groups (RG2) selected from hydroxyl groups, thiol groups and primary amino groups; The present invention relates to a process in which 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, particularly 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups.

[0016] This results in microparticles in which the shell of the organic wall material is formed by the reaction of at least one first shell-forming compound (SFC1) with at least one second shell-forming compound (SFC2). In other words, the wall material of the microparticles obtained by the process according to the invention consists essentially of the reaction product of at least one first shell-forming compound (SFC1) with at least one second shell-forming compound (SFC2). In this context, the term "essentially" is clearly understood to mean that the portion of the organic wall material formed by the reaction of the first and second shell-forming compounds amounts to at least 90% by weight, based on the total weight of organic matter in the wall material.

[0017] The microparticles obtainable by this process are novel and have particularly advantageous properties when the wall material is formed by a urea compound, an amide compound, a thiourethane compound, or a thiourea compound. When the functional group RG2 is a primary amino group or a thiol group, such wall material is formed in step iii). The microparticles obtainable by this process are particularly preferred when the wall material is formed by a urea compound, which is available when the functional group (RG1) is an isocyanate group and the functional group (RG2) is a primary amino group.

[0018] The present invention therefore also provides microparticles comprising at least one organic compound encapsulated by a shell of organic wall material formed by reaction of a first shell-forming compound (SFC1) with a second shell-forming compound (SFC2), either 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, in particular 1, 2 or 3, first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic acid 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, in particular 1, 2 or 3, second reactive groups (RG2) selected from primary amino groups and thiol groups, The present invention relates to a process in which 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, particularly 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups.

[0019] The present invention relates in particular to microparticles comprising at least one organic compound encapsulated by a shell of 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 invention, either 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, in particular 1, 2 or 3, first reactive groups (RG1) selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups and carboxylic acid 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, in particular 1, 2 or 3, second reactive groups (RG2) which are primary amino groups or thiol groups; The present invention relates to microparticles in which 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 2, 3, 4, 5 or 6, particularly 2, 3 or 4, especially 2 or 3 reactive groups.

[0020] The present invention has several advantages: The process of the present invention produces microparticles loaded with organic active compounds that allow for sustained release of the organic active compound by burst release triggered by mechanical pressure, diffusion or degradation of the biodegradable membrane, which results in a desired sustained release effect for certain applications. - At least one of the shell-forming materials has only one reactive functional group, and therefore no polymeric material is formed in this process, so the wall material of the microparticles obtainable by this process is a non-polymeric material of low and defined molecular weight. - The process of the present invention is much simpler, easier and less problematic than comparable processes which require separate steps to produce hollow particles, then to load the microparticles with aroma chemicals and finally to seal the porous surfaces of the pores, for example by applying heat or a coating. In particular, the process of the present invention does not require volatile organic solvents, especially halogenated hydrocarbon solvents, for encapsulation of the organic active compounds. In particular, no evaporation step is required to trigger shell formation by self-assembly. Therefore, the process is easier to implement, does not pose health risks, does not require additional solvent recycling, and limits waste management. By the process of the present invention, the surface porosity of the organic active compound-loaded microparticles is significantly reduced without causing significant destruction or agglomeration of the loaded microparticles due to prolonged exposure to heat. The reduced surface porosity of the loaded microparticles allows them to be stored for extended periods without significant loss of the organic active compound, which is particularly important in the case of sensitive active substances and / or volatile organic active substances.

[0021] The present invention also relates to the use of the microparticles described herein comprising encapsulated aroma chemicals as additives to impart scent or flavor to products selected from, for example, perfumes, laundry and cleaning products, cosmetics, personal care products, hygiene products, foods, food supplements, fragrance dispensers, and fragrances.

[0022] The present invention also relates to the use of the microparticles described herein for the controlled release of organic active compounds. In particular, the present invention relates to the use of the microparticles described herein containing encapsulated aromachemicals or pesticides for the controlled release of aromachemicals or pesticides, respectively.

[0023] Throughout this specification and application, the terms "organic active compound," "organic active substance," and "active compound" are used interchangeably. These terms are understood by those skilled in the art to mean organic chemical compounds that cause physiological effects in living organisms and plants, as well as substances that cause chemical effects or catalyze chemical reactions in the inanimate world. Examples of active substances are aroma chemicals, organic crop protection agents, organic pharmaceuticals, organic cosmetic active substances, and organic active substances for use in the construction sector, referred to as construction chemicals, in particular catalysts for products in the construction sector, such as crosslinking catalysts or polymerization catalysts. The term "organic active substance" also includes "metal-organic active substances."

[0024] The term "volatile organic active substance" refers to an organic or organometallic compound having a boiling 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.

[0025] In this specification and below, the term "water-immiscible" refers to a material having a solubility in deionized water of at most 5 g / L, in particular at most 1 g / L, at 20° C. and 1 bar. The solubility of a water-immiscible material in deionized water under the conditions given herein may be zero, i.e., below the detection limit.

[0026] The term liquid refers to a material that is in a liquid state at ambient conditions, i.e. a non-solid and non-gaseous material. In the context of the present invention, a liquid material preferably has a dynamic viscosity in the range of 0.2 to 2000 mPas, in particular in the range of 0.5 to 1000 mPas, at 20°C. Here and throughout this specification, ambient conditions refer to a temperature in the range of 20 to 25°C and atmospheric pressure, i.e. about 1 bar.

[0027] The term "low molecular weight organic active compound" generally refers to an organic or organometallic chemically active compound having a defined molecular weight Mn of less than 1000 daltons, typically in the range of 80 to 1000 daltons, and particularly in the range of 100 to 500 daltons. The molecular weight can be determined by mass spectrometry.

[0028] The term "sensitive active" refers to organic active compounds that are not stable to their environmental conditions and are damaged or degraded, for example, due to the pH of their environment or by oxidation.

[0029] In relation to the shell-forming compounds (SFC1) and (SFC2), those skilled in the art will clearly understand that the term "isocyanate group" means a functional group of formula -N=C=O. The term "isothiocyanate group" refers to a functional group of formula -N=C=S. The term "carbonyl halide group" refers to a group of formula -C(=O)-X, where X is a halogen, in particular chlorine or bromine, which may also be called carboxylic acid halide groups. The term carboxylic acid anhydride group refers to a group of formula -C(=O)-OC(=O)-R, where R is hydrogen or a hydrocarbon group preferably having 1 to 6 carbon atoms, such as C1-C6 alkyl or phenyl. The term "primary amino group" is clearly understood to mean a functional group of formula -NH2. The term "hydroxyl group" is clearly understood to mean a functional group of formula -OH. The term "thiol group" is clearly understood to mean a functional group of formula -SH. The aforementioned functional groups are attached to carbon atoms of the shell-forming compounds (SFC1) and (SFC2), respectively.

[0030] Unless otherwise specified, the term "room temperature" refers to a temperature of 22°C.

[0031] According to the present invention, the shell-forming compound (SFC1) has either a reactive group (RG1), i.e., a group selected from an isocyanate group, an isothiocyanate group, a carbonyl halide group, a carboxylic anhydride group, or a reactive group (RG2), i.e., a hydroxyl group and / or a primary amino group and / or a thiol group, preferably a primary amino group or a combination of a primary amino group and a hydroxyl group, particularly preferably a primary amino group.

[0032] Consequently, if the shell-forming compound (SFC1) has 1, 2, 3, 4, 5 or 6, particularly 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG1) per molecule, then the shell-forming compound (SFC2) must have 1, 2, 3, 4, 5 or 6, particularly 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG2) per molecule, provided that while the other shell-forming compound has 1, 2, 3, 4, 5 or 6, particularly 1, 2, 3 or 4, especially 1, 2 or 3 complementary reactive groups per molecule, 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. Similarly, if the shell-forming compound (SFC1) has 1, 2, 3, 4, 5 or 6, particularly 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG2) per molecule, then the shell-forming compound (SFC2) must have 1, 2, 3, 4, 5 or 6, particularly 1, 2, 3 or 4, especially 1, 2 or 3 reactive groups (RG1) per molecule, provided that while the other shell-forming compound has 1, 2, 3, 4, 5 or 6, particularly 1, 2, 3 or 4, especially 1, 2 or 3 complementary reactive groups per molecule, the shell-forming compound (SFC1) has only one reactive group (RG2) per molecule, or the shell-forming compound (SFC2) has only one reactive group (RG1) per molecule.

[0033] Thus, the reactive groups present in the shell-forming compound (SFC2) have complementary reactivity to the reactive groups present in the shell-forming compound (SFC1). Complementary reactivity means that the reactive groups (RG1) and (RG2) can react with each other by forming a covalent bond between the reactive centers of the reactive groups (RG1) and (RG2). As a result, in step iii), the first shell-forming compound (SFC1) contained in the emulsified water-immiscible liquid reacts with the second shell-forming compound (SFC2) present in the aqueous phase of the oil-in-water emulsion at the surface of the oil-in-water emulsion droplets. This results in the formation of a wall material on the surface of the water-immiscible liquid droplets, which forms the shell of the microcapsule and thus encapsulates the water-immiscible liquid droplets containing the organic active compound.

[0034] It is immediately apparent that the process of the present invention requires the following: (a) if the second shell-forming compound (SCF2) added in step iii) has 1, 2, 3, 4, 5 or 6 reactive groups whose reactivity is complementary to the reactivity of the reactive groups of the first shell-forming compound (SFC1), then the first shell-forming compound (SFC1) contained in the water-immiscible liquid containing the organic active compound to be encapsulated has exactly one reactive group (RG1) or (RG2) per molecule (hereinafter group (a) of embodiments); or (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 whose reactivity is complementary to the reactivity of the reactive groups of the second shell-forming compound (SFC2), then the second shell-forming compound (SFC2) added in step iii has exactly one reactive group (RG1) or (RG2) per molecule (hereinafter group (b) of embodiments).

[0035] It is also clear that in group (a) of embodiments, the water-immiscible liquid containing the organic active compound to be encapsulated does not essentially contain shell-forming compounds having more than one reactive group (RG1) or (RG2) per molecule, while in group (b) of embodiments, shell-forming compounds having more than one reactive group (RG1) or (RG2) per molecule are not essentially 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, particularly 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) is at least 90% by weight, particularly at least 95% by weight, based on the total amount of shell-forming compounds contained in the water-immiscible liquid. Similarly, in group (b) of embodiments, the relative amount of shell-forming compounds (SFC2) having exactly one reactive group (RG1) or (RG2) is at least 90% by weight, in particular at least 95% by weight or 100% by weight, based on the total amount of shell-forming compounds added in step iii of the process of the present invention. Accordingly, in group (b) of embodiments, the relative amount of shell-forming compounds having two or more reactive groups (RG1) or (RG2) is at most 10% by weight, in particular at most 5% by weight, based on the total amount of shell-forming compounds added in step iii.

[0036] It is immediately clear that the process of the present invention will work if shell-forming compound (SFC1) is a mixture of different shell-forming compounds (SFC1) having the same reactivity, and / or if shell-forming compound (SFC2) is a mixture of different shell-forming compounds (SFC2) having the same reactivity. It is also clear from the foregoing that shell-forming compounds (SFC1) and (SFC2) must not have any reactive groups other than reactive groups (RG1) and (RG2).

[0037] Depending on the selected combination of complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2), the organic wall or shell material is: urea compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, especially 2 or 3 urea groups, i.e. -NH-C(=O)-NH- groups, - urethane compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, in particular 2 or 3 urethane compound groups, i.e. -NH-C(=O)-O- groups, thiourethane compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, especially 2 or 3 thiourethane groups, i.e. -NH-C(=O)-S- groups, thiourea compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, and in particular 2 or 3, thiourea groups, i.e. -NH-C(=S)-NH- groups, - amide compounds having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, carboxamide groups, in particular 2 or 3 carboxamide groups, i.e. -C(=O)-NH- groups.

[0038] 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 or shell material is formed by a urea compound, a thiourea compound, a urethane compound, a thiourethane 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 or shell material is formed by a urea compound, a thiourea compound, a urethane compound, a thiourethane compound or a carboxamide compound having two, three or four, preferably two or three, and in particular two, groups selected from urea groups, thiourea groups, urethane groups, thiourethane groups and carboxamide groups.

[0039] More preferably, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected so that the organic wall or shell material is formed by urea compounds and urethane compounds 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 and urethane groups. Most preferably, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected so that the organic wall or shell material is formed by urea compounds, in particular urea compounds having 2, 3 or 4, preferably 2 or 3, in particular 2, urea groups.

[0040] In these cases, the process is preferably carried out so that the first shell-forming compound (SFC1) has one reactive group (RG1) which is an isocyanate group, while 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 or hydroxyl groups, thereby obtaining microparticles in which the wall or shell material is formed by a compound having, respectively, 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4 urea or urethane groups, preferably 2 or 3 urea or urethane groups, in particular 2 urea or urethane groups.

[0041] To produce microparticles whose organic wall material is formed by a compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, carboxamide groups, preferably 2 or 3, in particular 2, carboxamide groups, the process is preferably carried out so that the first shell-forming compound (SFC1) has one reactive group (RG1) which is a carbonyl halide or carboxylic anhydride group, in particular a carbonyl chloride group, while 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, thereby obtaining microparticles whose organic wall or shell material is formed by a compound having 2, 3 or 4, in particular 2 or 3, carboxamide groups, respectively.

[0042] In another group of preferred embodiments, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected so that the organic wall or shell material, respectively, is formed by a thiourea compound, in particular a thiourea compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3, in particular 2 thiourea groups. In these cases, the process is preferably carried out so that the first shell-forming compound (SFC1) has one reactive group (RG1) which is an isothiocyanate group, while 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, thereby obtaining microparticles in which the organic wall or shell material is formed by a compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4 thiourea groups, preferably 2 or 3 thiourea groups, in particular 2 thiourea groups, respectively.

[0043] In a further group of preferred embodiments, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected so that the organic wall or shell material, respectively, is formed by a thiourethane compound, in particular a thiourethane compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4, preferably 2 or 3, in particular 2 thiourethane groups. In these cases, the process is preferably carried out so that the first shell-forming compound (SFC1) has one reactive group (RG1) which is an isocyanate group, while 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 thiol groups, thereby obtaining microparticles in which the organic wall or shell material is formed by a compound having 1, 2, 3, 4, 5 or 6, in particular 2, 3 or 4 thiourethane groups, preferably 2 or 3 thiourethane groups, in particular 2 thiourethane groups, respectively.

[0044] In particular, the complementary reactive groups of the shell-forming compounds (SFC1) and (SFC2) are selected so that the organic wall or shell material is formed by 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) that is an isocyanate group, while using a second shell-forming compound (SFC2) having two reactive groups (RG2) that are primary amino groups.

[0045] The shell-forming compounds (SFC1) and (SFC2) are generally low molecular weight compounds, typically having a molecular weight of 1000 g / mol or less, e.g., in the range of 60 to 500 g / mol, and particularly in the range of 80 to 400 g / mol. Because the number of reactive sites on each of the shell-forming compounds (SFC1) and (SFC2) is limited to a maximum of six, and at least one of the shell-forming compounds (SFC1) and (SFC2) has only one reactive group each, the resulting wall material is formed by compounds having a maximum molecular weight of 2000 g / mol, typically up to 1600 g / mol, with a maximum molecular weight in the range of 200 to 1600 g / mol, and particularly in the range of 200 to 1200 g / mol, being particularly preferred. The term "maximum" molecular weight herein refers to the molecular weight of no 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 the well-established method of high-performance liquid chromatography-mass spectrometry (HPLC-MS).

