MXPA01002299A - Microcapsule formulations - Google Patents

Abstract

The invention relates to novel microcapsule formulations consisting of the following:A) a particulate disperse phase consisting of a) a reaction product of at least one diamine, polyamine, dialcohol, polyalcohol and/or aminoalcohol and an isocyanate mixture characterised in the description, optionally mixed with toluene diisocyanate;b) at least one agrochemical active agent from a particular group of substances and c) optionally, additives and B) a liquid, aqueous phase. The invention also relates to a method for producing the inventive formulations and to their use for applying the active agents that they contain. -

Description

MICROENCAPSULATED FORMULATIONS. FIELD OF THE INVENTION The present invention relates to new microencapsulated formulations of active agrochemical products, to a process for their preparation and to their use for the application of agrochemical active products. DESCRIPTION OF THE PRIOR ART It is already known to agitate agrochemical active products, in the form of concentrates and alumnable or water-wettable powders and spray on the plants of injectable liquids, ready for application, which are formed in this case . The drawback of this method is that it often has to be carried out at a great cost to guarantee sufficient protection for people who apply these injectable liquids. Furthermore, it has already been described that the agrochemical active products can be applied in the form of microencapsulated aqueous suspensions (cf. DE-A 3 016 189, DE-B 1 185 154, DE-B 1 248 016 and DE-A 2 734 577). However, it is unfavorable that such preparations tend, in many cases, to agglomeration and that the active components contained are not always released in. the quantities during the prolonged periods of time intended. Finally, it is clear from WO 98-29 360 that plant nutrients can be microencapsulated with the aid of mixtures of isocyanates and polyols. However, the use of such mixtures of isocyanates for the microencapsulation of agrochemical active compounds has not been disclosed to date. DETAILED DESCRIPTION OF THE INVENTION New microencapsulated formulations have now been found, Ref: 127411 which are constituted by A) a dispersed phase in the form of particles constituted by a) a reaction product of at least one diamine, polyamine, dialcohol, polyalcohol and / or aminoalcohol with a mixture of isocyanates, which is formed in the dimerization and / or the trimerization of hexamethylene-1,6-diisocyanate of the formula OCN-ICH-NCO (1) and / or in the reaction of hexamethylene-1, 6-diisocyanate of the formula (I) with water and / or carbon dioxide, if appropriate in a mixture with toluylene diisocyanate, b) at least one active fungicide from the group of amino derivatives, morpholino derivatives or azole derivatives and / or at least one product active insecticide of the group of esters of phosphoric acid, of pyrethroids or of carbamates and / or at least one herbicidal active product of the group of acetanilides and c) optionally additives, the particles of the dispersed phase having a size Particulate medium between 1 and 20 μm and B) an aqueous, liquid phase. It has also been found that the microencapsulated formulations according to the invention can be prepared if a) in a first step at least one fungicidal active is mixed from the group of the amino derivatives, the morpholino derivatives or the azole derivatives and / or at least one insecticidal active product from the group of esters of phosphoric acid, of pyrethroids, or of carbamates, and / or at least one herbicidal active product of the group of acetanilides with a mixture of isocyanates, which is formed in the dimerized and / or trimerized hexamethylene-1,6-diisocyanate of the formula OCN-ICH-NCO (I) and / or in the reaction of hexamethylene-1,6-diisocyanate of the formula (I) with water and / or carbon dioxide, if appropriate with toluylene diisocyanate, and optionally with an organic solvent and, if appropriate, with an emulsifier, β), the mixture thus obtained is subsequently dispersed in a second stage, in water, in given case, mixed with additives, and?) the dispe The reaction, thus obtained, is combined, in a third step, with at least one diamine, polyamine, dialcohol, polyalcohol and / or aminoalcohol, if appropriate in a mixture with water, and then, if necessary, additions are added. . Finally it has been found that the microencapsulated formulations according to the invention are suitable in a very good way for the application of agrochemical active products, which they contain, on plants and / or on their environment. It should be considered as extremely surprising that the microencapsulated formulations according to the invention are suitable for the application of the agrochemical active products, which contain, better than the preparations known before, closer in terms of their constitution. First of all, it is unexpected that, among the large number of isocyanates which are involved, the isocyanate mixture mentioned above, or the mixture of the reaction products of the isocyanates, can be used in a particularly good manner for manufacturing of microencapsulated formulations with the desired properties. The microencapsulated formulations according to the invention are characterized by a series of advantages. In this way they are able to release the active components for a prolonged period of time in the amount required in each case. It is also favorable that the compatibility with the plants of the contained active products is improved and, moreover, the acute toxicity of the active components is also reduced, so that the application of the microencapsulated formulations for the Service staff even without large security measures. The microencapsulated formulations according to the invention are characterized by the components contained in the dispersed phase and in the liquid phase. The isocyanate mixture mentioned in (a) is formed during the dimerization and / or trimerization of hexamethylene-1,6-diisocyanate and / or in the reaction of 1 mole of hexamethylene-1,6-diisocyanate and / or its dimers or trimers with 0.25 to 0.5 moles of water and / or 0.5 moles of carbon dioxide. The reaction products therefore consist of uretdiones, isocyanurates, biurets and / or oxadiazintriones of the hexamethylene-1,6-diisocyanate of the formula (I). Preferred mixtures are those in which the isocyanates of the formulas are contained(uretdione) (isocyanurate) (oxadiazintrione) R and R1 = H or (biuret).

