BR112014023886B1 - method for preparing granules, granules, and method for controlling phytopathogenic fungi and / or unwanted plant development and / or unwanted insect or mite attack and / or for regulating plant development - Google Patents

Abstract

1/1 summary "method" to prepare granules, granules, and method to control phytopathogenic fungi and / or unwanted plant development and / or unwanted attack by insects or mites and / or regulating the development of plants' the present invention relates to a method for preparing granules comprising the steps of a) preparing a slurry with adjuvant by grinding a composition§ aqueous a1 containing a pesticide and a silica absorber to produce a pesticide slurry and add an adjuvant to the pesticide slurry and b) granulating the slurry with an adjuvant, wherein the granulation comprises a granulation fluidized bed or sprouting bed granulation. whether it also concerns the granules obtainable by said method, which comprises 1 to 30% by weight of the pesticide, 10 to 35% by weight of the adjuvant, 8 to 30% by weight of the silica absorber and in which the weight ratio of the silica gel to the adjuvant is 2/1 to 1 / 3.5 and finally to a method for controlling phytopathogenic fungi and / or unwanted plant development and / or unwanted attack by insects or Expensive and / or to regulate the development of plants, where the granules obtained by said method are left to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and / or in unwanted plants and / or useful plants and / or their habitat.

Description

"METHOD FOR PREPARING BEADS, BEADS, AND, METHOD FOR CONTROLING PHYTOPATHOGENIC FUNGI AND / OR UNWANTED PLANT DEVELOPMENT AND / OR UNWANTED ATTACK OF INSECTS OR MITES AND / OR FOR REGULATING PLANT DEVELOPMENT"

Description [0001] The present invention relates to a method for preparing granules comprising the steps of A) preparing a slurry with adjuvant by a1) grinding an aqueous composition A1 containing a pesticide and a silica absorber to produce a paste pesticide fluid and add an adjuvant to the pesticide slurry or a2) crushing an aqueous composition A2 containing a pesticide, a silica absorber and an adjuvant and B) granulating the slurry with adjuvant. This further refers to granules obtainable by said method which comprises from 1 to 30% by weight of the pesticide, from 10 to 35% by weight of the adjuvant, 8 to 30% by weight of the silica absorber and in which the weight ratio from silica gel to adjuvant is 2/1 to 1 / 3.5 and finally to a method to control phytopathogenic fungi and / or unwanted plant development and / or unwanted attack by insects or mites and / or to regulate the development of plants, where the granules obtained by said method are allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and / or on the unwanted plants and / or the useful plants and / or their habitat. Combinations of the preferred embodiments with other preferred embodiments are within the scope of the present invention.

[0002] Usually, it is difficult to include adjuvants, especially liquid adjuvants in granular agrochemical formulations.

[0003] EP 1 974 609 describes a method for preparing granules by (1) forming an absorbate by mixing an adjuvant and a silica absorber, (2) forming an aqueous suspension by wet grinding, / 20 (3) addition absorbate to aqueous suspension and (4) granulation. This method has disadvantages, as does the requirement for the preparation, in an additional separate step, an adjuvant absorbate for silica.

[0004] US 6242382B1 describes, in Example 1, the mixing and grinding of a pesticide, Wettol® LF700 and Extrusil®, followed by fluidized bed granulation. This method has disadvantages, such as the chemical destruction of sensitive additives, such as Wettol® LF700 during crushing.

[0005] The objective of the present invention was to overcome these problems already mentioned. Another objective of the present invention was to avoid an additional step of absorption of the adjuvant to solid carriers before crushing. Another objective of the present invention was to avoid crushing sensitive additives, such as the adjuvant.

[0006] The objective was solved by a method for preparing granules that comprises the steps of

A) prepare an adjuvant slurry by grinding an aqueous composition A1 containing a pesticide and a silica absorber to produce a pesticide slurry and add an adjuvant in liquid form to the pesticide slurry and

B) granulating the slurry with adjuvant, wherein the granulation comprises a fluidized bed granulation or germinated bed granulation.

[0007] Suitable adjuvants are compounds, having negligible or even no pesticidal activity on their own and which improves the biological performance of the pesticide on the target. Additional examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

[0008] The adjuvant is preferably a liquid at 20 ° C and 1013 mbar. The freezing point of the adjuvant may be below 20 ° C, / 20 preferably below 10 ° C. The adjuvant may be insoluble in water or soluble in water, the latter being preferred.

