Zinpropylidazol dispersible granules

Abstract

The present invention relates to a water-dispersible granule containing a) dinpropylidaz, b) dioctyl sulfosuccinate, c) an alkyl naphthalene sulfonate formaldehyde condensate, d) lignin sulfonate I, in which the sulfonylation is present in the aliphatic portion of the lignin backbone, and e) lignin sulfonate II, in which the sulfonylation is present in at least the aromatic portion of the lignin backbone. The present invention also relates to a process for making the water-dispersible granule, an aqueous composition obtained by contacting the granule with water, a method of treating plant propagation material with the aqueous composition, and a method of controlling invertebrate pests by applying the aqueous composition.

Description

[Technical field]

[0001] The present invention relates to a water-dispersible granule containing dinpropyridaz, the invention also relates to a process for making the granule, an aqueous composition obtained by contacting the granule with water, a method for treating plant propagation material, a method for treating or protecting animals from infestation or infection by invertebrate pests, a method for eliminating or controlling invertebrate pests, and a method for protecting growing plants from attack or infestation by invertebrate pests. [Background technology]

[0002] Water dispersible granules ("WG") are a common formulation type of pest control compounds. WG formulations are easy for users to handle, do not contain organic solvents, have a long half-life period, and have high activity per mass ratio. WG formulations are usually added to water, such as in an aqueous tank mix, before application. The granules then disintegrate and their components dissolve or disperse in the aqueous continuous phase. It is generally desirable to produce granules that can be easily dispersed in aqueous media, and that such aqueous dispersions produced remain homogeneous. If particles settle, application rates will be discontinuous, and the settled particles may affect the viscosity profile of the aqueous composition, making spray nozzles prone to clogging. Therefore, if the aqueous composition shows signs of settling, it would be desirable to promote the redispersibility of the sediment to restore a homogeneous composition.

[0003] Regarding solid WG formulations, granules have the general advantage over powders that they form less dust. Inhalation of WG formulations can be harmful to the user, so it is desirable to reduce dust formation as much as possible. WG formulations may generate dust due to friction processes between particles. Friction can be influenced by modifying the surface of the granule, for example by creating a flat surface, and by increasing the integrity of the granule, i.e. by reducing the tendency to crack or break into pieces under external forces. Summary of the Invention [Means for solving the problem]

[0004] The present invention relates to a water-dispersible granule containing the insecticide dinpropyridaz. The granule has high dispersibility in aqueous compositions, produces little dust formation, and produces physically stable aqueous compositions. These effects are due to: a) zincpropylidazide, b) dioctyl sulfosuccinate, c) alkylnaphthalenesulfonate formaldehyde condensates, d) lignin sulfonates I, in which the sulfonylation is in the aliphatic portion of the lignin backbone; e) Lignin sulfonates II, in which the sulfonylation is present at least in the aromatic portion of the lignin backbone. This has been achieved by providing a water dispersible granule comprising:

[0005] Surprisingly, it has been discovered that a combination of additives b)-e) confers the above mentioned advantages, such that omission of any one of the additives significantly deteriorates the desired effect, which cannot be remedied by altering the concentration of the other constituents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Zinpropyridaz is the generic name for the compound 1-[1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide. Zinpropyridaz has a chiral center and two enantiomers have been documented (see ip.com IPCOM000256756D), 1-[(1R)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide (hereinafter referred to as the "R-enantiomer") and 1-[(1S)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide (hereinafter referred to as the "S-enantiomer"). The S-enantiomer and R-enantiomer are depicted in formulas IA and IB, respectively. [ka]

[0007] Thus, the term "zinpropyridaz" as used herein refers to the S-enantiomer, the R-enantiomer, and a racemic mixture thereof. Preferably, the term zinpropyridaz refers to a racemic mixture of the S-enantiomer and the R-enantiomer.

[0008] The water-dispersible granules typically contain particles containing ginpropyridaz. ginpropyridaz exists in at least two crystalline forms, hereinafter referred to as "polymorph A" and "polymorph B". ginpropyridaz, its anti-arthropod pest activity, and the general procedure for its preparation are known from WO 2012 / 143317. Applying these general procedures to the preparation of ginpropyridaz, the compound is obtained as a glass-like melt containing polymorph A. The suspended particles containing ginpropyridaz are usually associated with suspended crystalline particles of ginpropyridaz in polymorph A, polymorph B, or a mixture thereof. In one embodiment, the suspended particles containing ginpropyridaz are associated with suspended crystalline particles of ginpropyridaz in the form of polymorph A. In another embodiment, the suspended particles containing ginpropyridaz are associated with suspended crystalline particles of ginpropyridaz in the form of polymorph B.