Examples of such isocyanate mixtures are: Desmodur® N 3200 Desmodur® N 3300 Desmodur® N 3400 2H-1, 3,5-Oxadiazin-2,4,6- (3H, 5H) -trion-3,5- bis- (6-isocyanato-hex-l-yl). The isocyanate mixtures, indicated in (a), or the reaction products of mixtures of isocyanates, with known (see WO 98-29 360). The same is true for the toluene diisocyanate also mentioned in (a). Suitable amines of the groups indicated in (a) are aliphatic and alicyclic, primary and secondary diamines and polyamines. Examples which may be mentioned are ethylene diamine (1,2), diethylenetriamine, triethylene tetramine, bis- (3-aminopropyl) -amine, bis- (2-methylaminoethyl) -methyl-amine, 1,4-diamino-cyclohexane, 3- amino-1-methyl-amino-pro-pano, N-methyl-bis- (3-aminopropyl) -amine, 1,4-diamino-n-butane and 1,6-diamino-n-hexane. These diamines and polyamines are known compounds of organic chemistry. Suitable alcohols of the groups indicated in (a) are aliphatic primary and secondary dialcohols and polyalcohols. Examples which may be mentioned are: ethanediol, propanediol- (1, 2), propanediol- (1, 3), butane-diol- (1, 4), pentanediol- (1, 5), hexanediol- (1, 6), glycerin and diethylene glycol.

