EP2142293A2 - Enzymatic method for the production of microcapsules - Google Patents

Abstract

The invention relates to a method for the production of microcapsules that contain a capsule core containing an effective substance and a capsule shell containing a polymer, comprising the formation of the capsule shell by means of the enzyme-catalyzed polymerization of monomers that are present in an inverse mini-emulsion; and microcapsules and dispersions. The invention relates to the use of said microcapsules and dispersions containing microcapsules as components in dyes, cosmetics, pharmaceuticals, phytosanitary agents, fertilizers, additives for foods or animal feeds, adjuvants for polymers, paper, textiles, leather, or detergents and cleaning agents.

Description

 Enzymatic process for the preparation of microcapsules

The present invention is a process for the preparation of microcapsules comprising a polymer-containing capsule shell and a Kapstoffhülle containing effect. A further subject relates to microcapsules and dispersions containing microcapsules obtainable by the process according to the invention. A further subject matter relates to the use of said microcapsules and microcapsule-containing dispersions as a component in colorants, cosmetics, pharmaceuticals, crop protection agents, fertilizers, additives for food or animal feed, auxiliaries for polymers, paper, textile, leather, paints or detergents and cleaners.

Combinations of preferred features with other preferred features are encompassed by the present invention.

Microcapsules are known in various embodiments and are used depending on the tightness of the capsule wall for very different purposes. For example, they serve to protect core materials that are to be released only by targeted mechanical destruction of the capsule shell, for example, dye precursors for copying papers or encapsulated fragrances. Capsule shell materials based on gelatin, polyurethane resin, melamine-formaldehyde resin and polyacrylate are known in such fields of application. Other requirements are placed on wall materials for vegetable or pharmaceutically active substances as core materials, in which the permeability of the capsule shell is required, which enables a controlled release and the targeted transport of the active substances. Besides the capsules produced by chemical processes, here also known are mechanical-physical production processes.

For the production of microcapsules chemical or physical methods are generally known. In physical methods usually dissolved polymers are applied to the material to be encapsulated and transferred by physical methods, such as spray drying or solvent removal, in a solid capsule wall. In chemical methods, the solid capsule wall is formed by chemical reaction, for example by polymerization of monomers, on the material to be encapsulated. An additional physical step to form the solid microcapsule is not necessary.

Microcapsules comprising a polymer-containing capsule shell and an active substance-containing capsule core, as well as their production methods, are well known. Such microcapsules can be prepared starting from polymeric starting materials for the capsule shell.

Fig Thus, EP 1 421 990 relates to a process for the preparation of microcapsules wherein a polyester dispersed in a polyol is emulsified with an enzyme as an effect substance dispersed in a polyol.

US 4,637,905 relates to a process for the preparation of microcapsules having 1 to 2000 microns, wherein a dispersion of polylactic acid with a protein prepared as effect material, evaporates a portion of the solvent and finally the concentrated dispersion is added to a third solvent for encapsulation of the effect substance. WO 2002/069922 relates to microcapsules with an oxidoreductase-containing aqueous core and a polyester-containing shell. The preparation is carried out by emulsifying an aqueous enzyme solution with a polyester dissolved in an organic solvent, followed by introducing the primary emulsion into an aqueous solvent and then removing the organic solvents.

EP 1 275 378 relates to a physical process for the preparation of particulate constructs wherein an emulsion of synthase and alkyl coenzyme A is prepared, then polymerized, and finally the particulate by removal of the solvents

Construct is made.

US Pat. No. 6,022,500 relates to a physical process for the preparation of polymeric microspheres in which an emulsion of monomers is first used to prepare and isolate a polymeric microsphere which is subsequently brought into contact with a substance solution so that the microsphere is filled with this substance.

The use of enzymes for the polymerization of monomers in aqueous emulsion is generally known, for example from WO 2004/035801, WO 2006/058697 or WO 2006/058696. In each case polymer particles are formed with a massive polymer matrix.

DE 102005007374 relates to nanoparticles of the core-shell type. The shell defines a polymer that is hydrophobic and biocompatible. The polymer is, for example, polyacrylate, polyepoxide, polyurethane or polyester. The core defines an active which is enclosed by the polymer of the shell. The preparation is carried out by free-radical polymerization, polyaddition, polycondensation or enzymatic or anionic polymerization. Details of the method or examples are not mentioned.

The object of the present invention was to provide a novel process for the production of microcapsules comprising a polymer-containing capsule shell and an active substance-containing capsule core. In particular, it was an object of the present invention to provide a process in which the polymer-containing capsule shell is essentially built up from monomers only during the encapsulation. Another aspect of the object was to provide the polymer-containing capsule shell with mild reaction. production conditions, so that even sensitive effect substances can be encapsulated.

The object was achieved by a process for the production of microcapsules containing an active substance-containing capsule core and a polymer-containing capsule shell comprising the formation of the capsule shell by means of enzyme-catalyzed polymerization of monomers which are present in an inverse miniemulsion.

By means of the method according to the invention, an ensemble of microcapsules is generally produced. The inventive method usually leads to the same or similar shaped microcapsules. Microcapsules prepared according to the invention can take on any shape. They are preferably substantially spherical, for example, ideally spherical, constructed.

A microcapsule prepared according to the invention comprises a capsule shell and a capsule core. According to the invention, it is also intended to obtain a microcapsule comprising at least one capsule shell and at least one capsule core. For example, a microcapsule may have a capsule core and two capsule shells. Likewise, a microcapsule, for example, a plurality of capsule cores, for example two nebeneinan- or two nested capsule cores, and a capsule shell, for example, two side by side or nested capsule shells have. Preferably, a microcapsule comprises a capsule shell and a capsule core. The inventive method usually leads to the same or similar microcapsules. Since the method according to the invention produces an ensemble of microcapsules, a few microcapsules can differ in their construction and, for example, contain no capsule core.

The average diameter of the microcapsules (detectable as Z-means by light scattering of a 1 wt .-% aqueous dispersion of microcapsules obtainable by diluting the microcapsules with water and optionally separating an organic phase) can vary widely. It is generally more than 0.1 μm, preferably more than 0.6 μm, particularly preferably more than 0.8 μm. The diameter is preferably in the range from 0.1 to 2000 .mu.m, preferably from 0.6 to 1000 .mu.m, in particular from 0.8 to 800 .mu.m. A capsule diameter which is in the lower range is preferred if a higher mechanical stability of the microcapsules is desired. A diameter in the higher range is preferred in order to pack as much capsule content as possible in a small amount of wall material.

The thickness of the capsule shell can vary within a wide range. It is generally from 0.1 to 90%, preferably from 0.5 to 20% of the capsule radius (determinable by light / electron microscopy or light scattering). The surface of the microcapsules may have functional groups. It is preferably low, especially not functionalized, to prevent covalent or ionic interactions during storage or use. If the surface is poorly functionalized, preferably below 0.02 there are functional groups per nm ² on the surface (for example determinable by quantification of the functional groups by means of titration, by labeling with color reagents, or, if the groups have electric charges, by measurement of the electrophoretic mobility or the ζ potential). Functional groups on the surface are understood in accordance with the invention to be those which are introduced into the polymer surface in a targeted manner by means of special monomers. Terminal alcohol, acid or ester groups of the shell polymers are naturally present.

The capsule core comprises at least one effect substance. The effect substance is present in the core usually in solid, dissolved, emulsified or dispersed form. In a preferred embodiment, the capsule core comprises at least one effect substance and at least one inert substance, which is preferably a liquid. Suitable inert substances are, for example, all compounds present in the process according to the invention: dispersants, polar and / or nonpolar liquids, water or the catalytically active enzymes. In particular, the capsule core comprises at least one effect substance and at least one polar solvent. The capsule core may also contain an incompletely polymerized monomer. In a preferred embodiment, the capsule core comprises at least one polar liquid which forms the disperse phase of the inverse miniemulsion.

According to the invention, enzymes are used in the process for preparing the microcapsules which catalyze the polymerization of the monomers present in an inverse miniemulsion to form the capsule shell.

For describing enzymes, the EC classes developed by the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (NC-IUBMB) are used.

Suitable enzymes are all enzyme classes, preferably hydrolases and oxidoreductases, particularly preferably hydrolases. Also mixtures of different classes of enzymes are suitable.

Suitable hydrolases [EC 3.xxx] are, for example, esterases [EC 3.1.xx], proteases [EC 3.4.XX], hydrolases which react with other CN bonds as peptide bonds [EC 3.5. xx] or hydrolases that react with acid anhydrides [EC 3.6. xx]. Carboxylesterases [EC 3.1.1.1], lipases [EC 3.1.1.3] or cutinases [EC 3.1.1.47] are particularly advantageously used according to the invention. Examples thereof are lipomas from Achromobacter sp., Aspergillus sp., Candida sp., Candida antarctica, Mucor sp., Penicilium sp., Geotricum sp., Rhizopus sp., Burkholderia sp., Pseudomonas sp., Pseudomonas cepacia , Thermomyces sp., Porcine pancreas or sprouts and carboxylesterases from Bacillus sp., Pseudomonas sp., Burkholderia sp., Mucor sp., Saccharomyces sp., Rhizopus sp., Thermoanaerobium sp., pork liver or horse liver.

Of course, it is possible to use a single hydrolase or a mixture of different hydrolases. It is also possible to use the hydrolases in free and / or immobilized form.

Preference is given to using lipase from Pseudomonas cepacia, Burkholderia platarii or Candida antarctica type B in free or immobilized form (for example Novozym® 435 from Novozymes A / S, Denmark).

Preferred oxidoreductases [EC 1.x.x.x] are peroxidases [EC 1.11.1.x] and laccases [EC 1.10.3.2] in free or immobilized form. Enzyme-specific adjuvants such as iron salts, acetylacetone or hydrogen peroxide are well known to those skilled in the art.