[0009] In step A) (this means the time point when step A) is performed) the adjuvant is added in liquid form to the pesticide slurry. The adjuvant in step A) is preferably free of solids, such as solid carriers or solid absorbers. The adjuvant in step A) usually contains less than 5% by weight, preferably less than 2% by weight, and in particular less than 0.5% by weight of solids.

[0010] Typically, the adjuvant, which is added in step A) in liquid form to the pesticide slurry, is present in highly concentrated form. Preferably, the adjuvant that is added in step A) in liquid form to the pesticide slurry, has a purity of at least 50% by weight, more preferably at least 70% by weight, and in particular at least 90% by weight. Preferably, the adjuvant that is added in step A) in liquid form to the pesticide slurry, contains less than 50% by weight, more preferably less than 30% by weight, and in particular less than 10% by weight of other compounds.

[0011] Typically, step A) is carried out at temperatures between 5 and 200 ° C. Preferably, step A) is carried out at temperatures between 5 and 70 ° C, more preferably between 10 and 50 ° C and, in particular between 10 and 35 ° C.

[0012] The adjuvant is preferably an alkoxylate, more preferably a liquid alkoxylate. Examples of alkoxylates are compounds, such as alkanol alkoxylates, polyphenol polyglycol ethers, ethoxylated sorbitan fatty acid esters, alkyl polyglycosides, fatty acid glucamides, polyglycol fatty acid esters, fatty alcohols, amine acid alkoxylates, fatty acid alkoxylates fatty, polyglycerol fatty acid esters, fatty acid alkanolamides, polyether modified siloxanes or ethylene oxide / propylene oxide block polymers.

[0013] Preferred adjuvants are alkanol / 20 alkoxylates (preferably a liquid alkanol alkoxylate), such as those of formula (I) R ^a -O- (AO) mR ¹ formula (I) where [0014] R ^a is straight or branched alkyl or alkylene with 4 to

32, preferably from 10 to 22, carbon atoms,

AO is an ethylene oxide radical, propylene oxide radical, butylene oxide radical, pentylene oxide radical, styrene oxide radical or mixtures of the radicals mentioned above in random or block sequence, m is numbers of 1 at 30 and

R ¹ is hydrogen or alkyl with 1 to 4 carbon atoms.

Particularly preferred alkanol alkoxylates are those of formula (II)

R ^b -O- (EO) p- (PO) qR ¹ formula (II) where

R ^b is straight or branched alkyl or alkylene having 4 to 32, preferably 10 to 22, particularly preferably 6 to 18, carbon atoms,

EO is -CH2CH2-O-,

PO is -CH2-CH (CHs) -O- or - (CH2) 3-O-, p is numbers 0 to 20, preferably 3 to 10, in particular 4 to 8, q is numbers 1 to 25 , preferably from 4 to 15 and

R ¹ is hydrogen or alkyl with 1 to 4 carbon atoms, where the EO and PO units can occur in random sequence or as blocks.

[0015] In an additional embodiment, with the alkanol alkoxylate of formula (II),

R ^b is straight or branched alkyl or alkylene with 4 a / 20

32, preferably from 6 to 22, particularly preferably from 10 to 18, carbon atoms, q are numbers from 1 to 25, preferably from 3 to 15, and the other radicals as described above for formula (II). [0016] An additional particularly preferred embodiment are alkanol alkoxylates of the formula (III)

R ^c -O- (EO) p- (BO) qR ¹ formula (III) where

R ^c is straight or branched alkyl or alkylene with 4 to

32, preferably from 7 to 18, carbon atoms,

EO is -CH2CH2-O-,

BO is -C4H8O-, which can be linear or branched, p is numbers from 1 to 25, preferably from 3 to 12, in particular from 4 to 7, q is numbers from 1 to 25, preferably from 1 to 15, in particular from 1 to 7 and

R ¹ is hydrogen or alkyl with 1 to 4 carbon atoms, where the units EO and BO can occur in random sequence or as blocks.

[0017] An additional particularly preferred embodiment are alkanol alkoxylates of the formula (IV)

R ^d -O- (EO) pR ¹ formula (IV) where

R ^d is straight or branched alkyl or alkylene with 4 to

32, preferably 10 to 15, carbon atoms,

EO is -CH2CH2-O-, p is numbers from 1 to 10, preferably from 1 to 3,

R ¹ is hydrogen or alkyl with 1 to 4 carbon atoms.