These dialcoholes and polyalcohols are also known. As examples of aminoalcohols, indicated in (a), triethanolamine may be mentioned. These amino alcohols are also known. In the microencapsulated formulations according to the invention, one or more agrochemical active products indicated in (b) may be contained. The preferred fungicidal active compounds are in this case amino-derivatives, such as 8- (1, 1-dimethyl-ethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4,5] decan-2-methanamine. (Spiroxamine) and Fenpropidin and also morpholino-derivatives, such as Aldimorph, Dodemorph and Fenpropi orph. The preferred fungicidal active compounds in the present context are also Triadimefon, Triadimenol, Bitertanol, Dichlobutrazol, Tebuconazole, Propiconazole, Di-phenoconazole, Cyproconazole, Flutriafol, Hexaconazole, Myclo-butanil, Penconazole, Etaconazole, Bromuconazole, Epoxiconazole, Fenbuconazole, Tetraconazole, Diniconazole. , Flusilazole, Prochloraz, Metconazole, Ipconazole, Fluqinconazole, Triticonazole, Triflumizol, Imibenconazole, Imazalil and 2- [2- (l-chloro-cyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-di -hydro- [1, 2,4] -triazol-3-thione. As insecticidal active compounds of the groups indicated in (b), preference can be given to Azinphos-methyl, Azinphos-ethyl, Bromophos A, Chlorpyriphos, Chlorpyriphos M, Dichlorphos, Edifenpihos, Fenamiphos, Isofenphos, Malathion, Mesulfenphos, Parathion A, Parathion M, Pirimiphos. , Profenofos, Pyraclophos, Tebupirimfos, Beta-cyfluthrin, Cyfluthrin, Cypermethrin, Transfluthrin and Lambda-cyhalothrin, and also Aldicarb, Aldoxycarb, Aminocarb, Bendiocarb, Bufencarb, Butacarb, Butocarboxim, Butoxycarboxim, 2-sec-butyl-phenyl-methylcarbamate, Carbanolate , Carbaryl, Carbofuran, Cartap, Decarbofuran, Di etilan, Dioxacarb, Ethiophencarb, Fenetha-carb, Formetanate, Formparanate, Isoprocarb, Methiocarb, Methomyl, Mexacarbate, Nabam, Nitrilacarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Thiofaxos, Thiocarboxim, Thiram, trimethylphenyl methylcarbamate, 3,4-xylyl methylcarbamate and 3,5-xylyl methylcarbamate. As active herbicidal products of the acetanilides indicated in (b), it is possible to cite Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Petrilachlor and Propachlor. As additives, which may be contained in the microencapsulated formulations according to the invention, organic solvents, emulsifiers, protective colloids, thickeners, preservatives, defoamers, cold stabilizers and neutralizers are suitable. Suitable organic solvents are all the usual organic solvents which, on the one hand, are poorly miscible in water and, on the other hand, perfectly dissolve the active agrochemical products used. Preference is given to aliphatic and aromatic hydrocarbons, if appropriate halogenated, such as toluene, xylene, Solvesso®, tetrachloromethane, chloroform, methylene chloride and dichloromethane, and also also esters, such as ethyl acetate. Suitable emulsifiers are the usual surfactants present in agrochemical active product formulations. Examples which may be mentioned are ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, fatty acid esters, alkylsulfonates, alkyl sulfates and arylsuiphates. Suitable protective colloids (dispersing agents) are all the substances usually used for this purpose. Preference may be given to water-soluble, natural and synthetic polymers, such as gelatins, starches and derivatives and cellulose, especially cellulose esters and cellulose ethers, such as methylcellulose, polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, lignin sulphonates, polyvinylpyrrolidone and polyacrylamides. Suitable thickeners are all the products which are usually usable for this purpose in the agents for the treatment of plants. Preferred are Kelzan® (thixotropic thickening agent based on xanthan), silicic acids and attapulgite. Suitable preservatives are all the substances usually present for this purpose in the agents for the treatment of plants. Examples are Preventol® and Proxel®. Suitable defoamers are all the products which are usually usable for this purpose in the agents for the treatment of plants. Preference may be given to xylan derivatives, such as poly-lidimethylsiloxanes and magnesium stearate. As cold stabilizers, all the products which are usually usable for this purpose can act as agents for the treatment of plants. By way of example, urea, glycerin and propylene glycol may be mentioned. Suitable neutralizing agents are the customary acids and bases, for example phosphoric acid and aqueous ammonia solution can be mentioned.

The particles of the dispersed phase have a particle size which is generally between 1 and 20 μm, preferably between 3 and 15 μm. The aqueous phase of the microencapsulated formulations according to the invention consists essentially of water. It may also contain additives such as protective colloid emulsifiers, preservatives, defoamers and cold stabilizers. Preferably, those components which have already been mentioned as preferred for this substance are considered in this case. In addition, small quantities of organic solvents, as well as the remaining components of the aqueous phase, can also be contained in the aqueous phase. The composition of the microencapsulated formulations according to the invention may vary within certain limits. The proportion of the dispersed phase in relation to the formulation as a whole is generally between 30 and 70% by weight, preferably between 40 and 60% by weight. Also within the dispersed phase, the proportion of the individual components may vary within certain ranges. Thus, in the dispersed phase, the concentrations in the reaction product of isocyanate and diamine, polyamine, dialcohol, polyalcohol and / or aminoalcohol mixture are generally between 1 and 2% by weight, preferably between 2 and 10% by weight. weight, in agrochemical active products in general between 10 and 90% by weight, preferably between 20 and 80% by weight and in additives in general between 0 and 90% by weight, preferably between 10 and 80% by weight.