[0046] For the efficiency of the encapsulation process, it is advantageous for the first shell-forming compound to have 1, 2, 3, 4, 5 or 6, in particular 1, 2, 3 or 4, preferably 1, 2 or 3, more preferably 1 or 2, in particular 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 in particular 2, second reactive groups (RG2) per molecule, provided 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, in particular 1, 2, 3 or 4, preferably 1, 2 or 3, more preferably 1 or 2, and in particular 2, complementary reactive groups. In particular, the reactive groups (RG1) are isocyanate groups.

[0047] For the efficiency of the encapsulation process, it is particularly advantageous for the first shell-forming compound (SFC1) to have one first reactive group (RG1) per molecule, while the second shell-forming compound (SFC2) has one, two, three, four, five or six, in particular one, two, three or four, more in particular two or three, and especially two second reactive groups (RG2) per molecule. In this case, the first reactive groups (RG1) are in particular isocyanate groups.

[0048] 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 in particular 2 or 3, and especially 2, first reactive groups (RG1) per molecule, while 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.

[0049] Preferably, the combination of shell-forming compounds (SFC1) and (SFC2) is selected so that the reaction of shell-forming compound (SFC1) with shell-forming compound (SFC2) results in the formation of a urethane, urea or amide group.

[0050] Thus, a particular group of embodiments (1) relates to the process of 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 of embodiments (2) relates to the process of the invention wherein the first reactive group (RG1) is a carbonyl halide group or a carboxylic anhydride group and the second reactive group (RG2) is a primary amino group.

[0051] A further particular group of embodiments (3) relates to the process of 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.

[0052] Suitable combinations are shown in Table 1 below, where RG indicates the type of reactive group present in each of the shell-forming compounds (SFC1) and (SFC2), and n indicates the number of reactive groups (RG) present in each of the shell-forming compounds (SFC1) and (SFC2). Those skilled in the art will immediately understand that lines 1 to 8 of Table 1 relate to group (1) of embodiments, while the combinations given in lines 9 to 12 of Table 1 relate to group (2) of embodiments, and the combinations given in lines 13 to 18 of Table 1 relate to group (3) of embodiments.

[0053] [Table 1]

[0054] [Table 2]

[0055] Among the combinations shown in Table 1, the combinations shown in lines 1 to 4 and lines 9 and 10 are particularly preferred, and the combinations in lines 1 and 3 are more preferred.

[0056] Suitable shell-forming compounds having a reactive group (RG1) include, but are not limited to: - monoisocyanates from the group of aliphatic, cycloaliphatic, aromatic and araliphatic monoisocyanates; - diisocyanates from the groups of aliphatic, cycloaliphatic, aromatic and araliphatic diisocyanates; - triisocyanates from the groups of aliphatic, cycloaliphatic, aromatic and araliphatic triisocyanates; - monoacyl chlorides from the group of aliphatic monoacyl chlorides, alicyclic monoacyl chlorides, aromatic monoacyl chlorides and araliphatic monoacyl chlorides; - diacyl chlorides from the group of aliphatic diacyl chlorides, alicyclic bisacyl chlorides, aromatic bisacyl chlorides and araliphatic bisacyl chlorides; - monoisothiocyanates from the group of aliphatic monoisothiocyanates, cycloaliphatic monoisothiocyanates, aromatic monoisothiocyanates and araliphatic monoisothiocyanates; - diisothiocyanates from the group of aliphatic diisothiocyanates, cycloaliphatic diisothiocyanates, aromatic diisothiocyanates and araliphatic diisothiocyanates; and - Triisothiocyanates from the group of the aliphatic, cycloaliphatic, aromatic and araliphatic triisothiocyanates.

[0057] In the shell-forming compound having the reactive group (RG1), the isocyanate group, isothiocyanate group, and carbonyl chloride group are usually bonded to a carbon atom of an aliphatic, alicyclic, aromatic, or araliphatic group having 2 to 20 carbon atoms, and one, two, or three non-adjacent CH groups in the aliphatic or alicyclic group may be replaced by an oxygen atom or an N-methyl group, and one, two, or three non-adjacent CH groups in the aliphatic, alicyclic, aromatic, or araliphatic group may be replaced by N. Such groups include C1 to C 20 alkyl groups, C5-C optionally substituted with 1, 2, 3 or 4 C1-C4 alkyl groups 20 Examples include cycloalkyl groups, aryl groups such as a benzene group optionally substituted with one, two, three or four C1-C4 alkyl groups, phenylalkylbenzene groups optionally substituted with one, two, three or four C1-C4 alkyl groups, and diphenyl ether groups optionally substituted with one, two, three or four C1-C4 alkyl groups.

[0058] The prefix C is used herein and throughout this specification in connection with a compound or molecular moiety. n ~C m "C1 to C" respectively indicate the range of possible numbers of carbon atoms that a molecular moiety or compound may have.n The term "group" means a straight or branched chain saturated aliphatic group having 1 to n carbon atoms. n / C m The term "alkyl" refers to a mixture of two alkyl groups, one having n carbon atoms and the other having m carbon atoms.

[0059] For example, C1~C 20 The term alkyl refers to a group of linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, whereas the term C1-C4 alkyl refers to a group of linear or branched saturated hydrocarbon groups having 1 to 4 carbon atoms, and C5-C 20Alkyl refers to a straight-chain or branched saturated hydrocarbon group having 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-trimethylbutyl, 1,2-trimethylbutyl, 1,3-trimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylbutyl, 1,1,2-trimethylbutyl, 1,2-trimethylbutyl, 1,3-trimethylbutyl, 2,2-trimethylbutyl, 2,3-trimethylbutyl, 3,3-trimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethyl ... Examples of the methylpropyl group include 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, heneicosyldocosyl, and in the case of nonyl, examples thereof include isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyldocosyl, and mixtures of isomers thereof, particularly isononyl, isodecyl, and the like. Examples of C1-C4-alkyl are for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0060] As used herein, "C5-C 20 The term "cycloalkyl" refers to a saturated monocyclic or polycyclic, in particular a monocyclic, bicyclic or tricyclic (alicyclic) group that is unsubstituted or substituted by one, two, three or four C1-C4 alkyl groups, and 20The total number of carbon atoms in the cycloalkyl is 5 to 20, and the total number of ring 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 In "-cycloalkyl", one, two or three non-adjacent ring-forming CH groups may be replaced by oxygen atoms, and the remainder of the ring-forming atoms are carbon atoms. These groups are C3-C 20 -Also known as heterocycloalkyl, C3-C 20 The total number of carbon atoms in the -heterocycloalkyl ranges from 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, and the like. 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.

[0061] Aryl refers to phenyl, naphthyl and diphenyl optionally substituted with one, two, three or four C1-C4 alkyl groups.

[0062] Araliphatic groups, also called arylalkyl, refer to phenyl and naphthyl groups optionally substituted with one, two, three or four C1-C4 alkyl groups bearing further alkylene groups. Examples of arylalkyl include benzyl, phenethyl, phenylalkylbenzene groups and diphenylether groups, where the phenyl ring in the four groups mentioned is optionally substituted with one, two, three or four C1-C4 alkyl groups.

[0063] Examples of suitable monoisocyanates include C1-C 20 Alkyl isocyanates, such as methyl isocyanate, ethyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, C5 to C6 20 Included are cycloalkyl isocyanates such as cyclohexyl isocyanate, cycloheptyl isocyanate, and aryl isocyanates such as phenyl isocyanate and tolyl isocyanate.

[0064] 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-toluylene diisocyanate and isomeric mixtures thereof, and arylalkyl diisocyanates such as 2,4'- and 4,4'-diphenylmethane diisocyanate and mixtures thereof.

[0065] Examples of suitable triisocyanates include biureths and isocyanurates of the diisocyanates mentioned above.

[0066] Examples of suitable monoacyl chlorides include C1-C 20 Alkanoyl 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 to C6 20 Cycloalkanoyl chlorides such as cyclohexanoic acid chloride and aromatic carboxylic acid chlorides such as benzoyl chloride are included.

[0067] 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, brassylic acid dichloride, cyclohexanedioic acid dichloride, phthalic acid dichloride, and isophthalic acid dichloride.

[0068] Suitable shell-forming compounds having a reactive group (RG2) include, but are not limited to: a primary monoamine selected from the group consisting of aliphatic, cycloaliphatic and aromatic monoamines, - primary diamino compounds selected from the group consisting of aliphatic diamines, cycloaliphatic diamines and aromatic diamines; - primary triamino compounds selected from the group consisting of aliphatic triamines, cycloaliphatic triamines and aromatic triamines; - primary tetraamino compounds selected from the group consisting of aliphatic, cycloaliphatic and aromatic tetramines; - monoalcohols selected from the group consisting of aliphatic monoalcohols, cycloaliphatic monoalcohols and aromatic monoalcohols; - dialcohols selected from the group consisting of aliphatic diols, cycloaliphatic diols, aromatic diols and araliphatic diols; - trialcohols selected from the group consisting of aliphatic triols, cycloaliphatic triols, aromatic triols and araliphatic triols; - tetra-alcohols selected from the group consisting of aliphatic tetra-ols, cycloaliphatic tetra-ols, aromatic tetra-ols and araliphatic tetra-ols; - monothiols selected from the group consisting of aliphatic monothiols, cycloaliphatic monothiols and aromatic monothiols; - dithiols selected from the group consisting of aliphatic, cycloaliphatic, aromatic and araliphatic dithiols; - a trithiol selected from the group consisting of aliphatic trithiols, cycloaliphatic trithiols, aromatic trithiols and araliphatic trithiols; and a tetrathiol selected from the group consisting of aliphatic tetrathiols, alicyclic tetrathiols, aromatic tetrathiols and araliphatic tetrathiols.

[0069] In the aforementioned shell-forming compounds having a reactive group (RG2) of a primary amino group, the thiol group and hydroxyl group are usually bonded to a carbon atom of an aliphatic, alicyclic, or aromatic group having 2 to 20 carbon atoms, and one, two, or three non-adjacent CH2 groups in the aliphatic or alicyclic group may be replaced by an oxygen atom, and one, two, or three non-adjacent CH2 groups in the aliphatic, alicyclic, or aromatic group may be replaced by N. Such groups include C1 to C 20 alkyl groups, C5-C optionally substituted with 1, 2, 3 or 4 C1-C4 alkyl groups 20 Cycloalkyl groups, C6-C optionally substituted with 1, 2, 3 or 4 C1-C4 alkyl groups 20 Examples include bicycloalkyl groups, aryl groups such as a benzene group optionally substituted with one, two, three or four C1-C4 alkyl groups, a phenylalkylbenzene group optionally substituted with one, two, three or four C1-C4 alkyl groups, and a diphenyl ether group optionally substituted with one, two, three or four C1-C4 alkyl groups and a 1,3,5-triazine group.

[0070] Examples of suitable monoamines include C1-C 20Alkylamines, such as methylamine, ethylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, C5-C 20 Cycloalkylamines such as cyclohexylamine, cycloheptylamine, and arylamines such as phenylamine, benzylamine, phenethylamine, and tolylamine are included.

[0071] Examples of suitable diamines include diamino C2-C 20 Alkanes, 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, diamino-C5-C6 20 Cycloalkanes such as 1,2-, 1,3-, and 1,4-diaminocyclohexane and isophoronediamine, and arylamines such as o-, m-, and p-diaminobenzene and diamonotoluene isomers.

[0072] 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.

[0073] Examples of suitable tetraamines include N,N,N',N'-tetrakis(3-aminopropyl)-1,3-diaminopropane, N,N,N',N'-tetrakis-(2-aminoethyl)-1,3-diaminopropane, and tetraaminobenzene.

[0074] Examples of suitable monoalcohols include C1-C 20Alkanols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, n-hexanol, 2-hexanol, n-heptanol, n-octanol, isooctanol, 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.

[0075] Examples of suitable dialcohols include C2-C 20 Alkanediols such as 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tripropylene glycol, alicyclic 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.

[0076] Examples of suitable trialcohols include C3-C 20 Alkanetriols, such as glycerin, 2,2-bis(hydroxymethyl)-1-ethanol, 2,2-bis(hydroxymethyl)-1-propanol, 2,2-bis(hydroxymethyl)-1-butanol, triethanolamine, and tripronolamine, are mentioned.

[0077] Examples of suitable tetraalcohols include C3-C 20Alkanthraols, 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-diamino 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.

[0078] Examples of suitable monothiols include C1-C 20 Alkanethiols include, for example, thiomethanol, thioethanol, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, 2-thiobutanol, isobutyl mercaptan, tert-butanyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, n-hexyl mercaptan, 2-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, isooctyl mercaptan, and thiophenol.

[0079] Examples of suitable dithiols include C2-C 20 Alkanedithiols such as 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, alicyclic dithiols such as 1,2-, 1,3-, and 1,4-cyclohexanedithiol, aromatic dithiols such as benzenedithiol and biphenyl-4,4-dithiol.

[0080] In group (a.1) of preferred embodiments, the first shell-forming compound (SFC1) is selected from the group consisting of monoisocyanates, i.e. compounds having exactly one isocyanate group (NCO) per molecule, including aliphatic monoisocyanates, cycloaliphatic monoisocyanates and aromatic monoisocyanates, and the second shell-forming compound (SFC2) is selected from the group consisting of aliphatic diamines, aliphatic triamines, aliphatic tetramines, aliphatic pentamines, aliphatic hexamines, cycloaliphatic diamines, cycloaliphatic triamines, cycloaliphatic tetramines, cycloaliphatic pentamines, cycloaliphatic hexamines, aromatic diamines, aromatic triamines, aromatic tetramines, aromatic pentamines and aromatic hexamines. In this group of highly preferred 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, with aliphatic diamines, aliphatic triamines and aromatic triamines such as melamine (2,6,4-triamino-s-triazine) being particularly preferred.

[0081] In a particularly preferred group of embodiments (a.11), the first shell-forming compound (SFC1) is selected from the group consisting of aliphatic monoisocyanates, cycloaliphatic monoisocyanates and aromatic monoisocyanates, and 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, for example, selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane.

[0082] In a further group (b.1) of preferred embodiments, the first shell-forming compound (SFC1) is selected from the group consisting of isocyanates having at least two NCO groups per molecule, in particular 2, 3 or 4 NCO groups per molecule, and the second shell-forming compound (SFC2) is selected from the group consisting of aliphatic monoamines, cycloaliphatic monoamines and aromatic monoamines. In this group (b.1) of preferred embodiments, the isocyanates having at least two NCO groups are in particular aliphatic, aromatic or cycloaliphatic diisocyanates, in particular C2-C 20 Alkylene diisocyanates, such as hexamethylene diisocyanate, tetramethylene diisocyanate, 1,8-diisocyanatooctanoate, 1,10-diisocyanatodecane, C2-C 20 It may be a cycloalkylene diisocyanate such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, an aryl diisocyanate such as 2,4- and 2,6-toluylene diisocyanate and isomeric mixtures thereof, and an aryl alkyl diisocyanate such as 2,4'- and 4,4'-diphenylmethane diisocyanate and mixtures thereof.