The total amount of the enzymes used is generally from 0.001 to 40% by weight, often from 0.1 to 15% by weight and often from 0.5 to 10% by weight, based in each case on the total amount of monomers. The amount depends on the purity of the enzyme used. Technical or immobilized enzymes are usually used in higher amounts than purified enzymes. The skilled person will also adjust the amount of catalyst according to how fast the reaction is to proceed.

Enzyme-catalyzed polymerizations of monomers are well known, for example, from Kobayashi et al., Chem. Rev 2001, 101, 3793-3818. The person skilled in the art selects an enzyme catalyzing the polymerization, depending on the type of monomer. Oxidoreductases catalyze, for example, the polymerization of phenols, anilines or vinylic monomers. Hydrolases catalyze, for example, the polymerization of diols with diacids or diesters, of diamines with diacids or diesters, of lactones or of carbonates. The application of an enzyme-catalyzed polymerization can take place in the presence of other polymerization-catalyzing compounds. The application of an enzyme-catalyzed polymerization can also take place before or after non-enzymatically catalyzed polymerization.

Suitable monomers for the reaction with hydrolases are hydroxycarboxylic acid compounds, dialcohol compounds or diacid compounds, especially hydroxycarboxylic acid compounds. A combination of the above monomers is also possible, with the combination of dialcohol compounds and diacid compounds being preferred.

In a preferred embodiment, the monomers are combined with a starter monomer comprising a hydroxycarboxylic acid compound, dialcohol compound or is a diacid compound. The starter monomer is preferably a dialcohol compound as described below, especially ethylene glycol, 1,4-butanediol, glycerol, sorbitol, monosaccharide, disaccharide, polysaccharide or hydroxy-functional, dendritic polyesters based on 2,2-dimethylolpropionic acid (Boltorn® Types, commercially available from Perstorp).

Hydroxycarboxylic acid compounds which can be used are the free hydroxycarboxylic acids having at least one free alcohol group and at least one free carboxylic acid group, their C 1 -C 5 -alkyl esters and / or their lactones. Examples include glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid (6-

Hydroxycaproic acid), 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxycaproic acid, their cyclic derivatives such as glycolide (1, 4-dioxane-2,5-dione), D, L, D, L-dilactide (3,6-hydroxycaproic acid). Dimethyl-1,4-dioxane-2,5-dione), ε-caprolactone, β-butyrolactone, γ-butyrolactone, ω-dodecanolide (oxacyclotridecan-2-one), ω-undecanolide (oxacyclododecan-2-one) or ω-pentadecanolide (oxacyclohexadecan-2-one).

Also suitable as lactones are bis- or tris-lactones which contain two or three lactone groups. For example, (2,2'-bis (ε-caprolactone-4-yl) propane can be used.) Bis-lactones can be synthesized, for example, according to Palmgren et al., Journal of Polymer Science A, 1997, 35, 1635-1649. Likewise suitable are the esters of carbonic acid (carbonates), especially linear and cyclic aliphatic carbonates, preferably C 1 to C 6 -alkyl esters of carbonic acid, in particular trimethylene carbonate Carbonates which do not react with the particular enzyme, for example propylene carbonate, are unsuitable as monomers Hydroxycarboxylic acid compounds may also be used the thiocarboxylic acid analogous to the abovementioned hydroxycarboxylic acid compounds and their esters and thiolactones.

Of course, mixtures of different hydroxycarboxylic acid compounds can be used. Preferred hydroxycarboxylic acid compounds are lactones, in particular C 2 - to C 18 -alkylene lactones, very particularly preferably ε-caprolactone.

As dicarboxylic acid compounds, it is possible in principle to use all C 2 -C 4 aliphatic, C 3 -C 20 cycloaliphatic, aromatic or heteroaromatic compounds which have at least two carboxylic acid groups (carboxy groups, -COOH) or derivatives thereof. Particularly suitable derivatives are C 1 -C 10 -alkyl, preferably methyl, ethyl, n-propyl or isopropyl mono- or diesters of the aforementioned dicarboxylic acids, and also the corresponding dicarboxylic acid anhydrides. Examples of dicarboxylic acid compounds are ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nandanedioic acid (azelaic acid), Decanedioic acid (sebacic acid), undecanedioic acid, dodecane diacid, tridecanedioic acid (brassylic acid), C32 dimer fatty acid benzene-1, 2-dicarboxylic acid (Phthalic acid), benzene-1, 3-dicarboxylic acid (isophthalic acid) or benzene-1, 4-dicarboxylic acid (terephthalic acid), its methyl ester, for example methyl ethanedioate, dimethyl propanedioate, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexanedioate, heptanedioic dimethyl ester, octanedioic dimethyl ester, Dimethyl nonanedioate, dimethyl decanedioate, undecanedioic dimethylester, dodecanedioic acid dimethylester, tridecanedioic dimethylester, C32 dimer fatty acid dimethylester, dimethyl phthalate, dimethyl isophthalate or terephthalic acid dimethyl ester, and their anhydrides, for example butanedicarboxylic, pentanedicarboxylic or phthalic anhydride. Of course, mixtures of the aforementioned dicarboxylic acid compounds can be used. Oligoesters and polyesters having at least two free carboxy groups, in particular carboxy-terminated oligo- and polyesters, can likewise be used as the dicarboxylic acid component. Likewise, the esters of polycarboxylic acids such as citric acid and butanetetracarboxylic acid can be used.

Preference is given to using the free dicarboxylic acids, especially C ₄ to C 36 aliphatic dicarboxylic acids, in particular butanedioic acid, hexanedioic acid, decanedioic acid, dodecanedioic acid or their corresponding dimethyl and diethyl esters.

As the diol compounds, there can be used branched or linear alkanes having 2 to 18 carbon atoms, preferably 4 to 14 carbon atoms, cycloalkanes having 5 to 20 carbon atoms, or aromatic compounds containing at least two alcohol groups. Examples of suitable alkanediols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 1-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, 2,4-dimethyl-2-ethyl-1,3-hexanediol , 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol or 2,2, 4-trimethyl-1,6-hexanediol. Particularly suitable are ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1, 3-propanediol, 1, 6-hexanediol or 1, 12-dodecanediol. Examples of cycloalkanediols are 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol (1,2-dimethylolcyclohexane), 1,3 Cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1,4-cyclohexanedimethanol (1,4-dimethylolcyclohexane) or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

Examples of suitable aromatic diols are 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), 1,3-dihydroxynaphthalene, 1,5 Dihydroxynaphthalene or 1, 7-dihydroxynaphthalene. However, as diol compounds it is also possible to use polyether diols, for example diethylene glycol, triethylene glycol, polyethylene glycol (with more than 4 ethylene oxide units), propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (with more than 4 percent pylene oxide units) and polytetrahydrofuran (poly-THF), in particular diethylene glycol, triethylene glycol and polyethylene glycol (with more than 4 ethylene oxide units) are used. As poly-THF, polyethylene glycol or polypropylene glycol find compounds whose number average molecular weight (Mn) is usually in the range of 200 to 10,000, preferably from 600 to 5000 g / mol.

Also suitable are oligoesters and polyesters having at least two free alcohol groups, preferably dihydroxy-terminated oligo- and polyesters. Further examples of suitable diol compounds having more than two alcohol groups are glycerol, sorbitol, trimethylolpropane, pentaerythritol, monosaccharides such as fructose, glycosides or mannose, disaccharides such as sucrose, oligosaccharides and their substitution products, or cellulose derivatives such as acetates.

As diol compounds, it is also possible to use one of the abovementioned diol compounds analogous dithiol. Of course, it is also possible to use mixtures of the abovementioned diol compounds or dithiols.

Preference is given to aliphatic alkanediols and polyetherdiols, particularly preferably linear and branched aliphatic alkanediols having 2 to 18 carbon atoms, in particular ethylene glycol, 1,4-butanediol, 1,6-hexanediol, sorbitol and neopentyl glycol.

From the monomers described above, linear, branched or crosslinked polyesters can be formed, depending on whether difunctional monomers or higher-functional monomers are used.

Suitable monomers for reaction with oxidoreductases are phenols, anilines and vinylic monomers. Suitable phenols are phenol and mono- and polysubstituted phenol. Substituents may be, for example, halogen, C 1 -C 6 -alkyl, mono- or polynuclear aryl or amine. As anilines aniline and mono- and polysubstituted anilines are suitable. Substituents may be, for example, halogen, C 1 -C 6 -alkyl, mono- or polynuclear aryl or hydroxy. Suitable vinylic monomers are compounds having at least one non-aromatic double bond. Examples are (meth) acrylic acid and its C 1 to C 30 -aliphatic alkyl esters, itaconic acid and their C 1 to C 30 -aliphatic alkyl esters, or styrenes. Suitable styrenes are styrene and mono- and polysubstituted styrenes. Substituents can be, for example, halogen, C 1 -C 6 -alkyl, mono- or polynuclear aryl, amine or hydroxy.

Preference is given to vinylic monomers, in particular (meth) acrylic acid and their Ci to C3o-aliphatic alkyl esters or styrene.

The monomers are generally in the reaction mixture to 0.1 to 20 wt .-% by weight, preferably from 0.5 to 10 wt .-% by weight, in particular from 1 to 5 wt .-% by weight .-% based on the total batch included. In a preferred embodiment at least one lactone to 0.1 to 20 wt .-% by weight, preferably 0.5 to 10 wt .-%, in particular to 1 to 5 wt .-% based on the total amount.

According to the method of the invention, dispersants can be used. These may in principle be protective colloids, emulsifiers or mixtures thereof. It goes without saying that the emulsifiers and / or protective colloids are selected so that they are compatible in particular with the enzymes used and do not deactivate them.