The preparation of the microencapsulated formulations according to the invention is carried out according to the methods of proceeding from the microencapsulation. In general, this procedure is carried out in such a way that, in a first step of the process (step a), a solution consisting of one or more agrochemical active compounds, isocyanate of the formula (I), if appropriate mixed with toluene diisocyanate, is prepared. as well as, where appropriate, by the organic solvent and emulsifier. If the agrochemical active product is a solid substance, it will generally be used in the form of a solution in an organic solvent. If the agrochemical active product is liquid at room temperature, the use of an organic solvent will be unnecessary. As active agrochemicals, solvents and organic emulsifiers, preference is given in this case to those substances which have already been mentioned as being preferred in relation to the description of the microencapsulated formulations according to the invention. The amounts of the individual components will be chosen in such a way that in the resulting aqueous phase they are present in the concentrations that have already been cited as preferred. In this case, the proportion between the isocyanate mixture mentioned in (a) and the toluene diisocyanate can vary within a given ratio. In general, between 1 and 10 parts by weight, preferably between 0 and 5 parts by weight, of tolylene diisocyanate are used per 1 part by weight of the isocyanate mixture mentioned in (a). The solution prepared in step a of the process according to the invention is dispersed in the second process step (step β) in water, optionally mixed with additives. Suitable additives are protective colloids and emulsifiers in this case. Preference is given to those substances which have already been cited with or preferred in relation to the description of the microencapsulated solutions according to the invention as protective colloids or as emulsifiers. To obtain the dispersions, all the usual apparatuses for this purpose, which generate strong shear forces, can be used. By way of example, rotor-stator mixers and jet dispersers can be mentioned. The dispersion prepared in the step ß of the process according to the invention is combined in the third stage of the process (step?) Under stirring, firstly, with at least one diamine, polyamine, dialcohol, poly-alcohol and / or aminoalcohol. In this case, the amino- or alcohol-components are conveniently added in aqueous solution. Once the reaction has ended, which leads to the formation of the capsules, additives are also added if necessary. Preferred components of the reaction are, in this case, all those diamines, polyamines, dialcohols, polyalcohols and amino alcohols which have already been mentioned as being preferred in relation to the description of the microencapsulated formulations according to the invention. Are additives considered in the realization of the stage? of the process according to the invention thickeners, preservatives, defoamers, cold stabilizers and neutralization agents. Preferably, substances which have already been mentioned as thickeners, preservatives, defoamers, cold stabilizers and preferred neutralizing agents can be used in connection with the description of the microencapsulated formulations according to the invention.