[0018] Suitable silica absorbers are usually / 20 based on precipitated silicas, aluminum and / or calcium silicates and are commercially available as Sipernat® from Evonik Industries, Germany. The silica absorber is usually present as fine particle silica, such as in the form of a powder.

[0019] The silica absorber may have a particle size distribution (determined by laser diffraction, ISO 13320-1) D50 less than 60 pm, preferably D50 less than 15 pm, and in particular D50 less than that 10 pm. In another form, the silica absorber may have a particle size distribution (determined by laser diffraction, ISO 13320-1) D50 less than 60 pm and D90 less than 150 pm, preferably D50 less than 15 pm and D90 less than 25 pm and in particular D50 less than 10 pm and D90 less than 18 pm. The particle size distribution refers to the silica absorber before being subjected to crushing in step A).

[0020] The silica absorber may have a specific surface area (determined by an Areameter with nitrogen, ISO 5794-1, Annex D) less than 200 m ² / g, preferably less than 150 m ² / g, in particular less than 100 m ² / g. The surface area refers to the silica absorber before being subjected to crushing in step A).

[0021] The silica absorber can have an absorber capacity of 600 to 160 g, preferably 300 to 170 g and, in particular, 250 to 180 g DBP per 100 g of solid carrier (determined by DIN 53601).

[0022] Steps A) and B) are usually done in the given sequence. The adjuvant slurry can have a solid content of 10 to 70% by weight, preferably 20 to 60% by weight.

[0023] The grinding of the aqueous composition A1 can be carried out by conventional grinding processes, such as wet grinding (for example, by ball mill). The grinding can be continued until the desired particle size distribution of the slurry with / 20 adjuvant is obtained. Usually, the D50 particle size distribution of the slurry with adjuvant is 0.2 to 20 μm, preferably 0.5 to 5 μm.

[0024] The granulation of step B) comprises fluidized bed granulation or germinated bed granulation, wherein fluidized bed granulation is more preferred. Fluidized bed granulation is well known, such as from US 5,883,047.

[0025] The slurry with adjuvant can be subjected to fluidized bed granulation, the slurry with adjuvant being sprayed in the fluidized bed against the flow direction of the heated fluidized gas of the heated fluidized gas.

[0026] The inlet temperature of the fluidized gas is usually 50 to 220 ° C, in particular from 70 to 200 ° C.

[0027] The amount of fluidized gas is usually 10 to 500 and in particular 50 to 300 m ³ / minutes per m ² of incident flow area of the fluidized bed.

[0028] The spray rate and the concentration of the product in the aqueous solution or dispersion must, in this case, always be adapted to the particular conditions. The appropriate values can be determined by means of some routine tests.

[0029] For spraying with nozzle of the slurry with adjuvant, one or more nozzles of two substances or nozzles of three substances are preferably used, which are generated using an inert gas, in general, compressed air, of 1.2 (8.2 kPa) to 5.0 bar (34.4 kPa). The temperature of the compressed air is, in general, in the range of 15 to 100 ° C.

[0030] The process according to the invention can be carried out continuously or in batches.

[0031] The residual moisture of the granules obtained is preferably less than or equal to 4 weight percent, in particular less than or equal to 2 weight percent and, particularly preferably less than / 20 than or equal to 1 percent by weight.

[0032] The granules can have a D50 particle size distribution of 0.05 to 10 mm, preferably 0.1 to 5 mm. The granules can have a D90 particle size distribution of 0.1 to 15 mm, preferably 0.3 to 7 mm.

[0033] The granules may contain an anionic dispersant. The anionic dispersant can be solid at 20 ° C. Suitable anionic dispersants are alkaline, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid sulfonates and oils, ethoxylated alkylphenol sulfonates, alkoxylated arylphenols sulfonates, condensed naphthalene sulphonates, dodecyl sulfonates and dodecyl sulfates and alkylnaphthalenes, sulfosuccinates or sulfosuccinates. Examples of sulfates are fatty acid and oil sulfates, ethoxylated alkylphenols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, carboxylated alcohol or alkylphenol ethoxylates and alkaline polyacrylic acid salts, polyacrylic acid copolymers or polyacid comb polymers. Preferred anionic dispersants are sulfonates and carboxylates.