[0083] 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 required 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, particularly 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.

[0084] The total amount of shell-forming compounds (SFC1) and (SFC2) is preferably selected so 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, in particular in the range of 1:1 to 1:10. The total amount of shell material in the final microcapsules is therefore often in the range of 2 to 50% by weight, in particular in the range of 4 to 40% by weight, in particular in the range of 5 to 40% by weight, based on the total weight of the final microcapsules, i.e. based on the total weight of the water-immiscible liquid and the shell material obtained from the reaction of shell-forming compounds (SFC1) and (SFC2).

[0085] In the process of the present invention, the organic active compound to be encapsulated and the first shell-forming compound (SFC1) are present in a water-immiscible liquid. Herein and hereinafter, the term "water-immiscible liquid" refers to a liquid having a solubility in deionized water at 20°C and 1 bar of at most 5 g / L, in particular at most 1 g / L. The miscibility of the water-immiscible liquid with deionized water under the conditions given herein may be zero, i.e., below the detection limit.

[0086] 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, especially 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 dissolved in each other or are in solution in a water-immiscible organic solvent.

[0087] The term "water-immiscible organic solvent" refers to an organic solvent having a solubility in deionized water of at most 5 g / L, in particular at most 1 g / L, at 20° C. and 1 bar. The miscibility of a water-immiscible organic solvent with deionized water under the conditions given herein may be zero, i.e., below the detection limit.

[0088] In particular, the water-immiscible liquid is a solution of the organic compound to be encapsulated, a first shell-forming compound (SFC1), and optionally one or more organic water-immiscible solvents.

[0089] Suitable water-immiscible organic solvents are in particular hydrocarbons, such as aliphatic and cycloaliphatic organic solvents and aromatic solvents and mixtures thereof, C2-C6 20 -Mono- or dicarboxylic acids and C1-C 10 Esters with alkanols having a total of at least 6 carbon atoms, such as butyl acetate, hexyl acetate, isononyl acetate, isopropyl myristate, C6-C 10 Alkanols, fatty acid amides having a total of at least 8 carbon atoms, such as dimethylhexanamide and dimethyloctanamide, and mixtures of the aforementioned organic solvents.

[0090] Preferably, the organic solvent has a boiling point of at least 100°C at 1 bar, for example in the range 100 to 350°C.

[0091] The organic active compound can be any active compound that is primarily liquid at 20°C and 1 bar or that 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 at least 1.5. ow =C o / C w It has.

[0092] 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.

[0093] 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 which case the organic active compound or mixture of two or more organic active compounds is provided as a solution in a water-immiscible compound.

[0094] The organic active compound may be a single compound or a mixture of compounds, for example, a mixture of two, three, or more active compounds.

[0095] The organic active compound is often a low molecular weight organic active compound or a mixture of low molecular weight organic active compounds.

[0096] The organic active compound typically does not have reactive groups that are reactive with the reactive groups (RG1) and (RG2).

[0097] The organic active compounds may be selected from pesticides, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds such as polymerization catalysts, dyes and UV filters.

[0098] In one group of preferred embodiments, the organic active is an aroma chemical, particularly 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, particularly having a water solubility of 100 mg or less in deionized water at 25° C. In another group of preferred embodiments, the organic active 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 mixture of two or more aroma chemicals is provided as a solution in a water-immiscible compound.

[0099] The term "aromachemical" is understood by those skilled in the art to mean organic compounds that can be used as "odors" and / or "flavorings." In the context of the present invention, "odorants" are understood to mean natural or synthetic substances with a specific odor. In the context of the present invention, "flavorings" are understood to mean natural or synthetic substances with a specific flavor. In the context of the present invention, "odor" or "olfactory perception" is the interpretation of sensory stimuli sent from the chemical receptors of the nose or other olfactory organs to the brain of an organism. Odors can be the result of nasal sensory perception of odorants generated during inhalation. In this case, air acts as an odorant carrier.

[0100] Preferred aroma chemicals for loading the microparticles are selected, for example, from the following compounds:

[0101] Alpha-hexyl cinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably with a cis isomer content of more 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, styrenyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-acetonaphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (ISO E Super 3 ), Hexyl Salicylate, 4-tert-Butylcyclohexyl (Oryclone 1 ), 2-tert-butylcyclohexyl acetate (Agrumex HC 1 ), alpha-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-alpha-methylionone, alpha-isomethylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral 3 ), alpha-amylcinnamaldehyde, ethylene brassylate, (E)- and / or (Z)-3-methylcyclopentadec-4-enone (Muscenone 9 ), 15-pentadec-11-enolide and / or 15-pentadec-12-enolide (Globalide 1 ), 15-cyclopentadecanolide (Macrolide 1 ), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)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-buten-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 (Claritone1 ), 2,6-dimethyl-5-hepten-1-al (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butanal (Florhydral 2 ), 2-methyl-2-3-(3,4-methylenedioxyphenyl)propanal (Helional 3 ), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon 1 ), tetrahydro-2-isobutyl-4-methyl-2H-pyran (Dihydrorosenon 4 ), 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-benzodioxepin-3(4H)-one (Calone 19515 ), 3,3,5-trimethylcyclohexyl acetate (preferably with 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 ), prenyl 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 aromas.

[0102] Therefore, in the context of the present invention, the aforementioned aromas or odorants are preferably combined with the mixtures of the present invention.

[0103] Where product names are identified above, please see below for sources: 1 Trade name of Symrise GmbH, Germany; 2 Trade name of Givaudan AG, Switzerland; 3 Trade name of International Flavors & Fragrances Inc.,USA; 4 Trade name of BASF SE; 5 Trade name of Danisco Seillans SA, France; 9 Trade name of Firmenich SA, Switzerland; 10 A trade name of PFW Aroma chemicals BV, the Netherlands.

[0104] More specifically, the advantages of the present invention are manifested in the case of aroma chemicals selected from volatile fragrances and aroma mixtures comprising at least one volatile fragrance. Volatile fragrances are understood to mean fragrances that have a high vapor pressure at room temperature. A fragrance is considered to be a volatile fragrance, especially if it has the following properties: when a drop of volatile fragrance is applied to a piece of paper and left to evaporate under ambient conditions at room temperature (22°C), its odor is no longer perceptible to an experienced perfumer two 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 (Dihydrorosan®), prenyl acetate (=3-methylbut-2-enyl acetate), isoamyl acetate, dihydromyrcenol (2,6-dimethyloct-7-en-2-ol) and methylheptenone (6-methylhept-5-en-2-one). When aroma mixtures containing at least one volatile fragrance are used for the loading, the proportion of volatile fragrance 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.

[0105] Further odorants or aroma chemicals that can be combined with the aforementioned odorants to obtain odorant compositions can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969, Author's Edition, or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Ed., Wiley-VCH, Weinheim 2001. Specific examples that may be mentioned include:

[0106] Extracts from natural sources, for example, essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, e.g., ambra tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; baco leaf oil; cabreuva oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassia absolute; cassia Cedar absolute; Cedar leaf oil; Cedarwood oil; Cistus 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 Blaucz absolute; Oakmoss absolute; Elemi oil; Estragon oil; Eucalyptus citriodora oil; Eucalyptus oil; Fennel oil; Spruce needle oil; Galbanum oil; Galbanum resin; Geranium oil; Grapefruit oil; Guaiakwood oil; Gurjan balsam; Gurjan Balsam oil; Helichrysum absolute; Helichrysum oil; Ginger oil; Iris root absolute; Iris root oil; Jasmine absolute; Calamus oil; Blue camellia oil; Roman camellia oil; Carrot seed oil; Cascarilla oil; Pine needle oil; Spearmint oil; Cumin oil; Labdanum oil; Labdanum absolute; Labdanum resin; Lavandin absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Pressed lime oil; Linalool oil; Litose acicularia oil; Laurel Lupin leaf oil; Muss oil; Marjoram oil; Mandarin oil; Muss soya 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; Olibanum absolute; Olibanum oil; Opopanax oil; Orange blossom oil; Orange oil; Oregano oil; Palmarosa oil; Patchouli oil; Perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; Allspice oil;Pine oil; Pauly oil; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Dalmatian sage oil; Spanish sage oil; Sandalwood oil; Celery seed oil; Spike lavender oil; Star anise oil; Styrax oil; Tagit oil; Fir needle oil; Tea tree oil; Turpentine oil; Thyme oil; Tolu balsam; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; Verbena oil; Vetiver oil; Juniper berry oil; Wine yeast oil; Vermouth oil; Wintergreen oil; Ylang ylang oil; Hyssop oil; Civet absolute; Cinnamon leaf oil; Cinnamon bark oil; and fractions or components isolated therefrom.

[0107] The individual odorants may be, for example: - hydrocarbons, for example, 3-carene, α-pinene, β-pinene, α-terpinene, γ-terpinene, p-cymene, bisabolene, camphene, caryophyllene, cedrene, farnesene, limonene, longifolene, myrcene, ocimene, valencene, (E,Z)-1,3,5-undecatriene, styrene, diphenylmethane; aliphatic alcohols, such as hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol, 4-methyl-3-decen-5-ol; aliphatic aldehydes and their acetals, such as 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; Enal, heptanal diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde, (E / Z)-1-(1-methoxypropoxy)-3-hexene; aliphatic ketones and their oximes, such as 2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime, 2,4,4,7-tetramethyl-6-octen-3-one, 6-methyl-5-hepten-2-one; sulfur-containing aliphatic compounds, such as 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3-mercaptohexyl butyrate, 3-acetylthiohexyl acetate, 1-menthen-8-thiol; aliphatic nitriles, such as 2-nonenenitrile, 2-undecenenitrile, 2-tridecenenitrile, 3,12-tridecadienonitrile, 3,7-dimethyl-2,6-octadienenitrile, 3,7-dimethyl-6-octenenitrile; Esters of aliphatic carboxylic acids, for example (E) and (Z)-3-hexenyl formate, ethyl acetoacetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethylhexyl acetate, 3-methyl-2-butenyl acetate, (E)-2-hexenyl acetate, (E) and (Z)-3-hexenyl acetate, octyl acetate, 3-octyl acetate, 1-octen-3-yl acetate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, (E) and (Z)-3-hexenyl isobutyrate, hexyl crotonate, ethyl isovalerate, ethyl 2-methylpentanoate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, allyl heptanoate, ethyl octanoate, (E / Z)-ethyl-2,4-decadienoate, Methyl 2-octinate, Methyl 2-noninate, Allyl 2-isoamyloxyacetate, Methyl-3,7-dimethyl-2,6-octadienoate, 4-methyl-2-pentylcrotonate acyclic terpene alcohols, such as 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, pentanoates, hexanoates, crotonates, tiglinates, and 3-methyl-2-butenoates; acyclic terpene aldehydes and ketones, such as geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranyl acetone, and also the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, such as menthol, isopulegol, α-terpi Neol, terpinol-4, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol; linalool oxide, nopol, cedrol, ambrinol, vetiverol, guajol and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, and 3-methyl-2-butenoates; cyclic terpene aldehydes and ketones, such as menthone, isomenthone, 8-mercaptomenthan-3-one, carvone, camphor, fenchone, α-ionone, β-ionone, α-n-methylionone, β-n-methylionone, α-isomethylionone, β-isomethylionone, α-irone, α-damascone, β-damascone, β-damascenone, δ-damascone, γ-damascone, 1-(2,4,4-trimethyl-2-cyclohexen-1-yl) -2-Buten-1-one, 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methano-naphthalen-8(5H)-one, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, nootkatone, dihydronootkatone, 4,6,8-megastigmatrien-3-one, α-sinensal, β-sinensal, acetylated cedarwood oil (methyl cedryl ketone); cyclic alcohols, such as 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3-isocamphylcyclohexanol, 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; - alicyclic alcohols, such as 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; - cyclic and alicyclic ethers, such as cineole, cedryl methyl 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; cyclic and macrocyclic ketones, such as 4-tert-butylcyclohexanone, 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-cyclopentadecenone, 3-methyl-5-cyclopentadecenone, 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-cyclohexadecen-1-one, 7-cyclohexadecen-1-one, (7 / 8)-cyclohexadecen-1-one, 9-cycloheptadecen-1-one, cyclopentadecanone, cyclohexadecanone; alicyclic aldehydes, such as 2,4-dimethyl-3-cyclohexenecarbaldehyde, 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; alicyclic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-one, 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone, methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone, tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone; Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, 2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclohexyl acetate, 3,3,5-trimethylcyclohexyl acetate, decahydro-2-naphthyl acetate, 2-cyclopentylcyclopentylcrotonate, 3-pentyltetrahydro-2H-pyran-4-yl acetate. , decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate, 4,7-methano-3a,4,5,-6,7,7a-hexahydro-5 or -6-indenyl acetate, 4,7-methano-3a,4,5,-6,7,7a-hexahydro-5 or -6 indenyl propionate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate, 4,7 methanooctahydro-5 or 6-indenyl acetate; - esters of alicyclic alcohols, for example, 1-cyclohexylethyl crotonate; esters of alicyclic carboxylic acids, for example, allyl 3-cyclohexylpropionate, allyl cyclohexyloxyacetate, cis- and trans-methyldihydrojasmonate, cis- and trans-methyljasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate, ethyl 2-methyl-1,3-dioxolane-2-acetate; - aromatic aliphatic alcohols, for example, benzyl alcohol; 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; - esters of aromatic aliphatic alcohols with aliphatic carboxylic acids, such as benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenylethyl acetate, α,α-dimethylphenylethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, 4-methoxybenzyl acetate; - aromatic aliphatic ethers, such as 2-phenylethyl methyl ether, 2-phenylethyl isoamyl ether, 2-phenylethyl 1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, hydratropaldehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxine, 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine; - aromatic and araliphatic aldehydes, such as benzaldehyde, phenylacetaldehyde, 3-phenylpropanal, hydratropaldehyde, 4-methylbenzaldehyde, 4-methylphenylacetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 2-methyl-3-(4-isopropylphenyl)propanal, 2-methyl-3-(4-tert-butylphenyl)propanal, 2-methyl-3-(4-isobutylphenyl)propanal, 3-(4-tert-butylphenyl)propanal; nal, cinnamaldehyde, α-butylcinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-hydroxy-3-methoxy-benzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 2-methyl-3-(4-methoxyphenyl)propanal, 2-methyl-3-(4-methylenedioxyphenyl)propanal; aromatic and araliphatic ketones, such as acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthalenyl)-ethanone, 2-benzofuranylethanone, (3-methyl-2-benzofuranyl)ethanone, benzophenone 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone, 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5 indenyl]ethanone, 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; aromatic and aliphatic carboxylic acids and their esters, such as benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenyl acetate, ethyl phenyl acetate, geranyl phenyl acetate, phenylethyl phenyl acetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isoamyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3-phenylglycidate, ethyl 3-methyl-3-phenylglycidate; nitrogen-containing aromatic compounds, such as 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-pentenonitrile, 3-methyl-5-phenylpentanonitrile, methyl anthranilate, methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline, 6-isobutylquinoline, 6-sec-butylquinoline, 2-(3-phenylpropyl)pyridine, indole, skatole, 2-methoxy-3-isopropylpyrazine, 2-isobutyl-3-methoxypyrazine; phenols, phenyl ethers and phenyl esters, for example estragole, anethole, eugenol, eugenyl methyl ether, isoeugenol, isoeugenyl methyl ether, thymol, carvacrol, diphenyl ether, β-naphthyl methyl ether, β-naphthyl ethyl ether, β-naphthyl isobutyl ether, 1,4-dimethoxybenzene, eugenyl acetate, 2-methoxy-4-methylphenol, 2-ethoxy-5-(1-propenyl)phenol, p-cresylphenyl acetate; heterocyclic compounds, such as 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; lactones, such as 1,4-octanolide, 3-methyl-1,4-octanolide, 1,4-nonanolide, 1,4-decanolide, 8-decen-1,4-olide, 1,4-undecanolide, 1,4-dodecanolide, 1,5-decanolide, 1,5-dodecanolide, 4-methyl-1,4-decanolide, 1,15-pentadecanolide, cis- and trans-11-pentadecanolide, cis- and trans- ans-12-pentadecen-1,15-olide, 1,16-hexadecanolide, 9-hexadecen-1,16-olide, 10-oxa-1,16-hexadecanolide, 11-oxa-1,16-hexadecanolide, 12-oxa-1,16-hexadecanolide, ethylene 1,12-dodecanedioate, ethylene 1,13-tridecanedioate, coumarin, 2,3-dihydrocoumarin, octahydrocoumarin.