The polymerization can be carried out in the presence of protective colloids, if appropriate also in addition to emulsifiers. They generally have average molecular weights Mw of above 500, preferably of more than 1000 g / mol. Examples of protective colloids are polyvinyl alcohols, cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycols, graft polymers of vinyl acetate and / or vinylpropionate on polyethylene glycols, polyethylene glycols end-capped on one or both sides with alkyl, carboxyl or amino groups, polydiallyldimethylammonium chlorides and / or or polysaccharides such as, in particular, water-soluble starches or starch derivatives.

Often, only emulsifiers are used as dispersants. In general, emulsifiers are used whose relative molecular weights, in contrast to the protective colloids, are usually below 1000 g / mol. They may be anionic, cationic or nonionic in nature. Of course, in the case of the use of mixtures of surface-active substances, the individual components must be compatible with one another, which can be checked in case of doubt by means of fewer preliminary tests. In general, anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other.

If desired, the polymerization can also be carried out in the presence of finely divided, water-insoluble inorganic emulsifiers (so-called Pickering emulsifiers), for example barium sulfate.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation from 3 to 50, alkyl radical: C ₄ to C 12) and ethoxylated fatty alcohols (degree of ethoxylation from 3 to 80, alkyl radical: Cs to C 36). Examples include the Lutensol® A grades (C12 to Cu fatty alcohol ethoxylates, degree of ethoxylation from 3 to 8), Lutensol® AO grades (C13 to Cis oxo alcohol ethoxylates, ethoxylation levels of 3 to 30), Lutensol® AT grades (C16 to Cis fatty alcohol ethoxylates, degree of ethoxylation from 1 1 to 80), Lutensol® ON grades (C10 oxo alcohol ethoxylates, ethoxylates) from 3 to 11) and the Lutensol® TO grades (C13-oxoalcohol ethoxylates, degree of ethoxylation from 3 to 20) from BASF SE.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8 to C12), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation from 4 to 30, alkyl radical: C12 to C18) and ethoxylated alkylphenols (degree of ethoxylation from 3 to 50, alkyl radical: C ₄ to C 12), of alkylsulfonic acids (alkyl radical: C 12 to C 18) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis).

Further anionic emulsifiers further compounds of the general formula (I)

wherein R ¹ and R ^{2 are} H atoms or C ₄ - to C 24 -alkyl and are not simultaneously H atoms, and M ¹ and M ^{2 may be} alkali metal ions and / or ammonium ions proved. In the general formula (I), R ¹ and R ^{2 are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R ¹ and R ^{2 are} not both simultaneously H and Atoms are. M ¹ and M ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous compounds (I) are those in which M ¹ and M ^{2 are} sodium, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} an H atom or R ¹ . Frequently, technical mixtures are used which have a proportion of 50 to 90% by weight of the monoalkylated product, such as, for example, Dowfax® 2A1 (trademark of the Dow Chemical Company). Suitable cationic emulsifiers are generally cationic salts having Cβ to Cis-alkyl, -alkylaryl or heterocyclic radicals, for example primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding sulphate, the sulphates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffins, N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate, and the mini-surfactant N, N '- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl N-methylammonium sulfate and ethoxylated oleylamine (for example Uniperol® AC from BASF Aktiengesellschaft, about 12 ethylene oxide units). It is essential that the anionic counter groups are as low as possible nucleophilic, such as perchlorate, Sulfate, phosphate, nitrate and carboxylates such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids such as methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate , Tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

Preferred emulsifiers are nonionic emulsifiers, in particular ethoxylated alcohols and sorbitan esters, particularly preferably ethoxylated fatty alcohols and sorbitan fatty acid esters. Very particularly preferred mixtures include ethoxylated alcohols and sorbitan esters. In a preferred embodiment, the mixtures contain ethoxylated alcohols and sorbitan esters.

In a further preferred embodiment, a polymer based on the ene reaction product of polyisobutylene and maleic anhydride (PIBSA) and

Di (alkyl) ethanolamine suitable. In a further preferred embodiment block copolymers are suitable, as described in Macromolecules 38 (16), 6882-6887, block copolymers based on isoprene and methyl methacrylate as described in WO 2008/009424, or poly ((ethylene -co-butylene) -block-ethylene oxide).

The emulsifiers preferably used as dispersants are advantageously used in a total amount of 0.005 to 20 wt .-%, preferably 0.01 to 15 wt .-%, in particular 0.1 to 10 wt .-%, each based on the total mixture.

The total amount of the protective colloids used as dispersing agents in addition to or instead of the emulsifiers is often from 0.1 to 10% by weight and frequently from 0.2 to 7% by weight, based in each case on the overall batch.

The inverse miniemulsion according to the invention, in which the monomers are present, comprises a continuous nonpolar phase and a discontinuous polar phase. The polar phase comprises a polar liquid and the non-polar phase a non-polar liquid.

The effect substance is essentially in the discontinuous phase in solid, dissolved, emulsified or dispersed form. The monomers, dispersants or enzymes can be present both distributed in one of the two phases as well as in both phases, or at the interface of the two phases. In a preferred embodiment, the monomer is at least 50% by weight, preferably at least 60% by weight and in particular at least 80% by weight in the polar phase. In a further preferred embodiment, the polar liquid consists of at least one monomer and at least one effect substance.

The mean size of the droplets of the discontinuous phase of the inverse miniemulsion according to the invention can preferably be determined according to the principle of quasi-elastic dynamic light scattering on a 1% by weight miniemulsion obtainable by diluting the inverse miniemulsion with the appropriate continuous phase and optionally separating one organic phase (the so-called z-mean droplet diameter d _{z of} the unimodal analysis of the autocorrelation function). Further determination methods are light or electron microscopy, as well as Feldflußfraktionierung. According to the invention, the values for d _z thus determined for the inverse miniemulsions are normally below 10000 nm, often below 1000 nm, usually below 500 nm. The d _z range from 2000 nm to 1000 nm is favorable in accordance with the invention. In the normal case, d _{z is} according to the invention Inverse mini-emulsion to be used above 40 nm.

Suitable polar liquids are those whose solubility in the continuous nonpolar phase under reaction conditions is below 40% by weight, preferably below 10% by weight and in particular below 1% by weight (in each case based on the total amount of the continuous phase) that a separate discontinuous polar phase is present. In a preferred embodiment, the polar liquid at 20 ^° C. dissolves the polymer of the capsule shell at most to 10% by weight, preferably at most up to 3% by weight and especially at most up to 0.5% by weight, in each case based on the total mass of the polymer.

Suitable polar liquids are, for example, monools, such as Cs-Cβ-alkanols, in particular tert-butanol and tert. -Amyl alcohol, pyridine, poly-Ci-C4-alkylenglykoldi- Ci-C4-alkyl ethers, in particular polyethylene glycol di-Ci-C4-alkyl ethers, such. Dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, C 2 -C 4 -alkylene carbonates, in particular propylene carbonate, C 3 -C 6 -alkyl acetic acid esters, in particular tert-butylacetic acid esters, acetone, 1, 4-dioxane, 1, 3-dioxolane, tetrahydrofuran, Dimethoxymethane, dimethoxyethane, aqueous buffers or water. Of course it is also possible to use mixtures of the abovementioned solvents. Suitable polar liquids are also the abovementioned monomers or mixtures thereof.

The polar liquid may, for example, also comprise the effect substance used or may consist of it. Preferred polar liquid is propylene carbonate and propylene carbonate containing mixtures. In a preferred embodiment, the polar liquid is the monomer or monomers. When a lactone is used as the monomer, the polar liquid comprises less than 5% by weight, preferably less than 1% by weight and in particular less than 0.1% by weight of water. When the polar liquid contains water, it is advantageous if the aqueous reaction medium at room temperature (20 to 25 ⁰ C) has a pH of 2 to 1 1, often from 3 to 9 and often from 6 to 8. In particular, in the aqueous reaction medium, a pH is set in which the enzyme has a high catalytic activity and a long service life. The appropriate measures for pH adjustment, ie addition of appropriate amounts of acid, for example sulfuric acid, bases, for example aqueous solutions of alkali metal hydroxides, in particular sodium or potassium hydroxide, or buffer substances, for example KaIi- umdihydrogenphosphat / disodium hydrogen phosphate, acetic acid / sodium acetate, ammonium hydroxide / Ammonium chloride, potassium dihydrogen phosphate / sodium hydroxide, borax / hydrochloric acid, borax / sodium hydroxide or tris (hydroxymethyl) aminomethane / hydrochloric acid are familiar to those skilled in the art.

In order to further increase the polarity of the polar phase, it may additionally contain so-called hydrophilic agents. Suitable hydrophiles are, for example, organic or inorganic salts or uncharged, very polar compounds. Examples of inorganic salts are sodium nitrite, sodium chloride, potassium chloride, lithium chloride, rubidium chloride. Examples of organic salts are trialkylammonium salts, ionic liquids such as ethyl-methylimidazolium salts, or oligomers having stoichiometric proportions of anionic and cationic groups in the main or side chain. Preference is given to hydrophiles which do not reduce the catalytic activity of the enzymes.

Suitable nonpolar liquids are those whose solubility in the discontinuous polar phase at reaction conditions is below 10% by weight, preferably below 1% by weight and in particular below 0.1% by weight (in each case based on the total amount of the continuous phase) so that there is a separate continuous polar phase.

Suitable non-polar liquids are, for example, liquid aliphatic or aromatic hydrocarbons having 5 to 30 C atoms, for example n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n-nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene. Also suitable are hydrocarbon mixtures in the boiling range from 30 to 250 ⁰ C come as partially hydrogenated petroleum distillates (eg Isopar® brands Fa. Exxon Mobil). Also suitable are olefins, for example polyisobutylenes or C6 to C30 alpha-olefins. Also usable are hydroxy compounds, such as saturated and unsaturated fatty alcohols having 10 to 28 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, esters, such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and 1 to 10 carbon atoms in the alcohol moiety or esters of carboxylic acids and fatty alcohols having 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 carbon atoms in the alcohol moiety. Further suitable non-polar liquids are paraffin oil (linear hydrocarbon mixture), silicone oil (polysiloxane), perfluorinated hydrocarbons, fluorosilicone oil, perfluorinated polyether, fluorosilane or siloxane, such as dimethylsiloxane.