[0009] Polymorph A can be identified and distinguished from Form B by powder X-ray diffraction. The PXRD pattern of polymorph Form A recorded using Cu-Kα radiation (1.54178 Å) at 25° C. shows at least three of the following reflection angles, quoted as 2θ values: 16.16±0.10°, 20.36±0.10°, 23.92±0.10°, 24.29±0.10°, and 27.43±0.10°. These reflection angles are not present in Form B. In addition to these five reflection angles, Polymorph A may exhibit in such a diffractogram one or more, in particular at least two, often at least four, in particular at least six or at least eight, in particular all, of the following reflection angles, cited as 2θ values: 7.95±0.10°, 10.16±0.10°, 12.40±0.10°, 15.31±0.10°, 15.89±0.10°, 16.53±0.10°, 18.02±0.10°, 19.25±0.10°, 20.93±0.10°, 23.44±0.10°, 23.70±0.10°, 26.16±0.10°, 30.71±0.10° and 32.92±0.10°.

[0010] Among the peaks in the PXRD pattern of Polymorph A, those at the following 2θ values ​​are the most prominent: 10.16±0.10°, 15.31±0.10°, 15.89±0.10°, 16.16±0.10°, 16.53±0.10°, 19.25±0.10°, 20.36±0.10°, 20.93±0.10°, 23.44±0.10°, 23.70±0.10°, 23.92±0.10°, 224.29±0.10°, 26.16±0.10°, 30.71±0.10° and 32.92±0.10°.

[0011] When analyzed by differential scanning calorimetry (DSC), polymorph A exhibits a thermogram with a characteristic endothermic peak, also called the melting peak. The melting point is determined as the onset of the melting peak and is usually in the range of about 82°C to 87°C. The values ​​quoted herein relate to values ​​determined by DSC using an aluminium sealed cup, with a sample size of 1 to 10 mg, and applying a heating rate of 10 K / min.

[0012] Thermogravimetric analysis (TGA) revealed that no weight loss occurred upon heating, indicating that Form A does not contain solvent.

[0013] Polymorph B can be obtained as described in EP 19151447.0. Polymorph B can be identified by powder X-ray diffraction based on its powder X-ray diffractogram (hereinafter also referred to as powder X-ray diffraction pattern or PXRD pattern). Polymorph B recorded using Cu-Kα radiation (1.54178 Å) at 25° C. shows three reflection angles, quoted as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10°. In addition to these three reflection angles, Polymorph B may exhibit in such a PXRD pattern one or more, in particular at least two, often at least four, in particular at least six or at least eight, and in particular all, of the following reflection angles, cited as 2θ values: 7.99±0.10°, 10.07±0.10°, 12.38±0.10°, 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 18.03±0.10°, 19.29±0.10°, 20.22±0.10°, 20.96±0.10°, 23.40±0.10°, 23.70±0.10°, 26.09±0.10°, 27.26±0.10° and 32.91±0.10°.

[0014] Among these reflection angles, preferably at least one, in particular at least two, more particularly at least four, in particular at least six or all of the following reflection angles, cited as 2θ values, may be observed in such a PXRD pattern: 10.07±0.10°, 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 19.29±0.10°, 20.22±0.10°, 20.96±0.10° and 26.09±0.10°. In addition to these reflection angles, preferably a minimum of one, in particular at least two, more in particular at least four, in particular at least six or all of the following reflection angles, quoted as 2θ values, may be observed in such a PXRD pattern: 7.99±0.10°, 12.38±0.10°, 18.03±0.10°, 23.40±0.10°, 23.70±0.10°, 27.26±0.10° and 32.91±0.10°.

[0015] PXRD patterns for polymorphic form B recorded using Cu-Kα radiation (1.54178 Å) at 25° C. often exhibit three reflection angles, quoted as 2θ values: 20.69±0.10°, 24.15±0.10°, and 30.52±0.10°, as well as additional reflection angles, quoted as 2θ values: 15.31±0.10°, 15.97±0.10°, and 16.50±0.10°.

[0016] Alternatively, the PXRD pattern of polymorphic form B recorded using Cu-Kα radiation (1.54178 Å) at 25° C. shows three reflection angles, quoted as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10°, and additional reflection angles, quoted as 2θ values: 23.40±0.10° and 23.70±0.10°.

[0017] In particular, the PXRD pattern of polymorphic form B recorded using Cu-Kα radiation (1.54178 Å) at 25° C. shows three reflection angles, quoted as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10°, and additional reflection angles, quoted as 2θ values: 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 23.40±0.10° and 23.70±0.10°.