[0108] Additionally, suitable aroma chemicals are macrocyclic carbaldehyde compounds such as those described in WO 2016 / 050836.

[0109] Particularly preferred are mixtures of L-menthol and / or DL-menthol, L-menthone, L-menthyl acetate, or L-isopulegol, which are highly desirable analogs or substitutes for what is known as synthetic dementholized oil (DMOS). Mixtures of these minty compositions are preferably used in weight ratios of 20-40% L-menthol or DL-menthol, 20-40% L-menthone, and 0-20% L-menthyl acetate, or in weight ratios of 20-40% L-menthone, 20-40% L-menthone, and 0-20% L-isopulegol.

[0110] The aforementioned aromas and aroma mixtures can be used by themselves or in solvents that are not themselves aromas. Typical solvents for aromas are, in particular, those that have a boiling point above 150°C at standard pressure and do not dissolve the wall material, such as diols, e.g., propanediol and dipropylene glycol, C8-C 22 Fatty acid C1~C 10 -Alkyl esters, e.g., isopropyl myristate, di-C6-C 10 alkyl esters, such as dicapryl ether (Cetiol® OE from BASF SE), di-C1-C6 alkyl esters of aliphatic, aromatic or cycloaliphatic di- or tricarboxylic acids 10 alkyl esters, such as dialkyl phthalates, for example dimethyl and diethyl phthalate, and mixtures thereof, dialkyl hexahydrophthalates, for example dimethyl cyclohexane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate and diisononyl 1,2-cyclohexanedicarboxylate, and dialkyl adipates, for example dibutyl adipate (for example Cetiol® B from BASF SE), C8-C 22 Fatty acid triglycerides, such as vegetable oils or cosmetic oils, for example octanoyl / decanoyl triglycerides (for example the commercial product Myritol® 318 from BASF SE), dimethyl sulfoxide and white oil.

[0111] In a further group of embodiments, the low molecular weight organic active substance is an active pharmaceutical ingredient, abbreviated as API. The active pharmaceutical ingredient is typically an active therapeutic ingredient, an active diagnostic ingredient, an active preventive ingredient, and corresponding combinations of active ingredients. The active pharmaceutical ingredient can be in an amorphous state, a crystalline state, or a mixture thereof. The active pharmaceutical ingredient can be labeled with a detectable label, such as a fluorescent label, a radioactive label, or an enzymatically or chromatographically detectable species, and can be used in combination with this label to load the microparticles.

[0112] The API may have a water solubility of greater than 10 mg / mL in deionized water at 25° C. It is also possible to use active pharmaceutical ingredients with low water solubility as the active substance, for example, those with a water solubility of less than 10 mg / mL in deionized water at 25° C. In any case, the API should have a partition coefficient between the water-immiscible liquid and the aqueous phase of at least 1.0, especially at least 2.0.

[0113] Preferred active therapeutic, diagnostic and prophylactic components are APIs suitable for parenteral administration. Representative examples of suitable APIs are the following categories and examples of APIs and alternative forms of these APIs, such as alternative salt forms, free acid forms, free base forms and hydrates: Analgesics / antipyretics; antiasthmatics; antibiotics; antidepressants; antidiabetics; anti-inflammatory drugs / inflammatory inhibitors; antihypertensives; inflammation inhibitors; antineoplastic drugs; antianxiety drugs; immunosuppressants; antimigraine drugs; sedatives / hypnotics; antianginal drugs; antipsychotics; antimanic drugs; antiarrhythmic drugs; antiarthritic drugs; antigout drugs; anticoagulants; thrombolytic drugs; antifibrinolytic drugs; blood purifying drugs (hemorheological drugs); antiplatelet drugs / platelet aggregation inhibitors; anticonvulsants; antiparkinsonian drugs; antihistamines / antipruritics; calcium regulators; antibacterial drugs; antiviral drugs; antimicrobial drugs; antiinfective drugs; bronchodilators; corticosteroids; steroid compounds and hormones; hypoglycemic drugs; hypoglycemic drugs; lipid-lowering drugs; proteins; nucleic acids; drugs useful in stimulating erythropoiesis; antiulcer drugs / antireflux drugs; antiemetic drugs / antimosis drugs; oil-soluble vitamins and other drugs.

[0114] Suitable active pharmaceutical ingredients are mentioned, for example, in WO 2007 / 070852, in particular pages 15 to 19. In addition, suitable active ingredients and drugs are listed in Martindale: The Extra Pharmacopoeia, 30th edition, The Pharmaceutical Press, London 1993.

[0115] In another group of embodiments, organic active substance is pesticide compound, that is, organic compound for crop protection, also called organic crop protection agent.The pesticide for encapsulating in microparticles is for example, in particular selected from the group consisting of fungicide, insecticide, nematicide, herbicide, pheromone, also safener and growth regulator, and it can be comprised as a single compound or as a mixture of different pesticide compounds, for example, a mixture of two or more herbicides, a mixture of two or more fungicides, a mixture of two or more insecticides, a mixture of insecticide and fungicide, a mixture of one or more herbicides and safener, and a mixture of one or more fungicides and safener.

[0116] Typically, pesticides are liquid or solid at 20°C and 1 bar and are usually non-volatile. The vapor pressure is typically less than 0.1 mbar, especially less than 0.01 mbar, at 20°C. Pesticides that are particularly suitable for inclusion in the microcapsules of the present invention are slightly water-soluble or even insoluble in water, especially having a water solubility of 5 g / L or less, especially 2 g / L or less, in deionized water at 25°C.

[0117] Pesticides are known to those skilled in the art, for example from The Pesticide Manual, 17th edition, The British Crop Protection Council, London, 2015. Suitable crop protection agents are in particular listed on pages 10 to 15 of WO 2018 / 019629.

[0118] Examples of suitable insecticides are carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogues, alkyl halides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, compounds from the METI acaricide class, and unclassified insecticides such as chlorpicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amithras, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or agriculturally acceptable salts and derivatives thereof.

[0119] Examples of suitable fungicides are dinitroaniline, allylamine, anilinopyrimidine, antibiotic fungicides, aromatic hydrocarbons, benzenesulfonamides, benzimidazole, benzisothiazole, benzophenone, benzothiadiazole, benzotriazine, benzyl carbamate, carbamate, carboxamide, carboxylic acid diamide, chloronitrile, cyanoacetamide oxime, cyanoimidazole, cyclopropanecarboxamide, dicarboximide, dihydrodioxazine, dinitrophenylcrotonate, dithiocarbamate, dithiolane, ethylphosphonate, ethylaminothiazolecarboxamide, guanidine, hydroxy-(2-amino)pyrimidine, hydroxyanilide, imidazole, imidazolinone, isobenzofuranone, methoxyacrylate, methoxycarbamate, mol Compounds from the classes of holins, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothioates, phthalamic acid, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles, and agriculturally acceptable salts and derivatives thereof.

[0120] Examples of suitable herbicides are acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridins, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanedione, dinitroanilines, dinitrophenols, diphenyl ethers, glycine, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinedione, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, Compounds from the classes of phosphinic acids, phosphoramidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas, and agriculturally acceptable salts and derivatives thereof.

[0121] 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 dimethenamide, in particular its enantiomer, dimethenamide-P, clomazone, metolachlor, in particular its enantiomer, S-metolachlor, alachlor, cinmethylin.

[0122] In a further particular subgroup of this group of embodiments, the crop protection agent is a crop protection agent or mixture of crop protection agents, or a mixture of such active ingredients, that has low water solubility and a melting point of 110° C. or less. These include, for example, pyraclostrobin (64° C.), prochloraz (47° C.), metrafenone (100° C.), alphacypermethrin (79° C.) and pendimethalin (58° C.).

[0123] In a further particular 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.

[0124] Pheromones are well-known compounds used to control unwanted insects. For example, Metcalf, R.L. Lullmann'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), and the pheromones for Lepidoptera (Lipidoptera) in Table 4 are particularly suitable.

[0125] Examples of pheromones include volatile alkanols and alkenols having 5 to 18 carbon atoms, volatile alkanals and alkenals having 5 to 18 carbon atoms, alkanones having 6 to 18 carbon atoms, 1,7-dioxaspirononane and 3- or 4-hydroxy-1,7-dioxaspirondecane, benzyl alcohol, Z-(9)-tricosene (muscal), heneicosene, diacetyl, alkanoic acids having 5 to 16 carbon atoms, such as caprylic acid, lauric acid, α-pinene, methyl eugenol, ethyl dodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane-carboxylate, mycrenone, cucurbitacin, trimedlure (commercially available as Capilure®), and (E,E)8,10-dodecadien-1-ol (codormone).

[0126] Further examples of known pheromones are: Z-5-decenyl acetate, dodecanyl 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. 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, hexadecanyl acetate, Z-7-hexadecenyl Acetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecanyl 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, [beta]-ionone, ethylenediamine Stragol, eugenol, indole, 8-methyl-2-decylpropanoate, 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, decanol, 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-8,10-dodecadienol Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol, E,Z-7,9-dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11-tetradecenol, E-11-tetradecenol, Z-11-hexadecenol, Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10,1 2-Tetradecadienol, Z,Z-7,11-hexadecadienol, Z,E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecanal, 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, hexadecanal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal, Z-12-hexadecenal, Z-13-hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)-14-methyl-8-hexadecenal, 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, octadecanal, Z-11-octadecenal, E-13-octadecenal, Z-13-octadecenal, Z-5-decenyl-3-methylbutanoate disperlua: (+)cis-7,8-epoxy-2-methyloctadecane, Seedenol: 3-methyl-2-cyclohexen-1-ol, Sulcatol: 6-methyl-5-hepten-2-ol, Ipsenol: 2-methyl-6-methylene-7-octen-4-ol, Ipsdienol: 2-methyl-6-methylene-2,7-octadien-4-ol, Granrua I: cis-2-isopropenyl-1-methylcyclobutane-ethanol, Granrua II: Z-3,3-dimethyl-1-cyclohexane-ethanol, Granrua III: Z-3,3-dimethyl-1-cyclohexane-acetaldehyde, Granrua -A 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, [alpha]-pinene: 2,6,6-trimethylbicyclo[3,1,1]hepten-2-ene, [alpha]-caryophyllene: 4,11,11-trimethyl-8-methylene -bicyclo[7,2,0]undecane, Z-9-tricosene, ([alpha]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane, methyleugenol: 1,2-dimethoxy-4-(2-propenyl)phenol, lineatin: 3,3,7-trimethyl-2,9-dioxatricyclo[3,3,1,0]nonane, chalcoglan: 2-ethyl-1,6-dioxaspiro[4,4]nonane, 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-methyl) (Z)-3-methyl-6-(1-methylethenyl)-3,9-decadien-1-ol acetate, (E)-3,9-methyl-6-(1-methyl-ethenyl)-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-ethenyl)-3,9-decadien-1-ol propionate.

[0127] Preferred pheromones are Z-9-dodecenyl acetate (commercially available as RAK® 1 from BASF SE), (E7,Z9)-dodecadienyl acetate (commercially available as RAK® 2 from BASF SE), (E,E)-8,10-dodecadien-1-ol (commercially available as RAK® 3 from BASF SE), and Z-8-dodecenyl acetate.

[0128] Particularly preferred pheromones include (E,E)-8,10-dodecadien-1-ol, also known as codormone or codrua, and commercially available (e.g., as CheckMate® CM-F from Suterra LLC, USA; Isomate®-C Plus from Pacific Biocontrol Corp. USA; and RAK® 3 from BASF SE). Codormone can be used in pure form, in technical quality, or in mixtures with other pheromones.

[0129] The aforementioned pheromones may be combined with one or more attractants. Attractants are non-pesticidal materials that can act in one or more of the following ways: a) attracting insects to approach the composition or materials treated with the composition; b) attracting insects to contact the composition or materials treated with the composition; c) attracting insects to ingest the composition or materials treated with the composition; and d) attracting insects to return to the composition or materials treated with the composition. Suitable attractants include non-food attractants and food attractants, also known as feeding stimulants.

[0130] Suitable non-food attractants are usually volatile substances. Volatile attractants act as baits, and their types depend on the pests to be controlled in a known manner. Non-food attractants include, for example, natural or synthetic flavors. Suitable flavors include meat flavors, yeast flavors, seafood flavors, milk flavors, butter flavors, cheese flavors, onion flavors, and fruit flavors, such as apple, apricot, banana, blackberry, cherry, currant, currant, grape, grapefruit, raspberry, and strawberry flavors.

[0131] Suitable food attractants include: Proteins, including animal proteins 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.; Carbohydrates and hydrogenated carbohydrates, in particular mono- and disaccharides such as glucose, arabinose, fructose, mannose, sucrose, lactose, galactose, maltose, maltotriose, maltotetrose, maltopentose or mixtures thereof, such as molasses, corn syrup, maple syrup, invert sugar and honey; polysaccharides including starch, 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, isomaltrose, trehalose and maltitol, and maltitol-containing syrups.

[0132] Preferred attractants are ethyl 3-methylbutanoate, methyl salicylate, amyl acetate, limonene, or fruit extracts (e.g., apple extract made from dried and extracted apples contains fructose, glucose, sorbitol, and apple flavor). Mixtures of attractants are also suitable.

[0133] In a further group of embodiments, the organic active substance is an organic active substance suitable for cosmetic applications or an active mixture other than the aforementioned aromas. Preferred cosmetic active substances for loading the microparticles are in particular active plant ingredients and plant extracts.

[0134] 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, antidandruff agents, anti-inflammatory agents, keratinizing substances, antioxidant active ingredients and active ingredients acting as free radical scavengers, skin moisturizing or hydrating substances, refatting active ingredients, deodorizing active ingredients, soothing active ingredients, plant extracts, anti-lupus or anti-allergic active ingredients and mixtures thereof.