Preferred non-polar liquids are liquid aliphatic and aromatic hydrocarbons having 5 to 30 carbon atoms, in particular partially hydrogenated mineral oil distillates. In another embodiment, non-polar liquids are paraffin oil. Of course it is also possible to use mixtures of the abovementioned solvents.

The total amount of polar and nonpolar liquids is chosen so that the total batch reaches 100% by weight. It is generally from 10 to 90% by weight, preferably from 40 to 70% by weight, based on the total batch.

The quantitative ratio of polar to nonpolar liquid is chosen so that a discontinuous phase is formed which essentially contains the polar liquid. In a preferred embodiment, 20 to 80, preferably 40 to 70 wt .-% of nonpolar liquid used, each based on the total batch. In a further preferred embodiment, from 20 to 80% by weight, preferably from 30 to 60% by weight, of polar liquid is used, in each case based on the overall batch. In a further preferred embodiment, from 20 to 80, preferably from 35 to 55,% by weight of hydrocarbon mixtures and from 20 to 70% by weight, preferably from 30 to 60% by weight, of propylene carbonate are used, in each case based on the overall batch. Care must be taken that the miniemulsions do not undergo a phase reversal, i. that the hydrophobic continuous phase does not become the disperse phase.

Under effect substances are to be understood in the context of the invention substances which cause the user desired effects in the commercial application of the product according to the invention.

Effect substances are, for example, colorants, cosmetics, pharmaceuticals, crop protection agents, fertilizers, additives for food or animal feed, auxiliaries for polymers, paper, textile, leather or detergents and cleaners.

Examples of colorants are dyes, printing inks, pigments, UV absorbers, optical brighteners or IR dyes. While organic dyes have an absorption maximum in the wavelength range from 400 to 850 nm, optical brighteners have one or more absorption maxima in the range from 250 to 400 nm. Optical brighteners emit fluorescence radiation in the visible range when irradiated with UV light. Examples of optical brighteners are compounds from the classifications the bisstyrylbenzenes, stilbenes, benzoxazoles, coumarins, pyrenes and naphthalenes. Also suitable are markers for liquids, for example mineral oil markers. UV absorbers are generally UV-absorbing compounds which deactivate the absorbed radiation without radiation. Such compounds are used for example in sunscreens and for the stabilization of organic polymers.

Other suitable effect substances are cosmetics. Cosmetics are substances or preparations of substances that are exclusively or predominantly intended to be externally on the human body or in his oral cavity for cleaning, care, for

Protection, to maintain a good condition, to perfume, to change the appearance or to be used to influence the body odor. Also suitable are, for example, anti-insect agents, such as icaridine or N, N-diethyl-metatoluamide (DEET).

In addition, all drugs can be used as effect substances.

As effect substances and pesticides and fertilizers can be used. Suitable crop protection agents are acaricides, algicides, aphicides, bactericides, fungicides, herbicides, insecticides, molluscicides, nematicides, germination inhibitors, safeners or growth regulators. Fungicides are compounds that kill fungi and their spores or inhibit their growth. Insecticides are compounds that are especially effective against insects and their developmental forms. Herbicides are compounds which are active against generally all wild and cultivated plants that are undesirable at their respective location (harmful plants). Examples of fertilizers are mineral single or multi-nutrient fertilizers, organic and organic-mineral fertilizers or fertilizers with trace nutrients.

In a preferred embodiment, the effect substances are pesticides or mixtures of pesticides. In a further preferred embodiment, the crop protection agents are preferably herbicides, insecticides or fungicides.

The following list of plant protection products indicates, but is not intended to be limited to, any active ingredients.

The fungicide is selected from:

A) strobilurins:

Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin, Kresoxim-methyl, Metomino Strobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyribencarb, Trifloxystrobin, 2- (2- (6- (3-Chloro-2-methyl-phenoxy) -5-fluoro pyrimidin-4-yloxy) -phenyl) -2-methoxy-imino-N-methyl-acetamide, 2- (ortho - ((2,5-dimethylphenyl-oxymethylene) -phenyl) - Methyl 3-methoxyacrylate, 3-methoxy-2- (2- (N- (4-methoxy-phenyl) -cyclopropane-carboxymethoxysilanes) -methylo-acrylic acid methyl ester, 2- (2- (3- (2,6- di-chlorophenyO-i-methyl-allylideneaminooxymethy O-phenoxy-methoxyimino-N-methyl-acetamides; B) carboxamides:

- Carboxylic acid anilides: Benalaxyl, Benalaxyl M, Benodanil, Bixafen, Boscalid, Carboxin, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Isopyrazam, Isotianil, Kiralaxyl, Mepronil, Metalaxyl, Metalaxyl-M, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Tecloftalam, Thifluzamide , Tiadinil, 2-amino-4-methyl-thiazole-5-carboxylic acid anilide, 2-chloro-N- (1, 1, 3-trimethyl-indan-4-yl) -nicotinamide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (2 ', 4'-difluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (2', 4'-dichlorobiphenyl-2-yl) yl) amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (2 ', 5'-difluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole 4-carboxylic acid (2 ', 5'-dichlorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3', 5'-difluorobiphenyl-2-yl) -amide , 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3 ', 5'-dichlorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ( 3'-fluoro-biphenyl-2-yl) -a mid, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3'-chlorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (2 ') -fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (2'-chlorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H- pyrazole-4-carboxylic acid (3 ', 4', 5'-trifluorobiphenyl-2-yl) -amide, 3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxylic acid (2 ', 4', 5 '-trifluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid [2- (1,1,3,3,3,3-hexafluoropropoxy) -phenyl] amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid [2- (1, 1, 2,2-tetrafluoroethoxy) -phenyl] -amide, 3-difluoromethyl-1-methyl-1H-pyrazole 4-carboxylic acid (4'-trifluoromethylthiobiphenyl-2-yl) amide, N- (3 ', 4'-dichloro-5-fluoro-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H pyrazole-4-carboxylic acid amide, N- (2- (1, 3-dimethylbutyl) phenyl) -1,3,3-trimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid amide, N- (4'-chloro-3 ', 5'-difluoro-biphenyl-2-yl) -3-difluoromethyl-1-met hyl-1H-pyrazole-4-carboxylic acid amide, N- (4'-chloro-3 ', 5'-difluoro-biphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole 4-carboxylic acid amide, N- (3 ', 4'-dichloro-5'-fluorobiphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N- (3' , 5'-difluoro-4'-methyl-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (3 ', 5'-difluoro-4'-methyl biphenyl-2-yl) -3-trifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (2-bicyclopropyl-2-ylphenyl) -3-difluoromethyl-1-methyl-1H- pyrazole-4-carboxylic acid amide, N- (cis-2-bicyclopropyl-2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide, N- (trans-2-bicyclopropyl) 2-yl-phenyl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amide;

- Carboxylic acid morpholides: Dimethomorph, Flumorph; Benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-formylamino-2-hydroxybenzamide;

- Other carboxylic acid amides: carpropamide, diclocymet, mandipropamide, oxytetra- cyclin, silthiofam, N- (6-methoxypyridin-3-yl) cyclopropanecarboxamide;

C) Azoles:

- Triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole , Prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1- (4-chloro-phenyl) -2 - ([1, 2,4] triazol-1-yl) -cycloheptanol;

- imidazoles: cyazofamide, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole; Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

- Other: ethaboxam, etridiazole, hymexazole, 2- (4-chloro-phenyl) -N- [4- (3,4-dimethoxyphenyl) -isoxazol-5-yl] -2-prop-2-ynyloxy-acetamide ;

D) Nitrogen-containing heterocyclyl compounds

Pyridines: fluazinam, pyrifenox, 3- [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine, 3- [5- (4-methyl-phenyl) -2, 3-dimethyl-isoxazolidin-3-yl] -pyridine, 2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 3,4,5-trichloropyridine-2,6-dicarbonitrile, N- (1 - (5-Bromo-3-chloro-pyridin-2-yl) -ethyl) -2,4-dichloronotinamide, N - ((5-bromo-3-chloro-pyridin-2-yl) -methyl) -2,4 -dichlornicotinamid;

Pyrimidines: Bupirimat, Cyprodinil, Diflumetorim, Fenarimol, Ferimzone, Mepanipyrim, Nitrapyrin, Nuarimol, Pyrimethanil;

- piperazines: triforins;

- Pyrroles: fludioxonil, fenpiclonil;

- morpholines: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph;

- piperidines: fenpropidine; Dicarboximides: fluorimide, iprodione, procymidone, vinclozolin;

non-aromatic 5-membered heterocycles: famoxadone, fenamidone, octhilinone, trialnazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydropyrazole-1-thiocarboxylic acid S-allyl ester;

- others: acibenzolar-S-methyl, amisulbrom, anilazine, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomethine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, folpet, oxolinic acid, piperaline, proquinazid, pyroquilon, qui - Noxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propyl-chromen-4-one, 5-chloro-1 - (4,6-dimethoxypyrimidin-2-yl) -2-methyl-1 H-benzoimidazole, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a ] pyrimidine, 6- (3,4-dichlorophenyl) -5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6- (4-tert-butylphenyl) -

5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 5-methyl-6- (3,5,5-trimethyl-hexyl) - [1, 2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 5-methyl-6-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6-methyl-5 -octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6-ethyl-5-octyl- [1,2,4] triazolo [1,5-a] pyrimidine-7 -ylamine, 5-ethyl-6-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 5-ethyl-6- (3,5,5-trimethyl-hexyl) - [1, 2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6-octyl-5-propyl- [1,2,4] triazolo [1,5-a] pyrimidine-7 -ylamine, 5-methoxymethyl-6-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6-octyl-5-trifluoromethyl- [1,2,4] triazolo [1,5-a] pyiminim-7-ylamine and 5-trifluoromethyl-6- (3,5,5-trimethyl-hexyl) - [1, 2,4] triazolo [1, 5-a] pyrimidin-7-ylamine;