[0018] When analyzed by differential scanning calorimetry (DSC), polymorph B of the present invention shows a thermogram with a characteristic endothermic peak, also called the melting peak. The melting point is determined as the onset of the melting peak and is usually in the range of about 80°C to 90°C, in particular in the range of 82°C to 89°C. The values ​​quoted here relate to those determined by DSC using an aluminium closed cup, with a sample size of 1 to 10 mg and applying a heating rate of 10 K / min. Thermogravimetric analysis (hereinafter also referred to as TGA) revealed that no weight loss occurs upon heating, confirming the findings of single crystal X-ray studies that polymorph B is solvent-free.

[0019] The hydratable granules typically contain dinpropyridaz at a concentration of 10-90 wt%, preferably 20-80 wt%, more preferably 30-60 wt%, based on the total weight of the hydratable granule. The hydratable granules may contain dinpropyridaz at a concentration of at least 25 wt%, preferably at least 35 wt%, based on the total weight of the hydratable granule. The hydratable granules may contain dinpropyridaz at a concentration of up to 75 wt%, preferably up to 65 wt%, more preferably up to 55 wt%, based on the total weight of the hydratable granule.

[0020] The water-dispersible granule may contain additional pesticide actives. The term "pesticide actives" refers to a substance that imparts a desired biological activity to the pesticide formulation. Typically, the additional pesticide actives are pesticides. The pesticide actives can be selected from fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and / or growth regulators. In one embodiment, the pesticide actives are pesticides. In another embodiment, the pesticide actives are fungicides. In yet another embodiment, the pesticide actives are herbicides. Those skilled in the art are familiar with such pesticides, which can be found, for example, in Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are those from the carbamate, organophosphate, organochlorine, phenylpyrazole, pyrethroid, neonicotinoid, spinosyn, avermectin, milbemycin, juvenile hormone analogues, alkyl halides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, METI acarizide classes of insecticides, as well as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof. Suitable fungicides include dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic diamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes,Ethyl phosphonates, Ethylaminothiazolecarboxamides, Guanidines, Hydroxy-(2-amino)pyrimidines, Hydroxyanilides, Imidazoles, Imidazolinones, Inorganics, Isobenzofuranones, Methoxyacrylates, Methoxycarbamates, Morpholines, N-Phenylcarbamates, Oxazolidinediones, Oximinoacetates, Oximinoacetamides, Peptidylpyrimidine nucleosides, Phenylacetamides, Phenylamides, Phenylpyrroles, Phenylureas, Phosphonates, Phospho These fungicides are of the following categories: thiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidine amines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, and triazoles. Suitable herbicides include acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenols, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenanthracene, benzothiadiazinones ... noxy carboxylic acids, phenyl carbamates, phenyl pyrazoles, phenyl pyrazolines, phenyl pyridazines, phosphinic acids, phosphoramidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridine carboxylic acids, pyridine carboxamides, pyrimidine diones, pyrimidinyl (thio) benzoates, quinoline carboxylic acids, semicarbazones, sulfonyl amino carbonyl triazolinones, sulfonyl ureas, tetrazolinones, thiadiazoles, thiocarbamates,Herbicides of the following classes are suitable: triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, and ureas.Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene regulators, ethylene liberators, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulants, and other unclassified plant growth regulators.Suitable micronutrients are compounds that contain boron, zinc, iron, copper, manganese, chlorine, and molybdenum. Suitable nitrification inhibitors include linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), karanjin, brachialactone, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethylpyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (telazol, etridiazole), 2-sulfanilamidothiazole (ST). ), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazole thiourea (TU), N-(1H-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide, and N-(1H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, N-(3(5),4-dimethyl-pyrazol-1-ylmethyl)-formamide, neem, products based on neem components, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium terta board, zinc sulfate,2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA1") and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA2"), and / or their derivatives and / or their salts, glycolic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium glycolate, hereinafter referred to as "DMPG"), and / or its isomers and / or its derivatives, citric acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium citrate, hereinafter referred to as "DMPC"), and / or its isomers and / or its derivatives, lactic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium lactate, hereinafter referred to as "DMPL"), and / or its isomers and / or its derivatives, 3,4-dimethylpyrazole mandelic acid addition salt of azole (3,4-dimethylpyrazolium mandelate, hereinafter referred to as "DMPM") and / or its isomers and / or its derivatives, 1,2,4-triazole (hereinafter referred to as "TZ") and / or its derivatives and / or its salts, 4-chloro-3-methylpyrazole (hereinafter referred to as "ClMP") and / or its isomers and / or its derivatives and / or its salts, dicyandiamide and urine The reaction products are the reaction adduct of methyl guanidine with formaldehyde or triazonyl-formaldehyde-dicyandiamide adduct, 2-cyano-1-((4-oxo-1,3,5-triazinan-1-yl)methyl)guanidine, 1-((2-cyanoguanidino)methyl)urea, 2-cyano-1-((2-cyanoguanidino)methyl)guanidine, 3,4-dimethylpyrazole phosphate, allylthiourea, and chlorate. Examples of contemplated urease inhibitors include N-(n-butyl)thiophosphoric triamide (NBPT, Agrotain), N-(n-propyl)thiophosphoric triamide (NPPT), 2-nitrophenylphosphoric triamide (2-NPT), further NXPTs known to those skilled in the art, phenylphosphorodiamidates (PPD / PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see, for example, U.S. Pat. No. 8,075,659). Such mixtures of NBPT and NPPT include NBPT at a concentration of:It may be present in an amount of 40-95%wt.-%, preferably 60-80%wt.-%. Such a mixture is sold as LIMUS, which is a composition containing about 16.9wt.-% NBPT and about 5.6wt.-% NPPT and about 77.5wt.-% other ingredients including solvents and adjuvants.