[0135] Suitable artificial tanning actives for tanning skin without natural or artificial UV irradiation include, for example, dihydroxyacetone, alloxan, and walnut shell extract. Suitable keratin-hardening agents are typically active ingredients found in antiperspirants, such as aluminum potassium sulfate, aluminum hydroxide, and aluminum lactate. Antimicrobial actives are used to destroy and / or inhibit the growth of microorganisms, thus acting both as preservatives and as deodorants to reduce the formation or intensity of body odor. These include conventional preservatives well known to those skilled in the art, such as p-hydroxybenzoic acid esters, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, and salicylic acid. Examples of such deodorants include zinc ricinoleate, triclosan, undecylenic acid alkylolamide, triethyl citrate, and chlorhexidine. Suitable light filter active ingredients are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are those described above. Furthermore, p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, and camphor derivatives, as well as pigments that block UV rays, such as titanium dioxide, talc, and zinc oxide, are suitable. Suitable repellent active ingredients are compounds that repel or repel certain animals, especially insects, from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide, and the like. Suitable hyperemic substances that stimulate blood flow through the skin include, for example, essential oils, such as dwarf pine, lavender, rosemary, juniper berry, roasted chestnut extract, birch leaf extract, hayseed extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, and eucalyptus oil. Suitable keratolytic and keratinogenic substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable anti-dandruff active ingredients are, for example, sulfur, polyethylene glycol sorbitan monooleate, ricinol monooleate polyethoxylate, zinc pyrithione, aluminum pyrithione, etc.Suitable anti-inflammatory agents to combat skin irritation include, for example, allantoin, bisabolol, Dragosantol, chamomile extract, panthenol, and the like.

[0136] Further cosmetic active substances are aspalathin, glycyrrhizin, caffeine, proanthocyanidins, hesperetin, rutin, luteolin, polyphenols, oleuropein, theobromine, bioflavonoids and polyphenols.

[0137] Examples of plant extracts include acai extract (Euterpe oleracea), acerola extract (Malpighia glabra), horsetail extract (Equisetum arvense), agarius extract (Agarius blazei murill), aloe extract (Aloe vera, Aloe barbadensis), apple extract (Malus), artichoke leaf extract (Cynara scolymus), artichoke blossom extract (Cynara edulis), arnica extract (Arnica montana), oyster extract (Ostrea edulis), and others. edulis), Kanokosoul 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), Broccoli Extract (Brassica oleracea), Watercress Extract (Rorippa nasturtium), Painted Nettle Nettle Extract (Coleus forskohlii), Capsaicin Extract (Capsicum frutescens), Centella asiatica (Gotu kola)Kola extract, Cinchona extract, Cranberry extract (Vaccinium vitis-daea), Turmeric extract (Curcuma longa), Damiana extract (Tunera diffusa), Dragon fruit extract (Pitahaya), Echinacea purpurea extract, Wheat placenta extract, Edelweiss extract (Leotopodium alpinum), Ivy extract (Hedera helix), Bindi extract (Tribulus terrestris), Garcinia cambogia cambogia extract (Garcinia cambogia), Ginkgo biloba extract (Ginkgo biloba), Korean ginseng extract (Panax ginseng), Pomegranate extract (Punica granatum), Grapefruit extract (Citrus paradisi), Griffonia extract (Griffonia simplicifolia), Green tea extract (Camellia sinensis), Guarana extract (Paullinia cupana), Cucumber extract (Cucumis sativus), Dog rose extract (Rosa canina), Blueberry extract (Vaccinium mytilus) myrtillus), Hibiscus extract (Malvacea), Mallow extract, Honey extract, Hop extract (Humulus), Ginger extract (Zingiber officinale), Iceland moss (Icelandmoss extract (Cetraria islandica), jojoba extract (Simmondsia chinensis), St. John's Wort extract (Hypericum perforatum), coffee concentrate, cocoa bean extract (Theobroma cacao), cactus blossom extract, chamomile blossom extract (Matricaria recutita, Matricaria chamomila), carrot extract (Daucus carota), kiwi extract (Aperygidae), kudzu extract (Pueraria lobata) lobata), Coconut Milk Extract, Pumpkin Seed Extract (Curcurbita pepo), Cornflower Extract (Centaurea cyanus), Luteus Flower Extract, Dandelion Extract (Taraxacum officinale), Maca Extract (Lepidium peruvianum), Magnolia Blossom Extract, Mango Extract, Milk Thistle Extract (Silybum marianum), Marigold Extract (Calendula officiennalis), Yerba Mate Extract (Hex paraguariensis), Butcher's Broom Extract (Rugcus aculeatus) aculeatus), Seaweed Extract, Cranberry Extract (Vaccinium macrocarpon), Moringa Oleifera Extract, Moschus Malve Extract (Malva moschata), Evening Primrose Oil Extract (Azadirachta indicaindica), nettle extract (Urticaceae), olive leaf extract (Olea europea), orange extract (hesperidin), orchid extract, papaya extract (Carica papaya), peppermint extract, carica papaya extract (Geissospermum), bitter orange extract (Citrus aurantioum), lingonberry extract (Vaccinium vitas-ideea), African cherry extract (Prunus africana), sugar beet extract, resveratrol extract (Polygonum cuspidatum) cuspidatum), Rooibos Extract (Aspalasthus Linnearis), Roseblossom Extract, Horse Chestnut Extract (Aesculus hippocastanum), Rosemary Extract (Rosemarinus Officinalis), Red Clover Extract (Trifolium platense), Red Wine Extract (Vitis vinifera), Saw Palmetto Extract (Serenoa repens), Lettuce Extract (Lactuca sativa), Sandalwood Extract (Santalum rubrum), Sage Extract (Salvia officinalis) officinalis), Horsetail Extract (Equisetum), Yarrow Extract (Achillea millefolium), Black Pepper Extract (Piper nigrum)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 (Vitis vinifera), Grape Skin Extract (Vitis vinifera), Watercress (Rorippa amphibia), Willow Bark Extract (Salix Alba) alba), mugwort extract (Artemisia absinthium), white tea extract, yam root extract (Dioscorea opposita), yohimbe extract (Pausinystalia yohimbe), witch hazel extract (Hamamelis), cinnamon extract (Cinnamomum cassia Presl), lemon extract (Citrus), and onion extract (Allium cepa).

[0138] 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.

[0139] In a further group of embodiments, the low molecular weight organic active substance is an organic effect compound. Effect compounds are organic active substances that do not belong to the groups of pesticides, aroma chemicals, vitamins, AIPs, and cosmetic active substances. The group of effect compounds is typically not approved for agricultural use, human administration, cosmetic or dietary uses. These include, but are not limited to, compounds for construction chemistry, especially catalysts, but also dyes, UV stabilizers, polymerization inhibitors, oxidation stabilizers, etc. Preferred active substances to be encapsulated in microparticles for use in construction chemistry are, in particular, polymerization catalysts.

[0140] Useful polymerization catalysts include those suitable for curing reactive resins, especially addition resins, condensation resins, or oxidatively cured resins. For this purpose, the polymerization catalyst is a catalyst for free-radical polymerization, polycondensation, and / or polyaddition. Suitable catalysts for free-radical polymerization include, in particular, peroxide splitters and catalysts known from coating technology for oxidatively drying oil and alkyd resins as driers or siccatives. Suitable polycondensation catalysts are catalysts for silicone condensation and crosslinking. The polyaddition catalyst used can be, for example, a catalyst for curing epoxy resins. Additionally, the polyaddition catalyst used can be, for example, a urethanization catalyst conventionally used in polyurethane chemistry. These are compounds that promote the reaction of the reactive hydrogen atoms of the isocyanate-reactive component with an organic polyisocyanate.

[0141] Useful polymerization catalysts include tertiary amines, phosphines and organometallic salts, among others.

[0142] Tertiary amines useful as polymerization catalysts, particularly for polyaddition, include, 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'-tetramethylbutylenediamine, N,N,N',N'-tetramethylhexylene-1,6-diamine, N-N,N',N'',N'''-pentamethyldiethylenetriamine (PMDETA), N,N,N',N'',N'''-pentamethyldipropylene These include N,N,N-tris(3-dimethylaminopropyl)amine (PMDPTA), N,N,N-tris(3-dimethylaminopropyl)amine, bis(2-dimethylaminoethyl)ether (BDMAEE), bis(dimethylaminopropyl)urea, 2,4,6-tris(dimethylaminomethyl)phenol, its salt with 2-ethylhexanoic acid and its isomers, 1,4-dimethylpiperazine (DMP), 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), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,5-diazabicyclo[4.3.0]non-7-ene (DBN).

[0143] Further useful polymerization catalysts, particularly for polyaddition, include tris(dialkylamino)-s-hexahydrotriazines, especially 1,3,5-tris(3-[dimethylamino]propyl)hexahydrotriazine.

[0144] Phosphines useful as polymerization catalysts, particularly for polyaddition, are preferably tertiary phosphines, such as triphenylphosphine or methyldiphenylphosphine.

[0145] The organometallic salts useful as polymerization catalysts preferably have the general formula: L mM n+ nA - (In the formula, Ligand L is an organic group or organic compound selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, Ligand L has 1 to 20 carbon atoms, and m Ligands L are the same or different; m is 0, 1, 2, 3, 4, 5 or 6; M is a metal, n is 1, 2, 3 or 4, and Anion A - is a carboxylate ion, an alkoxylate ion, or an enolate ion).

[0146] 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 from lithium, potassium, cesium, tin, bismuth, titanium, zinc and zirconium.

[0147] The ligand L is preferably alkyl having 1 to 20 carbon atoms. More preferably, L is alkyl having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0148] The carboxylate ion preferably has the formula R 1 -COO - (In the formula, R 1 is selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, and R 1The group has 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 naphthenic acids.

[0149] The enolate ion preferably has the formula R 2 CH=CR 3 -O - (In the formula, R 2 and R 3 are each selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, and R 2 Groups and R 3 The groups each have up to 20 carbon atoms. Specific examples are ethyl acetonate, heptyl acetonate, or phenyl acetonate. The enolate ions are preferably derived from 1,3-diketones having 5 to 8 carbon atoms. Possible examples include acetyl acetonate, the enolate of 2,4-hexanedione, the enolate of 3,5-heptanedione, and the enolate of 3,5-octanedione.

[0150] The alkoxylate ion preferably has the formula R 4 -O - (In the formula, R 4 is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, and R 4 The group has up to 20 carbon atoms.

[0151] In certain embodiments, the organometallic compound is selected from the following: - alkali metal carboxylates, for example, lithium ethylhexanoate, lithium neodecanoate, potassium acetate, potassium ethylhexanoate, cesium ethylhexanoate; alkaline earth metal carboxylates, for example calcium ethylhexanoate, calcium naphthenate, calcium octoate (available as Octa-Soligen® Calcium from OMG Borchers), magnesium stearate, strontium ethylhexanoate, barium ethylhexanoate, barium naphthenate, barium neodecanoate; aluminum compounds, such as aluminum acetylacetonate, aluminum dionate (for example K KAT® 5218 from King Industries); zinc compounds, such as zinc diacetate(ll), zinc ethylhexanoate(ll) and zinc octoate(ll), zinc neodecanoate, zinc acetylacetonate; tin compounds, such as tin(II) carboxylates, for example 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, for example dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate, in particular dibutyltin dilaurate; titanium compounds, for example, tetra(2-ethylhexyl) titanate; zirconium compounds, such as zirconium ethylhexanoate, zirconium neodecanoate, zirconium acetylacetonate (for example K-KAT® 4205 from King Industries); zirconium dionates (for example K-KAT® XC-9213; XC-A 209 and XC-6212 from King Industries); zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate; bismuth compounds, such as bismuth carboxylates, in particular bismuth octanoate, bismuth ethylhexanoate, bismuth neodecanoate or bismuth pivalate (for example K-KAT® 348, XC-B221, XC-C227, XC 8203, XK 651 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals, and those from Shepherd Lausanne); - manganese salts, for example, manganese neodecanoate, manganese naphthenate; - cobalt salts, such as cobalt neodecanoate, cobalt ethylhexanoate, cobalt naphthenate; - iron salts, for example, iron ethylhexanoate; - mercury compounds, for example phenylmercury carboxylate;

[0152] Preferred organometallic compounds are dibutyltin dilaurate, dioctyltin dilaurate, zinc(II) diacetate, zinc(II) dioctanoate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth neodecanoate, bismuth dioctanoate and bismuth ethylhexanoate.

[0153] In the first step i. of the process of the present invention, a water-immiscible liquid is prepared by mixing at least one organic active substance, a shell-forming compound (SFC1), and, optionally, 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. The mixture may be shaken and / or stirred to achieve dissolution of the ingredients. Typically, the temperature for providing the water-immiscible liquid is not critical and is typically in the range of 5 to 80°C.

[0154] The concentration of the organic active compound encapsulated in the water-immiscible liquid can vary, typically in the range of 1 to 99% by weight, particularly 10 to 98.5% by weight, and particularly 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, particularly 1.5 to 25% by weight, and particularly 2 to 15% by weight, based on the total weight of the water-immiscible liquid. Preferably, the total amount of the shell-forming compound (SFC1) and the organic active compound encapsulated is at least 10% by weight, particularly 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.

[0155] In the second step ii., the water-immiscible liquid obtained in step i. is emulsified in an aqueous medium to form an oil-in-water emulsion (hereinafter also referred to as an o / w emulsion) of the water-immiscible liquid containing 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.

[0156] The aqueous phase usually contains at least one dispersant to stabilize the droplets of the o / w emulsion not only during its preparation in step ii. but also during the reaction of the shell-forming compounds (SFC1) and (SFC2) in step iii.

[0157] Dispersants suitable for stabilizing oil-in-water emulsions are general 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, polyvinylpyrrolidone, copolymers of vinylpyrrolidone and inorganic Pickering stabilizers.

[0158] 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 alone or in combination with water-soluble organic polymers.

[0159] Dispersants from the group of polysaccharides include, for example, cellulose derivatives such as hydroxyethyl cellulose, methylhydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose, methylhydroxypropyl cellulose, lignin sulfonates, and also mixtures of the above.

[0160] Preferred dispersants include at least one of partially or fully hydrolyzed polyvinyl acetate (polyvinyl alcohol) and methylhydroxy (C1-C4) alkyl cellulose, and mixtures thereof. Preferred dispersants also include Pickering systems, especially combinations of Pickering systems with one or more of the aforementioned organic polymeric dispersants, preferably partially or fully hydrolyzed polyvinyl acetate (polyvinyl alcohol) and methylhydroxy (C1-C4) alkyl cellulose, and mixtures thereof.

[0161] Among organic water-soluble polymers, partially hydrolyzed polyvinyl acetate, also called partially hydrolyzed polyvinyl alcohol (PVA), is particularly preferred, especially those having a degree of hydrolysis of 70% to 99.9%, in particular 75 to 99%, more particularly 80 to 95%. Additionally, PVA copolymers such as those described in WO 2015 / 165836 are also suitable. The PVA may in particular be a carboxy-modified anionic PVA. Such a carboxy-modified PVA preferably has a proportion of carboxyl groups of 1 to 6 mol %. In particular, the carboxy-modified PVA is used as a dispersant, and a 4 wt % aqueous solution thereof preferably has a viscosity of 20.0 to 30.0 mPa at 20°C. *The viscosity ranges from 0.0 to 0.25 s. Among the group of partially hydrolyzed polyvinyl alcohols, those having a degree of hydrolysis of 70% to 99.9%, particularly 75 to 99%, more particularly 80 to 95%, and particularly 85 to 95% are particularly preferred. Particularly preferred dispersants are carboxy-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 particularly 85 to 95%. Among these, those having a viscosity of 20.0 to 30.0 mPa (100 s) at 20°C in a 4% by weight aqueous solution are preferred. * Preferably, the viscosity is 0.05 s.