E) carbamates and dithiocarbamates

Thio and dithiocarbamates: Ferbam, Mancozeb, Maneb, Metam, Methasulphocarb, Metiram, Propineb, Thiram, Zineb, Ziram;

Carbamates: Diethofencarb, Benthiavalicarb, Iprovalicarb, Propamocarb, Propamocarb hydrochloride, Valiphenal, N- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid- (4-fluorophenyl) ester;

F) Other fungicides - guanidines: dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris (albesilat);

- antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxines, streptomycin, validamycin A;

Nitrophenyl derivatives: binapacryl, diclorane, dinobutone, dinocap, nitrothal-isopropyl, tecnazene;

Organometallics: fentin salts such as fentin acetate, fentin chloride, fentin hydroxide;

Sulfur-containing heterocyclyl compounds: dithianone, isoprothiolanes;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;

Organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophene, flusulphamide, hexachlorobenzene, pencycuron, pentachlorophenol and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N- (4-chloro-2-nitro-phenyl) -N-ethyl-4- methyl-benzenesulfonamide; Inorganic active ingredients: phosphorous acid and its salts, Bordeaux broth, copper salts such as copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

- Other: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine, metrafenone, mildiomycin, oxine-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N- (cyclopropylmethoxyimino- (6-difluoromethoxy-2,3-difluorophenyl) - methyl) -2-phenylacetamide, N '- (4- (4-chloro-3-trifluoromethylphenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamide, N' - (4- (4-Fluoro-3-trifluoromethylphenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamidine, N '- (2-methyl-5-trifluoromethyl-4- (3-trimethylsilanyl) propoxy) -phenyl) -N-ethyl-N-methylformamidine, N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy) -phenyl) -N-ethyl-N-methylformamidine;

G) growth regulator

Abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butraline, chlormequat (chlorequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipine, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfid , indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), metconazole, naphthalene acetic acid, N-6-benzyladenine, paclobutrazole, prohexadione (prohexadione-calcium), Prohydrojasmon, thidi- azurone, tri-penthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;

The herbicide is selected from:

Acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, meta la, metazachlor, napropamide, naproanilide, pethoxamide, pretilachlor, propachlor, thenylchloro;

Amino acid analogues: bilanafos, glyphosate, glufosinate, sulfosate; Aryloxyphenoxypropionates: Clodinafop, Cyhalofop-butyl, Fenoxaprop, Fluazifop, Haloxyfop, Metamifop, Propaquizafop, Quizalofop, Quizalofop-P-tefuryl;

Bipyridyls: diquat, paraquat;

Carbamates and thiocarbamates: asulam, butylates, carbamides, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinates, orbencarb, phenmedipham, prosulphocarb, pyributicarb, thiobencarb, triallates;

- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;

- Dinitroanilines: Benfluralin, Ethalfluralin, Oryzalin, Pendimethalin, Prodiamine, Triflura- Nn; Diphenyl ether: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;

Hydroxybenzonitriles: bromoxynil, dichlobenil, loxynil;

Imidazolinone: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; Phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;

- Pyrazines: Chloridazon, Flufenpyr-ethyl, Fluthiacet, Norflurazon, Pyridate;

Pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picoloram, picolinafen, thiazopyr, thiazopyr; Sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl,

Chlorosulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, lodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, Triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1 - ((2-chloro-6-propylimidazo [1,2-b] pyridazin-3-yl) sulfonyl) -3- (4,6-dimethoxypyrimidine) 2-yl) urea;

Triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozine, hexazinone, metachronon, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; Ureas: chlorotoluron, da- muron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, tebuthiuron;

- other inhibitors of acetolactate synthase: bispyribac sodium, cloransulam Methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, orthosulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxime, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfones, pyroxsulam;

- Other: Amicarbazone, Aminotriazole, Anilofos, Beflubutamide, Benazoline, Bencarbazone, Benfluresate, Benzofenap, Bentazone, Benzobicyclone, Bromacil, Bromobutide,

Butafenacil, butamifos, cafenstrole, carfentrazone, cinidone-ethyll, chlorthal, cinnamethyl, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanide, fentrazamide, flumiclorac-pentyl, flumioxazine, flupoxam , Fluorochloridones, flurtamones, indano-fan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazone, oxaziclomefones, pentoxazones, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxyfen , Pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3- [2- (2-methoxy-ethoxymethyl) -6-trifluoromethyl-pyridine-3-carbonyl] -bicyclo [3.2.1] oct-3-en-2-one, (3- [2-chloro-4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6- dihydro-2H-pymidin-1-yl) -phenoxy] -pyridin-2-yloxy) -acetic acid ethyl ester, θ-amino-δ-chloro-cyclopropyl-pyrimidin-4-ca methyl rboxate, 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -pyridazin-4-ol, 4-amino-3-chloro-6- (4-chlorophenyl) -5-fluoropyridine 2-carboxylic acid, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxy-phenyl) -pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6- (4- chloro-3-dimethylamino-2-fluoro-phenyl) -pyridine-2-carboxylic acid methyl ester.

The insecticide / nematicide is selected from:

Organo (thio) phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulphoton, ethion, fenitrothion, fenthione, isoxathione, malathion, methamidophosphate, methidathion , Methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone,

Phorates, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;

Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates;

- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyanothyrin, permethrin, prallethrin , Pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin,

Inhibitors of insect growth: a) Chitin synthesis inhibitors: Benzoylureas: Chlorofluorazuron, Cyramazine, Diflubenzuron, Flucycloxuron, Flufenoxuron, He- xaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) Juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spinotetramat;

Nicotine receptor agonists / antagonists: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1- (2-chlorothiazol-5-ylmethyl) -2-nitrimino-3,5-dimethyl- [1, 3,5] triazinane;

- GABA antagonists: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 - (2,6-dichloro-4-methyl-phenyl) -4-sulfinamoyl-1H-pyrazole-3-thiocarbon acid amide;

Macrocyclic lactones: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;

Mitochondrial Electron Transport Chain Inhibitor (METI) I Acaricides: Fenazaquin, Pyridaben, Tebufenpyrad, Tolfenpyrad, Flufenerim;

METI II and III substances: Acequinocyl, Fluacyprim, Hydramethylnon;

- decoupler: chlorfenapyr;

- inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; Inhibitors of the sloughing of insects: Cryomazine;

Inhibitors of mixed function oxidases: piperonyl butoxide;

Sodium channel blocker: indoxacarb, metaflumizone;

- Other: Benclothiaz, Bifenazate, Cartap, Flonicamid, Pyridalyl, Pymetrozine, Sulfur, Thiocyclam, Flubendiamid, Chlorantraniliprole, Cyazypyr (HGW86); Cynopyphron, Flupyrazofos, Cyflumetofen, Amidoflumet, Imicyafos, Bistrifluron, and

Pyrifluquinazon.

In a further preferred embodiment, the crop protection agents are preferably herbicides. In a further preferred embodiment, the plant protection agents are preferably insecticides. In a further preferred embodiment, the crop protection agents are preferably fungicides. In a further preferred embodiment, the fungicides are preferably azoles. In a further preferred embodiment, the azoles are preferably epoxiconazole, fluquinconazole or metconazole.

Further suitable effect substances are additives for food or animal feed, such as food colorants, amino acids, vitamins, preservatives, antioxidants, odorants or flavorings.

Examples of auxiliaries for polymers are flame retardants, viscosity improvers or polar liquids, as they can be used in the discontinuous phase. Examples of auxiliaries for paper are alkenylsuccinic anhydrides or dialkyldiketenes. Examples of detergents for detergents and cleaners are surfactants or emulsifiers, as they can also be used as dispersants in the inverse miniemulsion. Likewise, enzymes such as hydrolases or amidases can be used as auxiliaries.

Preferred effect substances are crop protection agents and fertilizers, in particular pesticides.

The effect materials can be used in pure form, technical grade, as an extract or in mixture with other effect substances. The effect substances are dissolved or in solid form in the dispersed phase. The total amount of effect substances is from 0.1 to 90% by weight, preferably from 5 to 50% by weight, based on the total batch.

The effect substances can be released from the microcapsules by diffusion through the capsule wall or by degradation of the capsule wall. The rate of release can be controlled selectively by internal and external influences which influence the diffusion or degradation.

Internal influences for controlling the release of the effect substance are, for example, the biodegradability, the chemical, mechanical and physical stability of the microcapsules and the polarity, thickness and uniformity (holes or defects) of the capsule wall. In addition, compounds according to the invention may preferably be present in the capsule interior or in the capsule wall, which influence the release, so-called releasers. Suitable release agents are, for example, enzymes, preferably lipases which hydrolyse the polyester. The enzymes may be the same ones used for the enzyme-catalyzed polymerization of the monomers. Acids, bases, radical formers or salts for generating an osmotic pressure are also suitable as releasers. Mixtures of releasers are also possible. The total amount of the releaser is generally from 0.01 to 20% by weight, based on the total batch. The amount depends on the desired release rate and the prevailing conditions. The skilled person will determine the rate of release of the effect substance by varying the amount under the intended release conditions.

External influences to control the release of the effect substance are, for example, acidic or basic conditions, microbiological or enzymatic degradation of the capsule wall, mechanical pressure or radiation, such as UV or electron radiation.

Further additives, for example preservatives, thickeners, release agents or protective colloids and emulsifiers, which can also be used in the process according to the invention, are known to the person skilled in the art and are added in customary amounts, depending on the desired use after the preparation of the microcapsules. The process according to the invention is advantageously carried out such that in each case at least one dispersant, at least one nonpolar liquid, at least one polar liquid, at least one monomer, at least one enzyme catalyzing the polymerization and at least one effect substance are combined in any order and an inverse miniemulsion is produced therefrom. It is also possible to produce premixes. Preferably, at least one enzyme catalyzing the polymerization is introduced into a previously prepared inverse miniemulsion.