In carrying out the process according to the invention, the proportion between isocyanate and the amino component. or alcohol may vary within certain limits. In general], from 0.8 to 1.5 equivalents of amine component or alcohol are used per 1 mole of isocyanate. Preferably, the isocyanate and amine or alcohol amounts are selected so that equimolar amounts of isocyanate groups and amino or hydroxy groups are present. The reaction temperatures in carrying out the process according to the invention can vary within certain limits. Work is carried out in the embodiment of the first stage in general at temperatures between 0 ° C and 40 ° C, preferably between 2 ° C and 30 ° C, of the second stage in general at temperatures between -10 ° C and +40 ° C, preferably between 0 ° C and 80 ° C, and in the third stage in general at temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 75 ° C. In the process according to the invention, it is generally carried out under atmospheric pressure. The microencapsulated formulations according to the invention are excellently suited for the application of the agrochemical active products, which they contain, on plants and / or on their environment. These guarantee the release of the active components in the quantities intended in each case for a prolonged period of time. The microencapsulated foundations according to the invention can be used in practice either as such or after previous dilution with water. The application is carried out in this case according to usual methods, that is to say, for example, by watering, injecting or spraying. The application rates of the microencapsulated formulations according to the invention can vary within wide limits. These depend on the corresponding agrochemical active products and their content in the microencapsulated formulations. The invention will be explained by means of the following examples. Preparation examples Example 1. A solution consisting of 30.6 g of ß-Cyfluthrin, 91.22 g of Solvesso® 150, 0.12 g of tristyrylphenol-ethoxylate and 1.58 g of Desmodur® N 3200 was disinterested with the aid of of a disperser at 10,000 revolutions per minute over the course of one minute, in 145.12 g of a 1% by weight solution of polyvinyl alcohol (Mowiol 26-88®) in water mixed with 0.06 g of a defoamer of sylicon. Then 0.86 g of triethanolamine are added. The reaction mixture obtained in this case is heated in the course of one hour at 70 ° C and then maintained, under slow stirring, for another 4 hours at 70 ° C. After cooling to room temperature, 30.0 g of a 2% by weight solution of Kelzan S® (xanthan-based thickener) in water and 0.54 g of preservative (Preventol® D7) are added. In this way 300 g of a microencapsulated formulation with a content of β-Cyfluthrin of 100 g / 1 and with an average particle size of 4.3 μm are obtained. Example 2. A solution consisting of 30.36 g ß-Cyfluthrin, 91.22 g of Solvesso® 150, 0.12 g of tristyrylphenol-ethoxylate and 3.17 g of Desmodur® N 3200 at 17 ° C is dispersed with the help of of a disperser at 10,000 revolutions per minute, over the course of one minute, in 145.12 g of a 1% by weight solution of polyvinyl alcohol (Mowiol 26-88®) in water mixed with 0.06 g of a silicone defoamer. Then 0.62 g of monoethylene glycol is added. The reaction mixture obtained in this case is heated in the course of one hour to 70 ° C and then maintained, under slow stirring, for another 4 hours at 70 ° C. After cooling to room temperature, 30.0 g of a 2% by weight solution of Kelzan S® (xanthan-based thickener) in water and 0.54 g of preservative (Preventol® D7) are added. In this way 300 g of a microencapsulated formulation with a content of β-Cyflutrin of 100 g / 1 and with an average particle size of 4 are obtained., 3 μm. Example 3. A solution of 75.8 g of Fenamiphos, 44.1 g of Solvesso® 200, 2.30 g of toluylene diisocyanate and 2.65 g of Desmodur® N 3400 is dispersed at 19 ° C with the aid of a dispersant a 5,500 revolutions per minute over the course of one minute, in 141.7 g of a 1% by weight solution of polyvinyl alcohol (Mowiol 26-88®) in water, in admixture with 0.06 g of a silicone defoamer. Then 2.72 g of a 50% by weight solution of diethylenetriamine in water are added. The mixture of: the reaction formed in this case is heated in the course of one hour at 70 ° C and maintained for another 4 hours, with stirring, at 70 ° C. After cooling to room temperature, 30.0 g of a 2% by weight solution of Kelzan® S (xanthan-based thickener) in water and 0.6 g of preservative (Preventol® D7) are added. In this way 300 g of a microencapsulated formulation with a content of Fenamiphos of 240 g / 1 and with an average particle size of 3.5 μm are obtained. Example 4 A microencapsulated formulation is prepared according to the method described in Example 3, using the following substances. Solution: 75.8 g of fenamiphos 45.4 g of Solvesso® 200 2.77 g of toluylene diisocyanate 2.16 g of 2H-1, 3,5-oxadiazin-2,4,6- (3H, 5H) -trion-3,5- bis- (6-i-socianato-hex-1-yl) Aqueous phase: 140.3 g of a 1% by weight solution of polyvinyl alcohol in water 0.06 g of silicone defoamer Amine: 2.92 g of solution 50% by weight of diethylene triamine Additives: 30.0 g of 2% by weight solution of Kelzan® S (xanthan-based thickener) 0.54 g of preservative (Preventol® D7). In this way 300 g of a microencapsulated formulation with a content of Fenamophos of 240 g / 1 and with an average particle size of 5.3 μm are obtained. Example 5 A mixture consisting of 158.9 g of Tebupirimfos, 3.03 g of toluylene diisocyanate and 3.5 g of 2H-1, 3,5-oxadiazin-2,4,6- (3H, 5H) - is dispersed. trion-3,5-bis- (6-isocyanato-hex-l-yl) at 14 ° C, with the aid of a disperser at 8,000 revolutions per minute in the course of 30 seconds, in 280.9 g of a 1% by weight of polyvinyl alcohol (Mowiol 26-88®) in water mixed with 0.1 g of a silicone defoamer. Then 3.6 g of a 50% by weight solution of diethylenetriamine in water are added. The reaction mixture formed in this case is heated to 70 ° C in the course of 2 hours and then maintained at 70 ° C for a further 4 hours under slow stirring. After the subsequent cooling at room temperature, 500 g of a 2% by weight solution of Kelzan® S (xanthan-based thickener) in water are added. In this way 500 g of a microencapsulated formulation with a Tebupyrimphos content of 300 g / 1 and with an average particle size of 4.7 μm are obtained. Example 6. A solution of 171 g of Tebupirimfos, 9 g of Solvesso® 200 and 17.3 g of Desmodur® N 3300 at 18 ° C is dispersed, with the aid of a disperser at 6,000 revolutions per minute, over the course of 1 minute, in 251 g of a 1% by weight solution of polyvinyl alcohol (Mowiol 26-88®) in water. Then 26.7 g of a 10% by weight solution of ethylenediamine in water are added. The reaction mixture formed in this case is heated in the course of 2 hours to 55 ° C and, under slow stirring, is maintained for another 4 hours at 55 ° C. After cooling to room temperature, 25.0 g of a 2% by weight solution of Kelzan® S (xanthan-based thickener) in water are added. In this way 500 g of a microencapsulated formulation with a Tebupyrimphos content of 320 g / 1 and with an average particle size of 5.1 μm are obtained. Application example. To test the release of the active compound, 3 g of a microencapsulated formulation are suspended in 1 liter of water and stirred for 48 hours at room temperature. Then 5 ml are taken respectively and centrifuged for the separation of the microcapsules. In the remaining aqueous phase, the content of active product is determined according to the HPLC method.