[0162] Among organic water-soluble polymers, methylhydroxy(C1-C4) alkylcelluloses are particularly preferred. Methylhydroxy(C1-C4) alkylcelluloses are understood to mean methylhydroxy(C1-C4) alkylcelluloses with various degrees of methylation and alkoxylation. Preferred methylhydroxy(C1-C4) alkylcelluloses have an average degree of substitution (DS) of 1.1 to 2.5 and a molar substitution (MS) of 0.03 to 0.9. Suitable methylhydroxy(C1-C4) alkylcelluloses are, for example, methylhydroxyethylcellulose or methylhydroxypropylcellulose. Particularly preferred is methylhydroxypropylcellulose, whose 2% aqueous solution has a viscosity in the range of 90 to 700 mPa·s, particularly in the range of 100 to 600 mPa·s, and especially in the range of 400 to 550 mPa·s, as determined by Brookfield RVT at 20 rpm and 20°C on an oven-dry basis. Particularly preferred is methylhydroxypropyl cellulose having a viscosity of 400 to 550 mPa·s in a 2% aqueous solution, as determined by Brookfield RVT at 20 rpm and 20°C on an oven-dry basis. This methylhydroxypropyl cellulose is commercially available, for example, as Ashland's Culminal MHPC 400 R. Non-limiting examples of commercially available methylhydroxypropyl cellulose having a viscosity within the above range include, for example, Ashland's Culminal MHPC 100, Culminal MHPC 400 R, and Culminal MHPC 500 RF.

[0163] Also preferred dispersants are salt polymers containing sulfonate groups. Such polymers include homopolymers and copolymers of ethylenically unsaturated sulfonic acids, such as 2-acrylamido-2-methylpropanesulfonic acid, optionally with one or more water-soluble monomers, such as acrylamide or methacrylamide and their salts. These also include salts of lignin-based sulfonic acids, also known as lignin sulfonates or lignosulfonates. Suitable lignin sulfonates may include, for example, sodium lignosulfonate, calcium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, potassium lignosulfonate, or sulfomethylated lignosulfonate. The aforementioned salts are particularly sodium or ammonium salts of polymers containing sulfonate groups.

[0164] Particularly suitable lignin-based sulfonic acids have an average molar weight Mw of at least 5,000 Da. Preferably, the average molar weight Mw ranges from 5,000 Da to 100,000 Da, as determined by gel permeation chromatography according to DIN 55672-3. Preferably, the lignin-based sulfonic acids have a degree of sulfonation of 1.0 to 2.5 moles per kilogram of lignosulfonic acid. The degree of sulfonation of the lignin-based sulfonic acids, as applied herein, is calculated from the sulfur content of the lignin-based sulfonic acid, as determined by atomic emission spectroscopy, minus the sulfonate content (determined according to DIN 38405 D52). Preferred lignin-based sulfonic acids are lignosulfonic acid, ethoxylated lignosulfonic acid, or oxidized lignin. A particularly preferred lignin sulfonate is sulfonated kraft lignin, available commercially, for example as Reax® 910 from Ingevity. Non-limiting examples of commercially available lignin sulfonates include, for example, Greensperse s7, Reax® 85, Reax® 88A, Reax® 907, Reax® 910, Polyfon®, Hyact, Kraftsperse 25m, and Borresperse NA. Greensperse s7, Kraftsperse 25m, and Reax® 85 (available from Ingevity) and Borresperse NA (available from Borregaard AS) contain sodium lignosulfonate. Reax® 88A, Reax® 907, Reax® 910, Polyfon®, and Hyact (available from Ingevity) contain sulfonated kraft lignin.

[0165] Among organic water-soluble polymers, polymers having carboxyl groups are also preferred.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.Polymers having carboxyl groups are typically used in their partially or completely neutralized form, where the carboxyl groups are converted into anionic carboxylate form.Typically, the counterion is selected from sodium and ammonium.

[0166] Another group of preferred dispersants are inorganic Pickering systems, especially colloidal silica or phyllosilicates.

[0167] In the context of the present invention, the term "colloidal silica," also referred to as colloidal silica dispersion, colloidal nanoparticulate silica, or colloidal silica sol, refers to a stable dispersion of amorphous microparticulate silicon dioxide (SiO2) having a particle size in the range of 3 to 200 nm, preferably 5 to 170 nm, and particularly 10 to 150 nm. In this context, the particle size of 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. Consequently, the particle size is at most 200 nm, preferably at most 170 nm, most preferably at most 150 nm, and particularly 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.

[0168] An example of a suitable colloidal silica sol is a colloidal silica sol having a particle size of 9 nm, commercially available, for example, from AkzoNobel under the trade name Bindzil® 30 / 360. 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, commercially available, for example, from AkzoNobel under the trade name Bindzil® 50 / 80. Further suitable silica sols are Bindzil® 15 / 500, Bindzil® 30 / 220, Bindzil® 40 / 200, Bindzil® CC151HS, Bindzil® CC301 (AkzoNobel), Nyacol® 215, Nyacol® 830, Nyacol® 1430, Nyacol® 2034DI as well as Nyacol® DP5820, Nyacol® DP5480, Nyacol® DP5540, etc. (Nyacol Products), Levasil® 100 / 30, Levasil® 10° F. / 30, Levasil® 100S / 30, Levasil® 200 / 30, Levasil® 200F / 30, Levasil® 300F / 30, Levasil® VP 4038, Levasil® VP 4055 (H.C. Starck / Bayer), or CAB-O-SPERSE® PG 001, CAB-O-SPERSE® PG 002 (aqueous dispersion of CAB-O-SIL®, Cabot), Quartron PL-1, Quartron PL-3 (FusoChemical Co.), Koestrosol 0830, Koestrosol 1030, Koestrosol 1430 (Chemiewerk Bad Koestritz).

[0169] In a preferred embodiment, the dispersant comprises a colloidal silica sol having a particle size in the range of 3 to 200 nm, particularly in the range of 5 to 170 nm, especially in the range of 10 to 150 nm, for example commercially available as Bindzil 50 / 80 from AkzoNobel.

[0170] In another preferred embodiment, the dispersant comprises a phyllosilicate, in particular a clay mineral that can swell in water, such as hectorite, montmorillonite, saponite, or a phyllosilicate with a particularly high content of smectite, in particular sodium smectite, such as Laponite™.

[0171] In particular, inorganic Pickering systems, such as modified colloidal silica and phyllosilicates, are used in combination with organic polymer dispersants, especially those from the group consisting of polyvinyl alcohols, to obtain particularly dense microparticles, with the inorganic Pickering system particles remaining on the surface of the microparticles.

[0172] To stabilize the oil-in-water 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 wt. %, particularly 0.2 to 5.0 wt. %, and more particularly 0.3 to 3.0 wt. %, based on the total weight of the aqueous phase.

[0173] With respect to the amount of water-immiscible liquid of step i. to be emulsified, the concentration of the dispersant and the relative amount of water-immiscible liquid of step i. to 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.

[0174] The weight ratio of the water-immiscible liquid prepared in step i. to the aqueous phase is typically in the range of 1:10 to 1.5:1, particularly in the range of 1:5 to 1.1:1, and especially in the range of 1:2 to 1:1.

[0175] To prepare and stabilize the oil-in-water emulsion in step ii., one or more emulsifiers can be used together with the aforementioned dispersants. In contrast to dispersants, emulsifiers typically have a lower molecular weight, generally less than 500 g / mol (number average). Emulsifiers having an HLB value according to Griffin of at least 10, particularly at least 15, are preferred. The HLB value according to Griffin (WC Griffin: Classification of surface-active agents by HLB. In: J. Soc. Cosmet. Chem. 1, 1949, pp. 311-326) (HLB = hydrophilic-lipophilic balance) is a dimensionless number between 0 and 20 that provides information about the water and oil solubility of a compound. Preferably, these are nonionic emulsifiers having an HLB value according to Griffin of at least 10, particularly at least 15. However, anionic and zwitterionic emulsifiers having an HLB value according to Griffin of at least 10, particularly at least 15, are also suitable. Such emulsifiers are generally used in an amount of 0.1 to 10% by weight, particularly 0.5 to 5% by weight, based on the total weight of the emulsion prepared in step II. Generally, one or more emulsifiers can be added to the water-immiscible liquid in step I prior to emulsification or to the aqueous medium.

[0176] Examples of suitable emulsifiers having an HLB value according to Griffin of at least 10 are: 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; - lactyl esters of fatty acid monoesters of glycerol; - lecithin; - ethoxylated castor oil, ethoxylated hydrogenated castor oil, having an ethoxylation degree of at least 20, for example from 20 to 60; - ethoxylated and / or propoxylated C with 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 from 10 to 50, stearyl alcohol ethoxylate-co-propoxylate having a degree of alkoxylation in the range from 10 to 50, isotridecyl ethoxylate having a degree of ethoxylation in the range from 10 to 50 and isotridecyl ethoxylate-co-propoxylate having a degree of alkoxylation in the range from 10 to 50; - Ethoxylated and / or propoxylated C4-C with a degree of alkoxylation ranging from 10 to 50 16 Alkylphenols, such as nonylphenol ethoxylates having a degree of ethoxylation in the range from 10 to 50 and octylphenol ethoxylates having a degree of ethoxylation in the range from 10 to 50.

[0177] Typically, the aqueous phase is water, which preferably contains a dispersant and optionally an emulsifier. Furthermore, the aqueous phase may contain an antifoaming agent. The concentration of the antifoaming agent in the aqueous phase is typically less than 2 g / kg, particularly less 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 that is miscible with water. The amount of such a solvent generally does not exceed 10 wt. %, particularly does not exceed 5 wt. % or 1 wt. %, based on the total weight of the aqueous phase.

[0178] Emulsifying the water-immiscible liquid provided in step i. in an aqueous medium to obtain an o / w emulsion in process step ii. can be carried out by standard procedures for producing emulsions. Typically, emulsification is achieved by stirring or shearing a mixture of an aqueous phase and the solution obtained in step i. or a combination of both.

[0179] Preferably, the aqueous phase containing the dispersant is first charged to the vessel, and the water-immiscible liquid provided in step i. is metered into this aqueous phase while the two liquids are mixed, for example by stirring or shearing. It is also possible to continuously combine the flow of the aqueous phase and the flow of the solution of step i. in a mixing chamber, and to continuously remove the o / w emulsion from the mixing chamber. The mixing chamber may have static or dynamic mixing elements.

[0180] The droplet size can be controlled depending on the energy input to the mixture of the aqueous phase and the water-immiscible liquid provided in step i. Furthermore, the type and amount of the dispersant mentioned above influences the size of the emulsion droplets at equilibrium. An appropriate amount can be routinely selected. 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 does not exceed 400 μm, particularly 200 μm, and especially 100 μm.

[0181] In this specification 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 particle size distributions determined by static laser light scattering according to ISO 13320:2009 on small particle samples. The abbreviation SLS is also used hereinafter for the expression "Static Laser Light Scattering according to ISO 13320:2009." In this context, a D[v,0.1] value means that 10% by volume of the particles in the measured sample have a particle diameter less than the value reported as D[v,01]. Thus, a D[v,0.5] value means that 50% by volume of the particles in the measured sample have a particle diameter less than the value reported as D[v,0.5], and a D[v,0.9] value means that 90% by volume of the particles in the measured sample have a particle diameter less than the value reported as D[v,0.9]. The D[4,3] value is the volume-weighted average determined by SLS, also known as the De Brouckere average, which corresponds to the mass average of the particles of the present invention. The D[3,2] value is the surface-weighted average determined by SLS, also known as the Sauter mean diameter (SMD).

[0182] Agitation typically produces droplets having an average droplet size D[v,0.5] of at most 400 μm or less, particularly at most 200 μm, particularly at most 100 μm, for example, in the range of 0.5 to 400 μm, particularly 1 to 200 μm, and particularly 1 to 100 μm, achieved by a device for generating a high shear field. It is also possible to introduce sufficient shear energy by vigorous agitation to achieve an average droplet size with a D[v,0.5] value in the range of 0.5 to 400 μm, preferably 1 to 200 μm, and particularly 1 to 100 μm. If even higher shear energy inputs are intended, it may be advantageous to use a device for generating a high shear field.

[0183] By adjusting the droplet size and droplet size distribution of the o / w emulsion, it is possible to adjust the particle size and particle size distribution of the final microparticles containing the organic active compound. 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 resulting microparticles loaded with the organic active compound.

[0184] Suitable agitator types include propeller agitators, impeller agitators, disk agitators, paddle agitators, anchor agitators, pitched blade agitators, cross beam agitators, helical agitators, screw agitators, and the like.

[0185] Suitable devices for shearing, i.e., generating a high shear field, include dispersers operating on the rotor-stator principle, i.e., rotor-stator mixers, such as toothed ring dispersers (also called gear dispersers), colloid mills and disc mills, high-pressure homogenizers (also called high-pressure mixers), and ultrasonic homogenizers. High shear can also be achieved by using single- or multi-stage dispersion disc or cross-blade agitators. High shear can also be achieved by passing the mixture through a microfluidic device. Among shearing devices, dispersers operating on the rotor-stator principle to generate a shear field, particularly toothed ring dispersers, are preferred. The diameters of the rotor and stator typically range from 1 cm to 40 cm, depending on the size and dispersion performance of the machine. The rotation speed of such dispersers is generally in the range of 500 to 20,000 rpm, particularly 1,000 to 15,000 rpm (revolutions per minute), depending on the type of design. Of course, machines with larger rotor diameters typically operate at the lower end of the rotational speed range, while machines with smaller rotor diameters typically operate at the higher end of the rotational speed range. The peripheral speed of the rotor is typically in the range of 5-50 m / s. The distance from the stationary to rotating parts of the dispersion tool is generally 0.1-3 mm.

[0186] As mentioned above, the droplet size can be controlled by the shear energy input to the mixture of the aqueous phase and the solution obtained in step i. The shear energy input can be derived directly from the power consumption of the device for generating the shear field, taking into account heat losses. Therefore, the shear energy input into the oil-in-water emulsion is preferably between 250 and 25,000 watts h / m. 3 Batch size. Calculated based on motor current, 500-15000, especially 800-10000 watt-h / m 3 Batch-sized energy input is particularly preferred.

[0187] In a preferred embodiment, emulsification is carried out so that the emulsion droplets of the o / w emulsion have an average diameter D[v,0.5] of at most 400 μm or less than 400 μm, for example, in the range of 0.5 to 400 μm, particularly in the range of 1 to 200 μm, and particularly in the range of 1 to 100 μm, as determined by light scattering. For this purpose, emulsification typically involves 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 device as described above. Mixing and homogenization can be carried out sequentially or simultaneously.