The process according to the invention preferably takes place in such a way that at least one dispersing agent is introduced into at least one subset of a liquid and a subset of the monomers. The effect substance and a partial amount of the monomers is separately introduced into at least a subset of the liquid. The two mixtures are combined and made an inverse miniemulsion. Subsequently, portions of the monomers and the enzyme are introduced into the mini-emulsion. "Subset of the monomers" in this context means between 0 and 100% of the total monomers contained in the reaction mixture. "At least one subset" means more than 0% of the amount contained in the total batch.

In a preferred embodiment, a partial amount of the monomers is introduced into the miniemulsion, wherein the partial amount is more than 1%, preferably more than 10%.

The process of the invention is generally carried out at a reaction temperature of 5 to 100 ⁰ C, often from 20 to 80 ⁰ C and often from 30 to 65 ⁰ C. In general, the process is carried out at a pressure (absolute values) usually from 0, 8 to 10 bar, preferably from 0.9 to 2 bar and in particular at 1 bar (atmospheric pressure). The person skilled in the art directs the reaction time according to the desired properties of the microcapsule, for example the degree of polymerization or the thickness of the capsule shell. After the desired reaction time, the enzyme may be destroyed or reused, the microcapsules isolated, or the reaction mixture otherwise isolated or further processed.

In general, the solid capsule shell of the monomers forms during the reaction time in the inverse miniemulsion catalyzing the enzyme. The formation of solid capsule shells produces a microcapsule suspension of microcapsules with a solid capsule shell from the miniemulsion.

The releaser can be introduced at any process step. If the releaser comprises an enzyme, it is preferably added after the emulsification. Other additives, such as preservatives, can be introduced at any process step. The preparation of the inverse miniemulsion, which must be present invention, can be done according to the prior art. For this, a macroemulsion is prepared by introducing energy into the mixture of the phases by shaking, whipping, stirring, turbulent mixing; by injecting one fluid into another; by vibrations and cavitation in the mixture (eg ultrasound); by emulsifying centrifuges; through colloid mills and homogenizers; or by means of a jet nozzle, as described for example in WO 2006/053712. The macroemulsion is converted by homogenization into a miniemulsion with droplet sizes below 1000 nm. Homogenization is preferably carried out at 0 to 100 ^° C. by use of ultrasound, high-pressure homogenizers or other high-energy homogenization apparatus, such as jet nozzles.

The polymers of the capsule shell can be postcrosslinked by known methods. Usually suitable are free-radical processes, for example by radical initiators or by UV-initiated crosslinking, or addition processes, for example with

Diisocyanates or carbodiimides or processes for transesterification of free OH groups, for example enzymatic transesterification or, for example, transesterification of citric acid triesters. The post-crosslinking can be carried out after completion of the capsule shell or simultaneously to the inventive production of the capsule shell.

The microcapsules prepared according to the invention can be provided with a second capsule shell by known methods, for example by organometallic-catalyzed radical polymerization, by enzyme-catalyzed polymerization, by polyaddition to produce polyurethane or epoxy resin as second shell, or by polycondensation to produce polyesters or polyamides.

Further use of the capsules is possible without further workup. After the preparation according to the invention of the microcapsules they can be isolated if necessary, that is to be freed from solvents. Suitable methods are, for example, evaporation, spray drying, freeze drying, centrifugation, filtration or vacuum drying. In a preferred embodiment, the microcapsules are not isolated after preparation.

Furthermore, the microcapsules can be converted into dispersions according to the invention by dispersing the microcapsules in water or aqueous solutions, for example by phase transfer methods or flush-analogous transfer methods.

The dispersion prepared according to the invention comprising microcapsules or the further processed product may be used as a component in colorants, cosmetics, pharmaceuticals, crop protection agents, fertilizers, food or animal food additives, auxiliaries for polymers, paper, textile, leather, paints or detergents and cleaners. be used. It is advantageous that the effect material can be selectively released again, especially in the biosphere, where polyester-degrading enzymes are ubiquitous.

In a preferred embodiment, the present invention relates to an agrochemical formulation comprising microcapsules according to the invention or microcapsules prepared according to the invention.

The term "formulation auxiliaries" in the context of the invention are auxiliaries which are suitable for the formulation of agrochemical active substances, such as solvents, carriers, surfactants (ionic or nonionic surfactants, adjuvants, dispersants), Preservatives, defoamers and / or antifreeze agents Seed treatment auxiliaries may optionally also be dyes, binders, gelling agents and / or thickeners.

In general, the agrochemical formulations may comprise 0 to 90% by weight, preferably 1 to 85% by weight, more preferably 5 to 80% by weight, and especially 5 to 65% by weight of formulation aid.

In a further preferred embodiment, the present invention relates to methods for controlling undesired plant growth, wherein the undesirable plants, the soil on which the unwanted plants grow, or their seeds are treated with an agrochemical formulation according to the invention.

In a further preferred embodiment, the present invention relates to methods for controlling unwanted insect or M on attack on plants and / or for controlling phytopathogenic fungi, wherein the fungi / insects, their habitat or to be protected against fungal or insect infestation plants or soils or the plants, the soil on which the plants grow, or their seeds are treated with an agrochemical formulation according to the invention.

In a further preferred embodiment, the present invention relates to methods for treating seed with an agrochemical formulation according to the invention and seed treated with an agrochemical formulation according to the invention.

Specifically, the agrochemical formulations according to the invention are suitable for controlling the following plant diseases:

Albugo spp. (White rust) on ornamental plants, vegetable crops (eg A. Candida) and sunflowers (eg BA tragopogonis); Alternaria spp. (Blackness, black spot) on vegetables, oilseed rape (for example BA brassicola or A. brassicae), sugar beet (for example BA tenuis), fruit, rice, soya beans and on potatoes (eg BA solani or A. alternata) and tomatoes (eg BA solani or A Alternata) and Alternaria spp. (Earwires) on wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, eg. BA tritici (leaf drought) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (Teleomorph: Cochliobolus spp.) On maize (for example BD maydis), cereals (for example BB sorokiniana: brown spot), rice (for example BB oryzae) and turf; Blumeria (formerly: Erysiphe) graminis (powdery mildew) on cereals (eg wheat or barley); Botryosphaeria spp. ('Black Dead Arm Disease') on vines (eg BB obtusa); Botrytis cinerea (Teleomorph: Botryotinia fuckeliana: gray mold, gray mold) on berry and pome fruit (including strawberries), vegetables (including salad, carrots, celery and cabbage), oilseed rape, flowers, vines, forestry crops and wheat (cereal); Bremia lactucae (downy mildew) on salad; Ceratocystis (Syn. Ophiostoma) spp. (Bläuepilz) on deciduous and coniferous trees, z. BC ulmi (elm dying, Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spot) on maize, rice, sugar beets (eg BC beticola), sugarcane, vegetables, coffee, soybeans (eg BC sojina or C. kikuchii) and rice; Cladosporium spp. on tomato (eg BC fulvum: velvet spot disease) and cereals, eg. BC herbarum (earwax) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (Anamorph: Helminthosporium or Bipolaris) spp. (Leaf spot) on corn (e.g., BC carbonum), cereals (e.g., BC sativus, anamorph: B. sorokiniana: brown spot) and rice (e.g., BC miyabeanus, anamorph: H. oryzae); Colletotrichum (Teleomorph: Glomerella) spp. (Burning spots, anthracnose) on cotton (eg BC gossypii), maize (eg BC graminicola: stalk rot and stinging spots), soft fruit, potatoes (eg BC coccodes: wilting), beans (eg BC Lindemuthiantum) and soybeans ( BC truncatum); Corticium spp., Z. BC sasakii (leaf sheath burn) on rice; Corynespora cassiicola (leaf spot) on soybeans and ornamental plants; Cycloconium spp., Z. BC oleaginum on olive; Cylindrocarpon spp. (for example, fruit tree crayfish or vine dying, Teleomorph: Nectria or Neonectria spp.) on fruit trees, grapevines (eg C. liriodendri, Teleomorph: Neonectria liriodendri, 'Black Foot Disease') and many ornamental shrubs; Dematophora (Teleomorph: Rosellinia) necatrix (root / stem rot) on soybeans; Diaporthe spp. z. BD phaseolorum (stalk disease) on soybeans; Drechslera (Syn. Helminthosporium, Teleomorph: Pyrenophora) spp. on maize, cereals such as barley (eg BD teres, nettles) and wheat (eg BD tritici-repentis: DTR leaf drought), rice and turf; Esca disease (grapevine dying, apoplexy) on grapevine caused by Formitiporia (Syn. Phellus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeoacrimonium chlamydosporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa; Elsinoe spp. on nuclear (E. pyri) and soft fruit (E. veneta: burning spots) and grapevine (E. ampelina: burning spots); Entyloma oryzae (leaf sting) on rice; Epicocum spp. (Earwires) on wheat; Erysiphe spp. (Powdery mildew) on sugar beet (E. betae), vegetables (eg BE pisi), such as cucumber (for example BE cichoracearum) and cabbage plants, such as rapeseed (for example, B. cruciferarum); Eutypa lata (Eutypa crab or ben, Anamorph: Cytosporina lata, Syn. Libertella blepharis) on fruit trees, vines and many ornamental shrubs; Exserohilum (Syn. Helminthosporium) spp. on maize (eg BE turcicum); Fusarium (Teleomorph: Gibberella) spp. (Wilt, root and Stängelfäu- Ie) on various plants, such. BF graminearum or F. culmorum (root rot and pigeon or whitish sprout) on cereals (eg wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides on maize; Gaeuman- nomyces graminis (blackleg) on cereals (eg wheat or barley) and maize; Gibberella spp. cereals (eg BG zeae) and rice (eg BG fujikuroi: Bakanae disease); Glomerella cingulata on grapevine, pome fruit and other plants and G. gossypii on cotton; Grainstaining complex of rice; Guignardia bidwellii (black rot) on grapevine; Gymnosporangium spp. on rosaceae and juniper, eg. BG sabinae (pear grid) on pears; Helminthosporium spp. (Syn. Drechslera, Teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., E.g. BH vastatrix (coffee leaf rust) of coffee; Isariopsis clavispora (Syn. Cladosporium vitis) on grapevines; Macrophomina phaseolina (Syn. Phaseoli) (root / stem rot) on soybeans and cotton; Microdochium (Syn. Fusarium) nivale (snow mold) on cereals (eg wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., Z. BM laxa, M. fructicola and M. fructigena (flower and lace drought) on stone fruits and other rosaceae; Mycosphaerella spp. on cereals, bananas, berry fruits and peanuts, such as. BM graminicola (anamorph: Septoria tritici, Septoria leaf drought) on wheat or M. fijiensis (black sigatoka disease) on bananas; Peronospora spp. (Downy mildew) on cabbage (for example BP brassicae), oilseed rape (for example P. parasitica), onion plants (for example P. destructor), tobacco (P. tabacina) and soybeans (for example P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. z. On grapevines (eg BP tracheiphila and P. tetraspora) and soybeans (eg BP gregata: stalk disease); Phoma Hungary (root and stem rot) on oilseed rape and cabbage and P. betae (leaf spots) on sugar beet; Phopsopsis spp. on sunflowers, grapevine (eg BP viticola: black spot disease) and soybeans (eg stalk rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spot) on maize; Phytophthora spp. (Wilt, root, leaf, stem and fruit rot) on various plants, such as on paprika and cucurbits (eg BP capsici), soybeans (eg BP megasperma, Syn. P. sojae), potatoes and tomatoes (eg. BP infestans: herbaceous and brown rot) and deciduous trees (eg BP ramorum: sudden oak mortality); Plasmodiophora brassicae (cabbage hernia) on cabbage, oilseed rape, radish and other plants; Plasmopara spp., E.g. BP viticola (vines-Peronospora, downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (Powdery mildew) of rosaceae, hops, kernels and berries, eg. BP leucotricha to apple; Polymyxa spp., Z. Cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and the virus diseases transmitted as a result; Pseudocercosporella herpotrichoides (straw break, teleomorph: Tapesia yallunae) on cereals, eg. Wheat or barley; Pseudoperonospora (downy mildew) on various plants, e.g. BP cubensis on cucurbits or P. humili Hop; Pseudopezicula tracheiphila (Red burner, Anamorph: Phialophora) on grapevine; Puccinia spp. (Rust disease) on various plants, eg. BP triticina (wheat brown rust), P. striiformis (yellow rust), P. hordei (dwarf rust), P. graminis (black rust) or P. recondita (rye brown rust) on cereals, such as. Wheat, barley or rye, and asparagus (eg BP asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (leaf drought) on wheat or P. teres (net stains) on barley; Pyricularia spp., E.g. BP oryzae (teleomorph: Magnaporthe grisea, rice leaf-fire) on rice and P. grisea on lawn and cereals; Pythium spp. (Turnip disease) on turf, rice, corn, wheat, cotton, oilseed rape, sunflower, sugar beets, vegetables and other plants (eg BP ultimum or P. aphanidermatum); Ramularia spp., Z. BR collo-cygni (speckle disease / sunburn complex / Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, eg. BR solani (root / stem rot) on soybeans, R. solani (leaf-sheathing) on rice or R. cerealis (pointed eye-spot) on wheat or barley; Rhizopus stolonifer (soft rot) on strawberries, carrots, cabbage, grapevine and tomato; Rhynchosporium secalis (leaf spot) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath blight) on rice; Sclerotinia spp. (Stem or white rot) on vegetables and crops such as oilseed rape, sunflowers (eg Sclerotinia sclerotiorum) and soybeans (eg BS rolfsii); Septoria spp. on different plants, eg. BS glycines (leaf spot) on soybeans, S. tritici (Sep- toria leaf drought) on wheat and S. (Syn. Stagonospora) nodorum (leaf and spice tan) on cereals; Uncinula (Syn. Erysiphe) necator (powdery mildew, anamorphic: Oidium tuckeri) on grapevine; Setospaeria spp. (Leaf spot) on maize (for example B. turcicum, Syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (Dust fires) on maize, (eg BS reiliana: flaming spirit), millet and sugarcane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powder scab) on potatoes and the viral diseases transmitted thereby; Stagonospora spp. on cereals, z. BS nodorum (leaf and tan, Teleomorph: Leptosphaeria [Syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato cancer); Taphrina spp., Z. BT deformans (curling disease) on peach and T. pruni (pocket disease) on plums; Thielaviopsis spp. (Black root rot) on tobacco, pome fruit, vegetable crops, soybeans and cotton, eg. BT basicola (Syn. Chalar elegans); Tilletia spp. (Stone or Stinkbrand) of cereals, such. BT tritici (Syn. T. caries, Weizensteinbrand) and T. controversa (Zwergsteinbrand) on wheat; Typhula incarnata (snow) on barley or wheat; Urocystis spp., E.g. BU occulta (stem brandy) on rye; Uromyces spp. (Rust) on vegetables, such as beans (for example, appendiculatus appendix, Syn. U. phaseoli) and sugar beet (for example, Betae); Ustilago spp. (Firefighting) on cereals (for example BU nuda and U. avaenae), maize (for example maydis: corn bump sting) and sugarcane; Venturia spp. (Scab) on apples (eg BV inaequalis) and pears; and Verticillium spp. (Deciduous and cloudy) on various plants, such as fruit and ornamental trees, vines, soft fruit, vegetables and crops, such as z. BV dahliae on strawberries, rapeseed, potatoes and tomatoes.

The agrochemical formulations according to the invention are also suitable for controlling harmful fungi in the protection of materials and buildings (eg wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products. In wood and building protection, particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The agrochemical formulations according to the invention are also suitable for controlling undesired plant growth. Control of undesired plant growth is the destruction of weeds. Weeds are understood in the broadest sense as all those plants that grow in places where they are undesirable, such as:

Dicotyledonous weeds of the genus: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xantium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum , Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Monocotyledonous weeds of the genus: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristyslis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ishaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Overall, the process according to the invention offers many advantages over conventional processes for the production of microcapsules: low reaction temperatures and largely neutral pH values allow the encapsulation of temperature- and pH-sensitive effect substances; the polymers for the capsule shell can be prepared directly in situ without consuming expensive storage; the polymer is produced by the enzyme at low temperatures and not by energy-consuming, classical polymerization processes, which usually require completely anhydrous conditions; the polymerization catalyst is very well biocompatible and can be reused as opposed to organometallic polymerization catalysts.

Likewise, the microcapsules prepared according to the invention and the dispersions containing microcapsules offer advantages: the capsule shell of the microcapsule is denser than in other manufacturing processes, it can be more easily varied in thickness or be provided with an additional capsule shell, they can optionally be selectively dismantled to release the effect substances. The capsule core of the microcapsules may comprise temperature-labile or otherwise sensitive effect substances, it may also comprise effect substances dissolved in polar liquid. Another advantage of the dispersions is that they can be obtained directly from the production process.

The following examples illustrate the invention without limiting it.

Examples

Starting Materials:

Suitable nonpolar phase was a partially hydrogenated mineral oil distillate having a boiling point 260-280 ⁰ C, for example, Isopar ^® by the company. Exxon Mobil Chemical, or a paraffin oil (white, CAS 8012-95-1) were used.

As the enzyme for polymerizing the monomers, an immobilized lipase of Candida antarctica type B was used, for example, an enzyme which is a Candida antarctica type B lipase immobilized on spherical polymer beads, available from Novozymes, Denmark.

A dispersant as a mixture of emulsifiers is used which contains ethoxilier- te fatty alcohols, and sorbitan fatty acid esters, for example, 51, 72 wt .-% Arlacel P134 ^® (polyethylene glycol-30 dipolyhydroxystearate, Fa. Uniqema), 34.48 wt .-% clamping ^® 85 (sorbitan trioleate, Fa. Uniqema) and 6.90 wt .-% Cremophor ^® A6 (Uniqema sorbitan monooleate, Fa.) (Ceteareth-6 and stearyl alcohol, Fa. BASF) and 6.9 wt .-% span ^® 80 wherein the wt .-% are based on the total amount of dispersant.

As dispersant B, a polyester-polyethylene oxide-polyester block copolymer was at a molecular weight of> 1000 g / mol is used, which is prepared by reacting condensed 12-hydroxystearic acid with polyethylene oxide according to the teaching of EP 0000424 B1 (Hypermer ^® B- 246, Croda).

As a dispersant, a C Polyethylenglykolsorbitanmonooleat with a Ethoxi- was lierungsgrad 20 used (Tween ^® 80).

The monomer used was ε-caprolactone for the preparation of the polymer-containing capsule shell, for example the company Fluka with a content of> 99%.

The effect substance used was a fungicidal pesticide, for example triticonazole. Alternatively, a colorant, for example, Basacid ^® Blue 756 (CI. Acid Blue 9, triphenylmethane dye, for example, available from BASF SE) was used as effect substance. Basacid® Blue 756 is insoluble in Isopar ^® V while it dissolves in propylene carbonate and caprolactone. As a further alternative, propylene carbonate was used as effect substance.