[0034] The granules can comprise auxiliaries. Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers, surfactants, emulsifiers, humectants, solubilizers, protective colloids, adhesives, thickeners, humectants, repellents, attractive, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents , dyes, thickeners and binders.

[0035] Solvents and liquid carriers are organic solvents, such as fractions of medium boiling mineral oil at / 20 high, for example, kerosene, diesel oil; vegetable or animal oils; aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, for example, ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example, cyclohexanone; esters, for example, lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, for example, N-methylpyrrolidone, fatty acid dimethylamides and mixtures thereof. Usually, the granules are essentially free of organic solvents, for example, they comprise less than 5% by weight, preferably less than 2% by weight, and in particular less than 0.2% by weight of organic solvent.

[0036] Suitable solid carriers are mineral earth, for example, talc, kaolin, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, for example, cellulose, starch; fertilizers, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, for example, cereal flour, bark flour, wood flour, nutshell flour and mixtures thereof. The silica absorber is not considered a solid carrier within the meaning of this invention. Solid carriers preferably have a low absorbent capacity, such as less than 160 g (preferably less than 130 g) DBP per 100 g of solid carrier (determined by DIN 53601). The granules may contain less than 30% by weight, preferably less than 20% by weight, and in particular less than 12% by weight of the solid carrier (e.g., the solid carrier having a low absorption capacity).

[0037] Suitable surfactants are active compounds on the surface, such as cationic, non-ionic and amphoteric surfactants, block copolymers, polyelectrolytes and mixtures thereof. Such surfactants can be used as an emulsifier, solubilizer, humectant, penetration enhancer, protective colloid or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.l: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. Or North American Ed.). The granules can contain the adjuvant, which also acts as surfactants. In the case, a surfactant is within the scope of the definition according to the adjuvant claim, it is not considered as a surfactant within the meaning of this invention.

[0038] Suitable non-ionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose or alkyl polyglycoside esters. Examples of polymeric surfactants are vinylpyrrolidone homo or copolymers, vinyl alcohols or vinyl acetate.

[0039] Suitable cationic surfactants are quaternary surfactants, for example, quaternary ammonium compounds with one or two hydrophobic groups or salts of long chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block copolymers are block copolymers of type A-B or A-B-A comprising blocks of polyethylene oxide and polypropylene oxide or type A-B-C comprising alkanol, polyethylene oxide and polypropylene oxide.

[0040] Suitable thickeners are polysaccharides (eg / 20 xanthan gum, carboxymethyl cellulose), anorganic clays (organically modified or unmodified), polycarboxylates and silicates.

[0041] Suitable bactericides are derived from bronopol and isothiazolinone such as alkylisothiazolinones and benzisothiazolinones.

[0042] Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

[0043] Suitable anti-foaming agents are silicones, long-chain alcohols and salts of fatty acids.

[0044] Suitable dyes (for example, red, blue, or green) are pigments of low water solubility and water-soluble pigments. Examples are inorganic dyes (for example, iron oxide, titanium oxide, iron hexacyanoferrate) and organic dyes (for example, alizarin-, azo- and phthalocyanine dyes).

[0045] The term pesticide refers to at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, protectors and / or development regulators. The preferred pesticides are fungicides, insecticides, herbicides and developmental regulators. Especially preferred pesticides are fungicides. Mixtures of pesticides from two or more of the classes mentioned above can also be used. The skilled worker is familiar with such pesticides, which can be seen, for example, in the Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. Suitable insecticides are insecticides from the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogues, alkyl halides, nereistoxine analogs of the compounds of organotin, diazyl and amine. , METI acarizides and insecticides such as chloropicrin, pimetrozine, flonicamid, clofentezine, hexitiazox, ethoxazole, diafentiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, / 20 hydramidone, rotamyrone, fluoramine, acequinone Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl oxide oxides, carbamates, carboxylic acids, carbamates, carboxylic acids, carbamates; cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazins, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolcarboxamides, guanidines, hydroxy- (2amino) pyrimidines, isoanilines, imidazoles, hydroxyanilides, hydroxy oxazolidinediones, oxyaminacetates, oxyaminacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propi onamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolcarboxamides, thiocarbamates, thiocarbides, thiocarboxides, thiofanzines, thiofanzines, thiofanzines, trioxides, thiofanzines, trioxides, thiofanzides, thiofanzines. Suitable herbicides are herbicides from the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridyl, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanodines, dinitroanilines, glycine oxides, dinitrophenoline , nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridines, pyridine, pyridimidines, pyridines, pyridines, pyridines, pyridines, pyridines, pyridines, pyridines thio) benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolocarboxines, triazolopyrimines, triazolopyrimidines, triazolone trines villages, ureas.