[0188] For example, the solution of step i. and the aqueous phase are mixed with stirring, and the resulting emulsion is then homogenized as described herein, for example, by: - Processing of emulsions using rotor-stator mixers, especially toothed rim mixers; - applying ultrasound to the emulsion; - Processing of emulsions with dispersing disc or cross-blade agitators with one or more stages; - passing the emulsion through a membrane device; - passing the emulsion through a high-pressure homogenizer; or a combination thereof.

[0189] Mixing and homogenization can also be carried out simultaneously. For example, the aqueous phase stream and the solution stream of step i. are continuously combined in a mixing chamber of a homogenizer, and the oil-in-water emulsion is continuously removed from the mixing chamber. The homogenizers described above can be used for this purpose and are adapted for continuous operation. For this purpose, primarily any of the homogenizers mentioned above can be used. Membrane devices and high-pressure homogenizers are preferred.

[0190] Emulsification is usually carried out at a temperature in the range of 5 to 80°C, in particular in the range of 10 to 60°C. The temperature of the mixture is preferably selected to have a temperature in the range of 10 to 60°C, in particular in the range of 10 to 40°C. Typically, emulsification is carried out at atmospheric pressure or at a pressure above atmospheric pressure, for example up to 2 bar. However, a slight vacuum may also be applied. Preferably, the vacuum is 800 mbar or more.

[0191] 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 is completed. This results in particularly uniform microparticles.

[0192] By adding the second shell-forming compound (SFC2) to the oil-in-water emulsion of step ii., it reacts with the first shell-forming compound (SFC1) as explained above, thereby forming shells on the surface of the droplets of water-immiscible liquid present in the emulsion obtained in step ii. of the process, thereby obtaining microparticles.

[0193] Typically, the second shell-forming compound (SFC2) may be added neat, or it may be added as an aqueous solution or emulsion, depending on its solubility in water.

[0194] The second shell-forming compound (SFC2) may be added all at once or within a specific time period, for example within 1 to 60 minutes, particularly within 5 to 30 minutes.

[0195] The temperature during the addition can vary depending on the reactivity of the shell-forming compounds (SFC1) and (SFC2), and is typically in the range of 0 to 60°C, especially in the range of 5 to 40°C. Higher temperatures typically result in a more rapid reaction, but potentially in a broader particle size distribution of the resulting microparticles. Particularly preferably, the temperature during the addition does not exceed 30°C.

[0196] After the addition is complete, the mixture of the oil-in-water emulsion obtained in step ii. and the second shell-forming compound (SFC2) may be reacted for an additional period to complete the reaction of the shell-forming compounds (SFC1) and (SFC2). This additional period is also referred to as the post-reaction period. Typically, 24 hours is sufficient to achieve complete reaction. During the post-reaction period, the temperature of the reaction mixture is typically in the range of 0 to 80°C, particularly in the range of 5 to 70°C.

[0197] During the addition and post-reaction period, the mixture may be shaken or stirred to achieve a more uniform reaction and to avoid settling of the particles before the reaction of the shell-forming compounds (SFC1) and (SFC2) is complete.

[0198] The process of the present invention results in an aqueous suspension of microparticles, which, as explained above, 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.

[0199] The microparticles obtainable by the process of the present invention preferably have a median particle diameter, 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.

[0200] The microparticles obtained by the process 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, in particular in the range of 1.0 to 80 μm.

[0201] The microparticles obtained by the process of the present 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 depressions in the wall material or protrusions in the wall material. The term "spherical" means that the particle has an approximately spheroidal shape, in particular a spherical shape, and in particular 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, in particular in the range of 1:1 to 1.5:1.

[0202] As mentioned above, step iii. results in an aqueous suspension of microparticles. The aqueous suspension may be used for further applications. However, it is also possible to isolate the microparticles 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 filtration or centrifugation, or by evaporating the water of the aqueous suspension, for example, in a spray drying apparatus. Whatever isolation technique is used, the microparticles can be dried. "Dried" is understood to mean that the loaded microparticles contain a residual amount of water of 5% by weight or less, preferably 1% by weight or less, based on the microparticles. Drying can be carried out, for example, in an air stream and / or by applying a vacuum, optionally in each case by heating. Depending on the size of the microparticles, this can be achieved by convection dryers, such as spray dryers, fluidized bed and cyclone dryers, contact dryers, such as pan dryers, paddle dryers, contact belt dryers, vacuum drying cabinets, or radiant dryers, such as infrared rotary tube dryers and microwave mixer dryers. It may also be possible to remove residual water present after isolation of the supported polymer particles from the aqueous suspension by rinsing with ethanol or acetone and / or blowing the microparticles dry with an inert gas such as air, nitrogen or argon. Optionally, pre-dried and / or preheated inert gas may also be used for this purpose. The supported polymer microparticles may preferably be washed with an aqueous solution of propanediol, for example as a 10% by weight solution, and then optionally dried.

[0203] Surprisingly, the organoleptic profile is not significantly affected by microencapsulation, in other words, the organoleptic profile of the loaded microcapsules corresponds closely to that of the unencapsulated aroma chemicals and does not change significantly over time.

[0204] The present invention further provides compositions of microparticles obtainable by the process of the present invention. The compositions of the present invention preferably contain a total amount of active organic chemicals of 1 to 98% by weight, particularly 5 to 96% by weight, and especially 10 to 90% by weight, based on the total weight of the microparticles. The components of the microparticles, i.e., the components 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 used in the production of the microparticles that are not removed, such as dispersants. The compositions of the present invention can be in the form of either a suspension or a powder, with suspensions being preferred.

[0205] The present invention further provides a product comprising the composition of the present invention, preferably a product comprising the composition of the present invention in a weight ratio of 0.01% to 80% by weight based on the total weight of the product.

[0206] The properties of the product are naturally driven by the properties of the organic active material, which in the case of aroma chemicals can typically be products including, for example, perfumes, laundry products, cleaning products, cosmetics, personal care products, hygiene products, food products, food supplements or fragrance dispensers.

[0207] In the case of pesticides, it is typically a pesticide formulation containing at least one pesticide in the form of microparticles obtainable by the process of the present invention, optionally one or more further pesticides, and suitable formulation auxiliaries. Suitable pesticide formulations include capsule suspensions and solid formulations such as powders or granules.

[0208] In the case of pharmaceutically active substances, it 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.

[0209] The present invention further provides the use of the composition of the present invention in the aforementioned products, preferably in products selected from perfumes, laundry products, cleaning products, cosmetics, personal care products, hygiene products, food, food supplements, fragrance dispensers and fragrances.

[0210] The compositions of the present invention, which contain fragrances as aroma chemicals, can be used in the manufacture of scented articles. The olfactory and also physical properties and non-toxicity of the compositions of the present invention highlight their particular suitability for the end uses mentioned.

[0211] The use of the present compositions has been found to be particularly advantageous in combination with the top notes of perfume compositions containing, for example, dihydrolosan, rose oxide, or other readily volatile fragrances, such as isoamyl acetate, prenyl acetate, or methylheptenone. In this case, the release of the important and desirable top notes is effectively delayed. Thus, the fragrance or aroma composition can be metered in the required amount at the appropriate time. In the described mint compositions of L-menthol, DL-menthol, L-menthone, and L-menthyl acetate, in addition to the aroma effect, a cooling effect can also be applied in a targeted manner, for example, in chewing gum, confectionery, cosmetics, and industrial applications such as textiles or superabsorbents. A further advantage is the high material compatibility of the compositions of the present invention, even when they contain reactive or relatively unstable components, such as aldehydes, esters, pyrans / ethers, which may undergo secondary reactions on surfaces.

[0212] These positive properties are beneficial for the use of the compositions of the present invention, with perfumery products, personal care products, hygiene products, fabric detergents, and solid surface cleaning products being particularly preferred.

[0213] The scented article is selected, for example, from perfume products, personal care products, hygiene products, fabric detergents and cleaning products for solid surfaces. Preferred scented articles of the present invention are also selected from: perfume products selected from perfume extracts, eau de parfum, eau de toilette, eau de cologne, eau de solide, extrait parfum, deodorants in liquid form, in gel form or in the form applied to a solid carrier, aerosol sprays, scented cleaners and fragrance oils; - aftershave lotions, preshave products, splash colognes, bar and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, oil-in-water, water-in-oil and water-in-oil-in-water cosmetic emulsions, e.g., skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions personal care products selected from: hair care products such as hair sprays, hair gels, hair setting lotions, hair conditioners, hair shampoos, permanent and semi-permanent hair dyes, hair styling compositions such as cold wave perms and hair smoothing compositions, hair tonics, hair creams and hair lotions, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, decorative cosmetic products such as eyeliners, eye shadows, nail polishes, make-up products, lipsticks, mascara, toothpaste, dental floss; - hygiene products selected from candles, lamp oil, incense, sprays, rust removers, scented freshening wipes, underarm pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, pocket tissues, dishwashing detergents, deodorants; - solid surface cleaning products selected from scented acidic, alkaline and neutral cleaning products, for example floor cleaners, window cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milks, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes, for example furniture polishes, floor waxes, shoe creams, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, limescale removers, grill and oven cleaners, algae and moss removers, mould removers, facade cleaners; - Textile detergents selected from liquid detergents, powder detergents, laundry pre-treatments such as bleaches, soaking agents and stain removers, fabric softeners, laundry soaps, laundry tablets.

[0214] In a further embodiment, the compositions of the present invention are suitable for use in surfactant-containing perfumed articles, since, particularly for the scent of surfactant-containing formulations, such as cleaning products (especially dishwashing compositions and all-purpose cleaners), odorants and / or odorant compositions with a rose top note and a pronounced naturalness are often desired.

[0215] In a further embodiment, the compositions of the present invention can be used as products to provide an attractive odor node to (a) hair or (b) textile fibers.

[0216] Thus, the compositions of the present invention are particularly well suited for use in surfactant-containing perfumed articles.

[0217] Preferably, the scented article is one of the following: - acidic, alkaline or neutral cleaning products, in particular selected from the group consisting of all-purpose cleaners, floor cleaners, window cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milks, solid and liquid toilet cleaners, powdered and foamed carpet cleaners, liquid detergents, washing powders, washing powders, laundry pre-treatments such as bleaches, soaking agents and stain removers, fabric softeners, laundry soaps, cleaning tablets, disinfectants, surface disinfectants, deodorants in liquid, gel or solid carrier form or applied as an aerosol spray; waxes and polishes, in particular selected from the group consisting of furniture polishes, floor waxes and shoe polishes, or - personal care products, in particular chosen from the group consisting of 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, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, etc., hair care products, such as hair sprays, hair gels, hair setting lotions, hair conditioners, permanent and semi-permanent hair dyes, hair styling compositions such as cold wave perms and hair smoothing compositions, hair tonics, hair creams and hair lotions, deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, etc., decorative cosmetic products.

[0218] Odors used according to the present invention or conventional components with which the odorant compositions of the present invention can be combined are common knowledge and are described, for example, in WO 2016 / 050836, the teachings of which are expressly incorporated herein by reference.

[0219] Likewise preferred is the use of the compositions of the invention for the controlled release of active substances such as crop protection agents and pharmaceutical agents. [Brief explanation of the drawings]

[0220] [Figure 1a-1b] 1A-1C are photomicrographs at two different magnifications of microparticles prepared by the protocol of Example 2. The photomicrographs were performed by scanning electron microscopy (SEM) as described below. DETAILED DESCRIPTION OF THE INVENTION

[0221] Example material: - Cinmethyline: exo-(±)-1-methyl 2-(2-methylbenzyloxy)-4-isopropyl-7-oxa-bicyclo[2.2.1]heptane; - Antifoam 1: Silicone SRE-PFL (Wacker Chemie AG); - Antifoaming agent 2:1-octanol - Hexyl salicylate: hexyl 2-hydroxybenzoate; - Laponite: synthetic phyllosilicate (LAPONITE-RD® BYK-Chemie GmbH); - Nile Red: 9-(diethylamino)-5 H-benzo[a]phenoxazin-5-one used as a lipophilic dye for fluorescence microscopy; - PVA 1: Polyvinyl alcohol, hydrolyzed 88%, M W :13,000-23,000; - PVA 2: Polyvinyl alcohol, 88% hydrolyzed, M W : about 31,000 (Poval® 4-88, Kuraray); - PVP: Polyvinylpyrrolidone K 90 from BASF SE - Water: Double distilled water unless otherwise stated.

[0222] Characterization of the prepared microparticles method Microscopy and particle size distribution Scanning electron microscopy (SEM) was used to observe the morphology of the finished capsules. To this end, the resulting microparticle slurry was diluted with water (1:20 w / w) and coated onto a glass slide using a Polos Spin 150i spin coater (2000 RPM for 20 seconds). The capsules were then sputter-coated with a 5 nm thick platinum layer. SEM images were recorded using a benchtop Hitachi TM3030 microscope.

[0223] The particle size distribution of the capsules is measured by laser diffraction according to ISO 13320 EN:2020-01 using a Malvern Mastersizer 2000. The data are processed according to Mie-Theory by software using the "Universal Model" provided by Malvern Instruments. The important parameters are d for n=10, 50 and 90. n value, d 10 , d 50 and d 90 value, and the D[3,2] value, i.e., the Sauter mean diameter. 50 The value is the volume-based mean median d, also called D[v,50]. 50 Particle size is diameter.

[0224] Determination of the release rate of active substances from microparticles To determine the release rate, the following release protocol was followed: 50 mg of the microparticle slurry obtained after synthesis was placed in a cylindrical dialysis tube (diameter: 1 cm, length: 2 cm, molecular weight cutoff: 14 kDa) along with 2 mL of 36% (v / v) aqueous 1-propanol solution. The bag was then dropped into 100 mL of 36% (v / v) 1-propanol, and the entire solution was gently stirred (approximately 100 RPM) on a magnetic stirrer at room temperature. The external medium was continuously circulated through a calibrated UV-visible spectrophotometer (Cecil Instruments, Cambridge, UK), and the concentration of hexyl salicylate released from the capsules into this medium was recorded over time. To calculate the rate of oil release from the capsules, 50 mg of the microparticle slurry was sonicated in 100 mL of 1-propanol for 1 hour and then stirred overnight on an orbital shaker. The same spectrophotometer was used to record the concentration of hexyl salicylate extracted into 1-propanol. This represented the maximum concentration of hexyl salicylate present in the slurry. This value was used as the denominator to calculate the percent of hexyl salicylate released from the capsules.

[0225] As a control experiment, to understand the resistance offered by the microcapsule shell to release, the same experiment was repeated by adding pure hexyl salicylate in the dialysis tubing instead of the capsules, and the leakage rate of non-encapsulated oil was recorded for comparison.

[0226] Microparticle preparation Example 1: 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 minutes until a clear aqueous solution was obtained. Then, 2.59 g of a 3.5 wt. % aqueous sodium chloride solution, 7.5 g of a 10 wt. % aqueous PVA solution, and 2 drops of antifoam agent 2 were added, and the entire solution was placed in an ultrasonic bath for 5 minutes. The 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. The aqueous phase was transferred to a jacketed reactor equipped with four baffles arranged diametrically opposite each other. Water was circulated outside the reactor using a water bath (Julabo Me v.2) for temperature control. A temperature of 10 °C was maintained throughout. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 minutes at 8000 RPM using a Silverson L4RT (rotor-stator dispersion tool). After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 1000 RPM. Then, 2.16 g of 1,8-diaminooctane dissolved in 20 g of water was added to the emulsion over 60 minutes using a syringe pump. After addition, the stirring speed was reduced to 600 RPM and maintained for 18 hours. Overall, 198 g of a uniform dispersion of spherical and monodisperse microcapsules (D[3,2] = 1.5 μm) with an organic crystalline shell was obtained.