For staining for light microscopy, the dye ^Sudan® Blue (anthraquinone dye, Cl. Solvent Blue 79, available, for example, from BASF SE) was used. It dissolves only in very hydrophobic media, such as Isopar ^® V and polycaprolactone. However, it is slightly soluble in water or propylene carbonate. example 1

The following amounts were used to prepare 80.0 g of inverse miniemulsion: 38.00 g partially hydrogenated mineral oil distillate 2.00 g dispersant A 0.80 g ε-caprolactone 39.20 g propylene carbonate 0-10 μl water

The dispersant was weighed into the sample vessel and dissolved in the partially hydrogenated mineral oil distillate. The caprolactone and propylene carbonate were added with vigorous stirring by magnetic stirring to the oil phase, then the water was added and pre-emulsified. Using Hielscher's ultrasonic processor UP 400S, an inverse miniemulsion was prepared from this under ice-cooling (5 min, 100%, sonotrode H7). The droplet size distribution of the miniemulsion at 200-1000 nm was determined by means of a light microscope (1000 × magnification). After the ultrasonic emulsification, 20 mg of enzyme was added to each reaction, and the miniemulsion was polymerized at 40 ^° C. for 24 hours. The microcapsules had a particle diameter of 5 to 20 μm (see Figure 1, for clarity, the capsule shell and the non-polar phase were stained with Sudan Blue).

Addition of water A) 0 μl water B) 1 μl water C) 2 μl water D) 10 μl water

Example 2

The following amounts were used to prepare 20.0 g of inverse miniemulsion: 9.50 g of partially hydrogenated mineral oil distillate 0.50 g of dispersant A 0.20 g of ε-caprolactone

9.80 g of propylene carbonate 2 μl of water

The dispersant was weighed into the sample vessel and dissolved in the partially hydrogenated mineral oil distillate. The propylene carbonate was added with vigorous stirring by magnetic stirring to the oil phase, then the water was added and pre-emulsified. Using ultrasound processor UP 400S from the company Hielscher was from it under ice cooling an inverse mini-emulsion prepared (5 min, 100%, sonotrode H7). The droplet size distribution of the miniemulsion at 200-1000 nm was determined by means of a light microscope (1000 × magnification). After the ultrasound emulsification, the caprolactone was added to the batch and gently stirred. 20 mg of enzyme was added and at 40 ⁰ C, the miniemulsion is polymerized for 24 hours. The microcapsules had a particle diameter of 5 to 20 μm. Figure 2 shows capsules with polycaprolactone shell in a continuous phase of partially hydrogenated mineral oil distillate stained with Sudan Blue. Individual bulk particles of polycaprolactone were also colored blue by Sudan Blue.

Example 3

The following quantities were used to prepare 20.0 g of inverse miniemulsion: 9.50 g of partially hydrogenated mineral oil distillate

0.50 g of dispersant A

0.20 g of ε-caprolactone

9.80 g of propylene carbonate

50 mg Basacid Blue 756 2 μl water

The dispersant was weighed into the sample vessel and dissolved in the partially hydrogenated mineral oil distillate. The Basacid Blue was dissolved in propylene carbonate with magnetic stirring, then the water was added. The propylene carbonate phase was added to the oil phase and pre-emulsified. Using Hielscher's ultrasonic processor UP 400S, an inverse miniemulsion was prepared from this under ice-cooling (5 min, 100%, sonotrode H7). The droplet size distribution of the miniemulsion at 200-1000 nm was determined by means of a light microscope (1000 × magnification). After the ultrasonic emulsification 20 mg of enzyme were added and at 40 ⁰ C, the mini-emulsion is polymerized for 24 hours.

The microcapsules had a particle diameter of 5 to 20 μm. Figure 3 shows microcapsules whose capsule core is colored by the effect substance Basacid Blue. The continuous phase is colorless. In addition, a ca 10 μm large, undissolved Basacid blue crystal can be seen and a ca. 30 μm long particle of polycaprolactone.

Example 4

The following amounts were used to prepare 20.0 g of inverse miniemulsion: 9.50 g of partially hydrogenated mineral oil distillate 0.50 g of dispersant A 1, 0 g of ε-caprolactone 8.55 g of propylene carbonate 0.45 g of triticonazole

The dispersant was weighed into the sample vessel and dissolved in the partially hydrogenated mineral oil distillate. The effect triticonazole was dissolved in propylene carbonate and caprolactone. The propylene carbonate phase was added to the oil phase and pre-emulsified. Using Hielscher's ultrasonic processor UP 400S, an inverse miniemulsion was prepared from this under ice-cooling (5 min, 100%, sonotrode H7). After the ultrasonic emulsification, 100 mg of enzyme was added, and at 60 ^° C., the miniemulsion was stirred for 24 hours. After the polymerization, a sample was diluted with paraffin oil and stained with Sudan Blue. In the microscope at 400x magnification clearly microcapsules (also burst) were to be recognized. The microcapsules have a particle diameter of <1 micron to 10 microns. Bulk polymer could not be identified. By adding water, the microcapsules can be converted into the aqueous phase.

Example 5

The following quantities were used to prepare an inverse miniemulsion: 22.8 g of partially hydrogenated mineral oil distillate 6.0 g of ε-caprolactone

19.2 mg D-sorbitol 329 mg triticonazole

1.20 g of dispersant B The dispersant was placed in a sample vessel and dissolved with stirring in partially hydrogenated mineral oil distillate. In another vessel triticonazole was dissolved in a mixture of caprolactone and sorbitol. The homogeneous solutions were then mixed together and pre-emulsified by stirring with the magnetic stirrer (60 min at room temperature). Using ultrasound (ultrasound processor UP 400S from Hielscher), an inverse miniemulsion was prepared therefrom while cooling with an ice bath (5 min, 100% with sonotrode H7) and polymerized at 60 ^° C. for 48 h after addition of 100 mg of enzyme. Electron micrographs show the resulting spherical particles with particle sizes of 1-10 microns.

Example 6

The following amounts were used to prepare an inverse miniemulsion: 45.60 g of paraffin oil 11, 34 g of ε-caprolactone

18.3 mg glycerol

60 mg dispersant C 658 mg triticonazole 2.40 g dispersant B

The dispersants were placed in a sample vessel and dissolved in paraffin oil with stirring. In another vessel, triticonazole and glycerol were dissolved in caprolactone. The homogeneous solutions were then mixed together and pre-emulsified by stirring with a magnetic stirrer for 60 minutes at room temperature. By means of ultrasound (ultrasonic processor UP 400S of the company. Hielscher) was prepared therefrom while cooling with an ice bath, an inverse miniemulsion (5 min, 100% with solar notrode H7) and after addition of 100 mg of enzyme for 48 h at 60 ⁰ C polymer Siert. Electron microscopic investigations show spherical particles with sizes of 1-10 μm.

Example 7

The following quantities were used to prepare the inverse miniemulsion: 120 g of partially hydrogenated mineral oil distillate 24.0 g of propylene carbonate 6.0 g of ε-caprolactone 19.2 mg of D-sorbitol 1, 65 g of triticonazole 3.0 g of dispersant B

The dispersant was placed in a sample vessel and dissolved with stirring in partially hydrogenated mineral oil distillate. In another vessel triticonazole and D-sorbitol were dissolved in a mixture of caprolactone and propylene carbonate. The homogeneous solutions were then mixed together and pre-emulsified by stirring with a magnetic stirrer for 60 minutes at room temperature. Using ultrasound (ultrasound processor UP 400S from Hielscher), an inverse miniemulsion was prepared therefrom while cooling with an ice bath (5 min, 100% with sonotrode H7) and polymerized at 60 ^° C. for 48 h after addition of 100 mg of enzyme. In light micrographs (1000x magnification), the resulting capsules showed particle sizes of 1-10 microns.

Claims

claims

1. A process for the preparation of microcapsules containing an effect-containing capsule core and a polymer-containing capsule shell comprising the formation of the capsule shell by means of enzyme-catalyzed polymerization of monomers which are present in an inverse miniemulsion.

2. The method of claim 1, wherein the disperse phase of the inverse miniemulsion comprises a polar liquid.

3. The method according to any one of claims 1 to 2, in which the enzyme comprises a hydrolase.

4. The method according to any one of claims 1 to 3, wherein the enzyme comprises a lipase or esterase.

A process according to any one of claims 1 to 4, wherein the monomer comprises a lactone.

6. The method according to any one of claims 1 to 2, wherein the enzyme comprises an oxidoreductase.

7. The method according to any one of claims 1 to 6, in which the effect substance is a colorant, cosmetic, Pharmakum, pesticides, fertilizers, food or animal feed additive, auxiliaries for polymers, paper, textile, leather or

Washing and cleaning agent is.

8. Process according to one of claims 1 to 7, in which the effect substance is a plant care agent or a fertilizer.

9. The method according to any one of claims 1 to 8, in which at least one releaser is present, which influences the rate of release of at least one effect substance from the microcapsules according to the invention.

The method of claim 9, wherein the releaser comprises at least one enzyme.

1 microcapsules obtainable by a method according to any one of claims 1 to 10.

12. Dispersions containing microcapsules according to claim 11.

Fig

13. Use of microcapsules obtainable according to one of claims 1 to 10 as a component in colorants, cosmetics, pharmaceuticals, crop protection agents, fertilizers, food or animal food additives, auxiliaries for polymers, paper, textile, leather or detergents and cleaners.

14. Use of dispersions containing microcapsules obtainable according to one of claims 1 to 10 as a component in colorants, cosmetics, pharmaceuticals, pesticides, fertilizers, food or animal food additives, auxiliaries for polymers, paper, textile, leather, paints or detergents and cleaners ,

15. An agrochemical formulation comprising microcapsules according to claim 11 or prepared according to one of claims 1 to 10.

16. A method for controlling undesired plant growth, characterized in that the unwanted plants, the soil on which the unwanted plants grow, or their seeds treated with a formulation according to claim 15.

17. A method for controlling unwanted insect or mite infestation on plants and / or for controlling phytopathogenic fungi, characterized in that the fungi / insects, their habitat or to be protected against fungal or insect infestation plants or soils or the plants , the soil on which the plants grow, or their seeds treated with a formulation according to claim 15.

18. Seed treated with a formulation according to claim 15.