[0046] In another form of the pesticide it may be N- [4,6-dichloro-2 - [(diethylambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5 (trifluoromethyl ) pyrazole-3-carboxamide; N- [4-chloro-2 - [(diethyl-lambda-4sulfanylidene) carbamoyl] -6-methyl-phenyl] -2- (3-chloro-2-pyridyl) -5 (trifluoromethyl) pyrazol-3-carboxamide; N- [4-chloro-2 - [(di-2-propyl-lambda-4sulfanylidene) carbamoyl] -6-methyl-phenyl] -2- (3-chloro-2-pyridyl) -5 (trifluoromethyl) pyrazole-3 -carboxamide; N- [4,6-dichloro-2 - [(di-2-propyl-lambda-

4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazol-3-carboxamide; N- [4,6-dichloro-2 - [(diethyl-lambda-4sulfanylidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (difluoromethyl) pyrazole-

3-carboxamide; N- [4,6-dibromo-2 - [(di-2-propyl-lambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-

3-carboxamide; N- [4-chloro-2 - [(di-2-propyl-lambda-4-sulfanilidene) carbamoyl] -6-cyano-phenyl] -2- (3-chloro-2-pyridyl) -5 (trifluoromethyl) pyrazole -3-carboxamide; or N- [4,6-dibromo-2 - [(diethyl-lambda-

4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazol-3-carboxamide.

[0047] The pesticide preferably has a melting point of at least 30 ° C and, in particular, at least 50 ° C.

[0048] The pesticide is preferably insoluble in water. Usually, the pesticide has a solubility in water at 20 ° C of up to 10 g / l, preferably up to 1 g / l, and in particular up to 0.2 g / l.

[0049] The granules may contain from 0.1 to 50% by weight, preferably from 5 to 35% by weight, and in particular from 10 to 25% by weight of the pesticide.

/ 20 [0050] The granules may contain at least 10% by weight, preferably at least 13% by weight, and in particular at least 17% by weight of the adjuvant. The granules can contain up to 40% by weight, preferably up to 35% by weight, and in particular up to 30% by weight of the adjuvant.

[0051] The granules may contain at least 4% by weight, preferably at least 8% by weight, and in particular at least 10% by weight of the silica absorber. The granules can contain up to 45% by weight, preferably up to 35% by weight, and in particular up to 25% by weight of the silica absorber.

[0052] The weight ratio of the silica gel to the adjuvant can be from 2/1 to 1 / 3.5, preferably from 1.5 / 1 to 1 / 2.5 and, in particular, from 1.1 / 1 to 1 / 1.9.

[0053] The granules may contain at least 3% by weight, preferably at least 6% by weight, and in particular at least 10% by weight of the anionic dispersant. The granules can contain up to 60% by weight, preferably up to 50% by weight, and in particular up to 40% by weight of the anionic dispersant.

[0054] The granules can contain 5 to 35% by weight of the pesticide, 13 to 35% by weight of the adjuvant, 8 to 35% by weight of the silica absorber and optionally 6 to 50% by weight of the dispersant. The granules can preferably contain 10 to 25% by weight of the pesticide, 17 to 30% by weight of the adjuvant, 10 to 25% by weight of the silica absorber and optionally 10 to 40% by weight of the dispersant.

[0055] Usually, the sum of all components present in the granules added up to 100%.

[0056] The present invention also relates to granules obtainable by the method (preferably obtained by) according to the invention and comprise 30% by weight of pesticide, / 20 to 35% by weight of adjuvant, 30% by weight of silica absorber, optionally filled to 100% by weight with anionic dispersant, and in which the weight ratio of the silica gel to the adjuvant is 2/1 to 1 / 3.5.

[0057] Preferably, the granules are obtainable by the method according to the invention and comprise 5 to 35% by weight of the pesticide, 13 to 35% by weight of the adjuvant, 8 to 35% by weight of the silica absorber, (and optionally 6 to 50% by weight of the dispersant) and the weight ratio of the silica gel to the adjuvant is 2/1 to 1 / 3.5.