The results can be seen in the following table. Table 1.

It is noted that, with regard to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (9)

CLAIMS Having described the invention as above, it is claimed as a property of the second ccpterrido the following claim cpes: 1.- Microencapsulated formulations, consisting of? X? A dispersed phase
1. A) in faene, of particles characterized perqué are replaced per a) a reaction product of at least one diamine, polyamine, dialcohol, polyalcohol and / or aminoalcohol with a mixture of isocyanates, which is formed in the dimerization and / or trimerization of hexamethylene-1,6-diisocyanate of the formula OCN-ÍCH ^ -NCO (I) / or in the reaction of hexamethylene-1,6-diisocyanate of the formula (I) with water and / or carbon dioxide, optionally in a mixture with toluylene diisocyanate, b) al less an active fungicide of the group of amino derivatives, morpholino derivatives or azole derivatives and / or at least one insecticidal active product from the group of esters of phosphoric acid, pyrethroids or carbamates and / or at least one herbicidal active product from the group of acetanilides as well as c) e: n if given additives, the particles of the dispersed phase having an average particle size between 1 and 20 μm and B) an aqueous phase, liquid
2. 2. - Microencapsulated foimulations according to claim 1, characterized in that they contain Spiroxamine as a fungicidal active product.
3. 3. Microencapsulated fomulations according to claim 1, characterized in that they contain Fenpropidin as a fungicidal active product.
4. 4.- Microencapsulated foimulations according to claim 1, characterized in that they contain Fenamiphos as insecticidal active product.
5. 5. Microencapsulated fomopulations according to claim 1, characterized in that they contain Tebupirimfos as an insecticide active product.
6. 6. Microencapsulated formations according to claim 1, characterized in that they contain Cyfluthrin as insecticidal active product.
7. 7. Microencapsulated fomopulations according to claim 1, characterized in that they contain Betacyfluthrin as an insecticidal active product.
8. 8. Process for obtaining microencapsulated formulations according to claim 1, characterized in that a) in a first step, at least one active fungicide is mixed from the group of amino-cerivatives, morpholino-derivatives or azole. derivatives and / or at least one insecticidal active product from the group of esters of phosphoric acid, of pyrethroids, or of carbamates, and / or at least one herbicidal active product of the group of acetanilides with a mixture of isocyanates, which dimerization and / or trimerization of hexamethylene-1,6-diisocyanate of the formula OCN-ICH-NCO (I) and / or in the reaction of hexamethylene-1,6-diisocyanate of the formula (I) with water and / or carbon dioxide, if appropriate with toluylene diisocyanate, and optionally with an organic solvent and optionally with an emulsifier, β) the mixture thus obtained is then dispersed, in a second step, in water, if necessary, mixed with additives, and?) the dispersion, thus obtained, is combined, in a third step, with at least one diamine, polyamine, dialcohol, polyalcohol and / or aminoalcohol, in the given case in mixture with water, and then added, if necessary, also additives.
9. 9. Use of the microencapsulated formulations according to claim 1, for the application of the agrochemical active products, which they contain, on plants and / or their environment. SUMMARY OF THE INVENTION New microencapsulated formulations consisting of A) a dispersed phase in the form of particles constituted by a) a reaction product of at least one diamine, polyamine, dialcohol, polyalcohol and / or aminoalcohol with a mixture of isocyanates, which is formed in the dimerization and / or the trimerization of hexamethylene-1,6-diisocyanate of the formula (I): OCN-fCH-NCO and / or in the reaction of hexamethylene-1,6-diisocyanate of the formula (I) ) with water and / or carbon dioxide, if appropriate in a mixture with toluylene diisocyanate, b) at least one agrochemical active product chosen from a certain group of substances, as well as; c) if necessary additives, and B) an aqueous, liquid phase. a procedure for obtaining these formulations and their use for the application of the active products they contain.