[0227] Example 2: 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 minutes until a clear aqueous solution was obtained. Then, 2.59 g of a 3.5 wt. % aqueous sodium chloride solution, 7.5 g of a 10 wt. % aqueous PVA solution, and 2 drops of antifoam agent 2 were added, and the entire solution was placed in an ultrasonic bath for 5 minutes. The oil phase was prepared by mixing 21.25 g of cinmethylin with 3.75 g of cyclohexyl isocyanate and 2 mg of Nile Red dye. The aqueous phase was transferred to a jacketed reactor equipped with four baffles arranged diametrically opposite each other. Water was circulated outside the reactor using a water bath (Julabo Me v.2) for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 minutes at 8000 RPM using a Silverson L4RT (rotor-stator dispersing tool) while maintaining the temperature at 10°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 1000 RPM. Then, 2.16 g of 1,8-diaminooctane dissolved in 20 g of water was added to the emulsion over 60 minutes using a syringe pump. After addition, the stirring speed was reduced to 600 RPM, and the temperature was increased to 20°C. These conditions were maintained for 18 hours. Overall, 198 g of a uniform dispersion of spherical and monodisperse microcapsules (D[3,2] = 4 μm) with an organic crystalline shell was obtained. D[v,10]=2.6μm, D[v,50]=5.7μm, D[v,90]=14.8μm

[0228] Example 3 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 minutes until a clear aqueous solution was obtained. Then, 2.59 g of a 3.5 wt. % aqueous sodium chloride solution, 7.5 g of a 10 wt. % aqueous PVA solution, and 2 drops of antifoam agent 2 were added, and the entire solution was placed in an ultrasonic bath for 5 minutes. The 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. The aqueous phase was transferred to a jacketed reactor equipped with four baffles arranged diametrically opposite each other. Water was circulated outside the reactor using a water bath (Julabo Me v.2) for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 minutes at 8000 RPM using a Silverson L4RT (rotor-stator dispersing tool). A temperature of 10°C was maintained during emulsification. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 1000 RPM. Next, 3.61 g of 1,8-diaminooctane dissolved in 20 g of water was added to the emulsion over 60 minutes at 10°C using a syringe pump. After addition, the stirring speed was reduced to 600 RPM, and the temperature was increased to 20°C and maintained for 18 hours. Overall, 198 g of a uniform dispersion of spherical and monodisperse microcapsules (D[3,2] = 2.3 μm) with an organic crystalline shell was obtained.

[0229] Example 4: The aqueous phase was prepared as follows: 142.5 g of water was introduced into a beaker. 1.2 g of Laponite was added while stirring using a silent crusher (rotor-stator dispersion tool). The powder was dispersed for 10 seconds at 7,000 rpm. 7.5 g of a 10% by weight solution of PVA 2 and 2 drops of antifoam agent 1 were then added. The dispersion was placed in an ultrasonic bath (Transonic 470 / H) for 5 minutes. The oil phase was obtained by mixing 21.25 g of dibutyl adipate with 3.75 g of cyclohexyl isocyanate. An emulsion was produced using a Silverson L5M (rotor-stator dispersion tool). The oil phase was added to the aqueous phase and homogenized at 10,000 rpm for 7 minutes. The emulsion was then transferred to a glass reactor equipped with an anchor stirrer. The medium was cooled to 10°C while stirring at 300 rpm. Once at temperature, 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 an additional 4 hours. The bath was then removed, the temperature was slowly raised to room temperature, 23°C, and stirring was maintained for an additional 15 hours. Overall, 198 g of a uniform dispersion of nearly spherical and monodisperse microcapsules (D[3,2] = 11.9 μm) with an organic crystalline shell was obtained.

[0230] Example 5 The aqueous phase was prepared as follows: 140 g of water was introduced into a beaker. 1.2 g of Laponite was added while stirring using a silent crusher (rotor-stator dispersion tool). The powder was dispersed for 10 seconds at 7,000 rpm. 2.59 g of a 3.5 wt.% aqueous solution of sodium chloride, 7.5 g of a 10 wt.% aqueous solution of PVA2, and 2 drops of antifoam agent 1 were then added. The dispersion was placed in an ultrasonic bath (Transonic 470 / H) for 5 minutes. The oil phase was obtained by mixing 21.25 g of dibutyl adipate with 3.75 g of cyclohexyl isocyanate. An emulsion was produced using a Silverson L5M (rotor-stator dispersion tool). The oil phase was added to the aqueous phase and homogenized at 8,000 rpm for 7 minutes. The emulsion was then transferred to a glass reactor equipped with an anchor stirrer. The medium was cooled to 10 °C while stirring at 300 rpm. Once at temperature, 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 an additional 4 hours. The bath was then removed, the temperature was slowly raised to room temperature, 23°C, and stirring was maintained for an additional 15 hours. Overall, 198 g of a uniform dispersion of nearly spherical and monodisperse microcapsules (D[3,2] = 5.9 μm) with an organic crystalline shell was obtained.

[0231] Example 6: To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 10°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Then, 1.24 g of 1,6-hexanediamine dissolved in 10 g of water was added dropwise to the emulsion over 9 minutes. After addition, the stirring and temperature were maintained for an additional 18 hours. Overall, 98 g of a uniform dispersion of spherical microcapsules (D[3,2]=9 μm) with an organic crystalline shell was obtained.

[0232] Example 7: To prepare the aqueous phase, 3 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 8 g of hexyl salicylate and 2 g of cyclohexyl isocyanate. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersion tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Next, 1.38 g of 1,8-diaminooctane dissolved in 10 g of water was added dropwise to the emulsion over 15 minutes using a syringe pump. After the addition, stirring and temperature were maintained for a further 18 hours. Overall, 100 g of a homogeneous dispersion of spherical microcapsules (D[3,2]=6 μm) with an organic crystalline shell was obtained.

[0233] Example 8: To prepare the aqueous phase, 3.6 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. 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. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Next, 1.38 g of 1,8-diaminooctane dissolved in 10 g of water was added dropwise to the emulsion over 15 minutes using a syringe pump. After the addition, stirring and temperature were maintained for an additional 18 hours. Overall, 108 g of a uniform dispersion of spherical microcapsules (D[3,2] = 5.8 μm) with an organic crystalline shell was obtained.

[0234] Example 9: To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate, 2 g of cyclohexyl isocyanate, and 2 mg of Nile Red dye. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Then, 1.35 g of 1,7-diaminoheptane dissolved in 10 g of water was added dropwise to the emulsion over 15 minutes using a syringe pump. After the addition, stirring and temperature were maintained for an additional 18 hours. Overall, 108 g of a uniform dispersion of spherical microcapsules (D[3,2] = 5.3 μm) with an organic crystalline shell was obtained.

[0235] Example 10: To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate, 2 g of cyclohexyl isocyanate, and 2 mg of Nile Red dye. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Next, 1.48 g of 1,8-diaminooctane dissolved in 10 g of water was added dropwise to the emulsion over 15 minutes using a syringe pump. After the addition, stirring and temperature were maintained for an additional 18 hours. Overall, 108 g of a uniform dispersion of spherical microcapsules (D[3,2] = 5.2 μm) with an organic crystalline shell was obtained.

[0236] Example 11 To prepare the aqueous phase, 1.6 g of PVP was dissolved in 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. The oil phase was added to the aqueous phase in the reactor and homogenized at 5000 RPM for 5 minutes using a Silverson L4RT (rotor-stator dispersion tool) to generate an oil-in-water emulsion. The temperature was maintained at 20°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Then, 1.48 g of 1,8-diaminooctane dissolved in 10 g of water was added dropwise to the emulsion over 5 minutes. After addition, the stirring and temperature were maintained for an additional 18 hours. Overall, 100 g of a uniform dispersion of spherical microcapsules (D[3,2]=4.3 μm) with an organic crystalline shell was obtained.

[0237] Example 12 To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of cyclohexyl isocyanate. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12 °C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 180 RPM. Next, 0.92 g of 1,8-diaminooctane and 0.16 g of tris(2-amino-ethyl)amine were mixed together and dissolved in 10 g of water. The amine solution was added dropwise to the emulsion over 15 minutes using a syringe pump. After addition, stirring and temperature were maintained for an additional 18 hours. Overall, 105 g of a uniform dispersion of spherical microcapsules (D[3,2] = 6 μm) with an organic crystalline shell was obtained.

[0238] Example 13 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 minutes until a clear aqueous solution was obtained. 4.0 g of a 10 wt% aqueous solution of PVA1 was then added, and the entire solution was placed in an ultrasonic bath for 5 minutes. The oil phase was prepared by mixing 11.33 g of hexyl salicylate with 2.0 g of toluene-2,4-diisocyanate. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing for 5 minutes at 5000 RPM using a Silverson L4RT rotor-stator dispersing tool. A temperature of 12°C was maintained during emulsification. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 400 RPM. Then, 2.27 g of cyclohexylamine dissolved in 20 g of water was added to the emulsion over 15 minutes at 12°C using a syringe pump. After addition, the temperature was raised to 30°C and maintained with stirring for 18 hours. Overall, 77 g of a uniform dispersion of spherical and monodisperse microcapsules (D[3,2] = 3.1 m) with an organic crystalline shell was obtained.

[0239] Example 14 To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of isophorone diisocyanate. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 400 RPM. 2.27 g of cyclohexylamine was then dissolved in 10 g of water. This amine solution was added dropwise to the emulsion over a 15-minute period using a syringe pump. After the addition was complete, the temperature was increased to 20°C and stirring and temperature were maintained for an additional 18 hours. Overall, 95.2 g of a uniform dispersion of spherical microcapsules (D[3,2] = 1.7 μm) with an organic crystalline shell was obtained.

[0240] Example 15 To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate and 2 g of sebacoyl dichloride. The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT (rotor-stator dispersing tool) at 5000 RPM for 5 minutes. The temperature was maintained at 12°C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 400 RPM. Next, 1.65 g of cyclohexylamine was dissolved in 10 g of water. This amine solution was added dropwise to the emulsion over a 15-minute period using a syringe pump. After the addition was complete, the temperature was increased to 20°C and stirring and temperature were maintained for a further 18 hours. Overall, 96 g of a uniform dispersion of spherical microcapsules (D[3,2] = 9.6 μm) with an organic crystalline shell was obtained.

[0241] Example 16 To prepare the aqueous phase, 4 g of a 10 wt% aqueous solution of PVA1 was mixed with 80 g of water. The oil phase was prepared by mixing 11.33 g of hexyl salicylate, 2 g of cyclohexyl isocyanate, and 0.046 g of 1,4-diazabicyclo[2.2.2]octane (DABCO). The aqueous phase was transferred to a jacketed reactor. A water bath (Julabo Me v.2) was used to circulate water outside the reactor for temperature control. An oil-in-water emulsion was generated by adding the oil phase to the aqueous phase in the reactor and homogenizing with a Silverson L4RT rotor-stator dispersing tool at 5000 RPM for 5 minutes. The temperature was maintained at 12 °C. After emulsification, the Silverson was replaced with an overhead stirrer (IKA Eurostar) equipped with a Rushton turbine, and the emulsion was stirred at 400 RPM. Next, 1.18 g of 1,6-hexanediol was dissolved in 10 g of water. This solution was added dropwise to the emulsion over 15 minutes using a syringe pump. After addition was complete, the temperature was increased to 20°C, and stirring and temperature were maintained for an additional 18 hours, then increased to 50°C and maintained for 2 hours. Overall, 87 g of a uniform dispersion of spherical microcapsules (D[3,2] = 3.8 μm) with an organic crystalline shell was obtained.

[0242] release rate The slurries obtained in Examples 1 (with Laponite) and 10 (without Laponite) were tested using the method for determining release rate described above. To understand the resistance to release offered by the microparticle shell, dissolution and leakage of unencapsulated hexyl salicylate were also observed in comparison using the same method. It was found that the microparticles of Examples 1 and 10 prepared using PVA1 or a combination of PVA1 and Laponite1 produced similar results, since in each case only less than 20% of the hexyl salicylate was released after about 5 hours, at which point about 90% of the unencapsulated hexyl salicylate had already leaked out.

Claims

1. 1. A method for making microparticles comprising at least one organic active compound encapsulated by a shell of an organic wall material, 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 to the emulsion obtained in step ii., thereby obtaining an aqueous suspension of the microparticles. wherein either 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 acid 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; A method wherein 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.

2. 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, while 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. 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, RG2 being in particular an amino group or a combination of an amino group and a hydroxyl group; ii. The method of claim 1 or 2, wherein the first reactive group (RG1) is selected from a carbonyl halide group and a carboxylic acid anhydride group, and the second reactive group (RG2) is a primary amino group.

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

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

6. The method according to any one of claims 1 to 5, having at least one of the following characteristics (a) to (d): (a) the organic active compounds to be encapsulated are selected from pesticides, aroma 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 water-immiscible liquid at 25°C and 1 bar; (d) the weight ratio of said shell-forming compound to said water-immiscible liquid is in the range of 1:1 to 1:

50.

7. 7. The method of claim 6, wherein the organic compound to be encapsulated is an aroma chemical or a pesticide.

8. 8. The method according to any one of claims 1 to 7, wherein the emulsification step ii. is carried out in the presence of at least one dispersing agent, in particular selected from the group consisting of polysaccharides, polyvinyl alcohols, polymers containing sulfonate groups, polymers containing carboxylate groups, polyvinylpyrrolidone copolymers of vinylpyrrolidone and inorganic Pickering stabilizers.

9. The method of claim 8 , wherein the dispersing agent comprises at least a phyllosilicate.

10. 10. The method of any one of claims 1 to 9, wherein emulsifying comprises mixing the solution of step i. with an aqueous phase and homogenizing the mixture.

11. 1. A microparticle comprising at least one organic active compound encapsulated by a shell of 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 one of the first shell-forming compound (SFC1) or the second shell-forming compound (SFC2) has from 1 to 6 first reactive groups (RG1) per molecule selected from isocyanate groups, isothiocyanate groups, carbonyl halide groups, and carboxylic acid anhydride groups, and the other shell-forming compound has from 1 to 6 second reactive groups (RG2) per molecule selected from primary amino groups and thiol groups, and wherein 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.

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

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

14. 14. Microparticles according to any one of claims 11 to 13, wherein the encapsulated organic compounds are selected from pesticides, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effect compounds.

15. The microparticles according to any one of claims 11 to 14, comprising inorganic Pickering-based particles.

16. A product comprising the microparticles according to 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. 16. Use of microparticles according to any one of claims 11 to 15 containing encapsulated aroma chemicals as an additive to impart a scent or flavour to a product selected from perfumes, laundry and cleaning products, cosmetics, personal care products, hygiene products, food, food supplements, fragrance dispensers and fragrances.

18. Use of the microparticles according to any one of claims 11 to 15 for the sustained release of said organic active compound.

Images