[0058] More preferably, the granules are obtainable by the method according to the invention and comprise 10 to 25% by weight of the pesticide, 17 to 30% by weight of the adjuvant, 10 to 25% by weight of the silica absorber, (and optionally 10 to 40% by weight of the dispersant) and wherein the weight ratio of the silica gel to the adjuvant is 1.5 / 1 to 1 / 2.5.

[0059] The present invention also relates to a method to control phytopathogenic fungi and / or unwanted plant development and / or unwanted attack by insects or mites and / or to regulate plant development, where the granules obtainable by the method of according to the invention are left to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and / or on the unwanted plants and / or the useful plants and / or their habitat.

[0060] When used in plant protection, the amounts of active substances applied are, depending on the desired effect group, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0 , 9 kg per ha, in particular from 0.1 to 0.75 kg per ha. [0061] The user applies the composition according to the invention in the form of a ready-to-use liquid usually from a pre-dosing device, a backpack sprayer, a spray tank, a spray plane, or an irrigation system . Usually, the agrochemical composition is made with water, also and / or even auxiliary to the concentration of the desired application and the spray liquid ready for use is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the spray liquid ready for use are applied per hectare of the useful agricultural area.

[0062] The present invention offers several advantages: several silica absorbers can be applied in the method, even those with a low surface area, or with a high particle size, or with a low absorption capacity; the granules may contain a high concentration of the adjuvant, especially the liquid adjuvant; the granules are stable in storage, for example, even at elevated temperatures up to 54 ° C; the granules show no pie formation on storage; there is no loss of adjuvant during the preparation of the granules; the granules disperse easily in the water dispersion and these form a stable dispersion. In addition, there is no time consuming and expensive requirement to prepare in an additional separate step an absorbate of the silica adjuvant. In addition, crushing the aqueous composition results in the smaller particles (compared to crushing without water) in the pesticidal slurry that it is important to allow for a fluidized bed or germinated bed granulation. In addition, the present invention avoids an additional step of absorbing the adjuvant to solid carriers before crushing; and the present invention avoids crushing sensitive additives, such as the adjuvant.

Examples [0063] Silica A: precipitated silica powder, average particle size 3 pm, particle size D50 4.5 pm, absorption DBP 210 g / 100 g, specific surface (nitrogen) 50 m ² / g.

[0064] Loader A: Natural kaolin clay powder, density 2.6, insoluble in water.

/ 20 [0065] Adjuvant A: C12-18 propoxylated, ethoxylated, nonionic and liquid alcohol, freezing point -7 ° C, insoluble in water, dynamic viscosity at 23 ° C about 110 to 125 mPas.

[0066] Adjuvant B: propoxylated, ethoxylated, non-ionic and liquid C12-18 alcohol, freezing point -5 ° C, insoluble in water, dynamic viscosity at 23 ° C about 95 to 110 mPas.

[0067] Adjuvant C: non-ionic, liquid, alkoxylated fatty alcohol, insoluble in water, dynamic viscosity at 23 ° C about 70 to 80 mPas.

[0068] Adjuvant D: non-ionic, liquid alkoxylated fatty alcohol. [0069] Adjuvant E: non-ionic, liquid alkoxylated fatty alcohol, liquid, soluble in water, dynamic viscosity at 23 ° C about 80 to 90 mPas.

[0070] Adjuvant F: modified polyether trisiloxane soluble in water, liquid, viscosity at 25 ° C about 50 to 80 mPas, spill point below -10 ° C.

[0071] Adjuvant G: Alkoxylated phosphoric acid ester of water-soluble fatty alcohol, liquid, acid value 200 to 220 mgKOH / g, water content about 13%, freezing point -4 ° C.

[0072] Adjuvant H: C12-18 propoxylated, ethoxylated, non-ionic and liquid alcohol, dynamic viscosity at 20 ° C about 90 to 105 mPas.

[0073] Anti-foam A: Silfoam® SRE, a nonionic, aqueous silicone emulsion, 33% solid content.

[0074] Dispersant A: Polyalkyl naphthalene sulfonate powder, soluble in water.

[0075] Dispersant B: Sodium dodecyl sulfate.

[0076] Dispersant C: Sodium salt of naphthalenesulfonic acid, formaldehyde-polycondensate, powder soluble in water.

[0077] Dispersant D: Sodium lignosulfonate, powder soluble in water. [0078] Dispersant E: Sodium lignin sulfonate, powder soluble in water.

[0079] Dispersant F: Sodium polycarboxylate (polymer of 2,518 / 20 furandione with 2,4,4-trimethylpentene, sodium salt), water-soluble powder.

[0080] Example 1 [0081] An aqueous suspension was prepared by grinding a composition containing the dimetomorphic pesticide, the silica absorber A and optionally still additives in a ball mill (cf Tables 1 and 2). The particle size resulting from the pesticide was D50 <2 pm.

[0082] The liquid adjuvant and Anti-foam A were added to the aqueous suspension (i.e., the aqueous slurry from step A) according to the invention).

[0083] Finally, the granules were prepared by injecting the suspension with adjuvant (solid content 40% by weight) in a fluidized bed granulation device (product temperature 55 ° C). the water content was below 2% by weight. The granules had a particle size of about D50 = 0.6 mm and D90 = 1.0 mm. The composition of the resulting granules, which each contains 20% by weight of dimetomorph, 2% by weight Anti-foam A, and Dispersant A to 100% by weight, is summarized in Tables 1 and 2. The composition of the resulting granules, which contains each 20 % by weight of dimetomorph and 2% by weight of Anti-foam A, is summarized in Table 3. The amount of adjuvant in the granules was analyzed and confirmed by HPLC, thus no adjuvant was evaporated during granulation.

Table 1: Composition of granules (% by weight)

THE B Ç Silica A 15 25 17.5 Adjuvant A 25 30 30 Dispersant B 1.5 1.5 1.5

[0084] Table 2: Composition of granules (% by weight)

D AND F G H I J K Silica A 12.5 19 16 16 16 16 16 16 Adjuvant B 20 30 Adjuvant C 25 Adjuvant D 25 Adjuvant E 25 Adjuvant F 25 Adjuvant G 25

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Adjuvant H 25 Dispersant B 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Charger A 10

Table 3: Composition of granules (% by weight)

M N O P Q R Silica A 12.5 12.5 12.5 16 16 16 Adjuvant A 20 20 20 15 15 15 Adjuvant C 10 Adjuvant D 10 Adjuvant E 10 Charger A 10 10 10 Dispersant B 1.5 1.5 1.5 1.5 1.5 1.5 Dispersant C 12 Dispersant D Ad 100 Dispersant E Ad 100 Dispersant F Ad 100 Dispersant A Ad 100 Ad 100 Ad 100

Example 2 [0085] An aqueous suspension was prepared by grinding a composition containing proexadione-calcium, trinexapac-ethyl, the silica absorber Silica A and additional additives in a ball mill (see below). The particle size resulting from the pesticide was D50 <2 pm.

[0086] Liquid adjuvant and anti-foam A were added to the aqueous suspension. Finally, the granules were prepared by injecting the suspension with adjuvant into a fluidized bed granulation device as described in Example 1.

[0087] The final granules contained 5% proexadion-calcium, 7.5% trinexapac ethyl, 1% antifoam A, 15% silica A, 10% lignosulfonic acid sodium salt, 5% anionic surfactant, 7, 5% Adjuvant A, 7.5% Adjuvant D, 2% water and ammonium sulfate up to 100% by weight. The granules had a particle size distribution around D50 = 0.6 mm and D90 = 1.0 mm.

Example 3 [0088] The storage capacity of the granules prepared in examples 1A, D, I, J and P was tested after two weeks of storage at 54 ° C according to CIPAC MT 46.1.1 (Table 4-6). The / 20 pie formation was tested while storing under a pressure of 25 g / cm ² . The particle size distribution was determined by a Malvern Mastersizer after dilution with water (D50 and D90 shown as 1 '/ US). To determine the dispersion stability at 2% dilution in a cylinder in the form of a 100 ml graduated cone was prepared. The sediment volume was checked after 2 hours of storage. The pH value was determined at a concentration of 1% by weight in water at 20 ° C.

Table 4: Storage stability after 2 weeks at 54 ° C

Sample 1A Initial 1A Stored 1D Initial Stored 1D Pie formation none none none none pH 8.2 8.4 8.5 8.6 particle size D50: 1.8 / 1.3 μιη D90: 18.9 / 5.8 μιη D50: 4.5 / 1.7 μιη D90: 29.6 / 11.4 μιη D50: 1.5 / 1.4 μιη D90: 5.7 / 4.8 μιη D50: 1.8 / 1.4 gm D90: 8.2 / 5.5 μιη Dispersion stability 0.25 ml no skimming 0.65 ml no skimming <0.1 ml no skimming 0.1 ml no skimming

Table 5: Storage stability after 2 weeks at 54 ° C

Sample 1I Home 1I Stored 1J Home 1J Stored Pie formation none none none none pH 8.5 8.5 2.5 2.5 size of D50: 1.3 / 1.2 μιη D50: 1.3 / 1.5 μιη D50: 1.3 / 1.3 μιη D50: 1.5 / 1.6 μιη particle D90: 3.8 / 4.0 μιη D90: 6.3 / 6.0 μιη D90: 5.0 / 5.4 μιη D90: 6.8 / 6.7 μιη Stability of <0.05 ml <0.05 ml <0.05 ml <0.05 ml dispersal no skimming no skimming no skimming no skimming

Table 6: Storage stability after 2 weeks at 54 ° C

Sample 1P Initial 1P Stored Pie formation none none pH 8.2 8.1 particle size D50: 2.2 / 1.6 μιη D90: 6.8 / 4.9 μιη D50: 2.4 / 1.8 μιη D90: 6.9 / 5.3 μιη Dispersion stability <0.05 ml no skimming 0.05 ml no skimming

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Claims (13)

1. Method for preparing granules, characterized by the fact that it comprises the steps of A) preparing an adjuvant slurry by grinding an aqueous composition A1 containing a pesticide and a silica absorber to produce a pesticide slurry and adding an adjuvant in liquid form to the pesticide slurry, and B) granulate the slurry with adjuvant, where the granulation comprises a fluidized bed granulation or germinated bed granulation, and where the adjuvant is an alkoxylate alkanol of formula (I) R ^a -O- (AO) mR ¹ (I) where R ^a is straight or branched alkyl or alkylene having 4 to 32, preferably 10 to 22, carbon atoms, AO is an ethylene oxide radical, propylene oxide radical, butylene oxide radical, pentylene oxide radical, styrene oxide radical or mixtures of the radicals mentioned above in random or block sequence, m is numbers of 1 at 30 and R ¹ is hydrogen or alkyl with 1 to 4 carbon atoms. 2. Method according to claim 1, characterized by the fact that the adjuvant is a liquid at 20 ° C. Method according to claim 1 or 2, characterized in that the adjuvant in step A) contains less than 5% by weight of solids. Method according to any one of claims 1 to 3, characterized in that the pesticide has a melting point of at least 30 ° C. 5. Method according to any one of claims 1 to Petition 870190060136, dated 06/27/2019, p. 11/13 2/3 4, characterized by the fact that the granules contain at least 12% by weight of the adjuvant. 6. Method according to any one of claims 1 to 5, characterized by the fact that the silica absorber has a particle size distribution D50 less than 15 pm and D90 less than 25 pm. 7. Method according to any one of claims 1 to 6, characterized by the fact that the silica absorber has a specific surface area of less than 200 m ² / g. 8. Method according to any one of claims 1 to 7, characterized by the fact that the granules contain at least 8% by weight of the silica absorber. 9. Method according to any one of claims 1 to 8, characterized by the fact that the granules contain at least 10% by weight of an anionic dispersant. Method according to any one of claims 1 to 9, characterized in that the granules contain less than 12% by weight of a solid carrier with low absorption capacity. Method according to any one of claims 1 to 10, characterized in that the granules comprise less than 5% by weight of organic solvents. 12. Granules obtainable by the method as defined in any of claims 1 to 11, characterized by the fact that they comprise 1 to 30% by weight of the pesticide, 10 to 35% by weight of the adjuvant, 8 to 30% by weight of the silica absorber and wherein the weight ratio of the silica gel to the adjuvant is 2/1 to 1 / 3.5. 13. Method to control phytopathogenic fungi and / or Petition 870190060136, dated 06/27/2019, p. 12/13 3/3 unwanted plant development and / or unwanted attack by insects or mites and / or to regulate plant development, characterized by the fact that the granules obtainable by the method, as defined in any of claims 1 to 11, are left to act on particular pests, their habitat or the plants to be protected from the particular pest, the soil and / or unwanted plants and / or useful plants and / or their habitat.