[0021] The granules may contain further pesticidal active substances in a wide range of concentrations, for example from 5 to 95 wt%, preferably from 10 to 80 wt%, more preferably from 25 to 60 wt%, based on the total weight of the granule.

[0022] The water-dispersible granules are solid at 20° C. The water-dispersible granules may contain up to 5 wt %, preferably up to 3 wt %, more preferably up to 2 wt %, especially up to 1 wt %, of liquid, based on the total weight of the granule.

[0023] The hydratable granules also contain dioctyl sulfosuccinate (CAS number 577-11-7). The hydratable granules usually contain dioctyl sulfosuccinate at a concentration of 0.15-0.6 wt%, preferably 0.175-0.5 wt%, based on the total weight of the granule. The hydratable granules may contain dioctyl sulfosuccinate or a salt thereof at a concentration of at least 0.18 wt%, preferably at least 0.2 wt%, based on the total weight of the granule. The hydratable granules may contain dioctyl sulfosuccinate at a concentration of up to 0.8 wt%, preferably up to 0.5 wt%, more preferably up to 0.4 wt%, based on the total weight of the granule.

[0024] The water dispersible granules also contain naphthalene sulfonate formaldehyde condensates, which are obtained by the condensation reaction of naphthalene sulfonate with formaldehyde. Such compounds are often referred to alternatively as alkylnaphthalene sulfonate condensates. Ullmann's Encyclopedia of Industrial Chemistry, 7 thAs described in the 1990s American Chemical Society, Vol. 13, No. 1, pp. 1111-1115, 1990, Edition, Wiley-VCH Verlag, ISBN 9783527306732, Chapter Naphthalene Derivatives, the condensation reaction of formaldehyde with naphthalene sulfonate gives the compounds shown in Schemes 1 and 2: [ka] Both dimers of naphthalenesulfonates according to formula (I) and polymers according to formula (II) are obtained, where the index n indicates the number of repeat units in the oligomeric or polymeric condensation product, as shown in Figure 1. Typically, the index n ranges from 2 to 1000,000, preferably from 2 to 1,000, for example from 2 to 100.

[0025] It will therefore be understood that the term naphthalenesulfonate formaldehyde condensate can refer to a mixture of a compound of formula (I) and a compound of formula (II) in a wide range of ratios, for example, the weight ratio of the compound of formula (I) to the compound of formula (II) ranges from 10,000:1 to 1:10,000, preferably from 100:1 to 1:100, more preferably from 10:1 to 1:10. In one embodiment, the term "naphthalenesulfonate formaldehyde condensate" refers to a compound of formula (I). In another embodiment, the term "naphthalenesulfonate formaldehyde condensate" refers to a compound of formula (II).

[0026] The pesticide active suspending agent may contain the naphthalene sulfonate formaldehyde condensate in a concentration of 1.2-2.5 wt%, preferably 1.5-2.0 wt%, based on the total weight of the granule. The pesticide active suspending agent may contain the naphthalene sulfonate formaldehyde condensate in a concentration of at least 1.3, preferably at least 1.4 wt%, based on the total weight of the granule. The pesticide active suspending agent may contain the naphthalene sulfonate formaldehyde condensate in a concentration of up to 1.9 wt%, preferably up to 1.8 wt%, based on the total weight of the granule.

[0027] The weight ratio of the naphthalene sulfonate formaldehyde condensate to the dioctyl sulfosuccinate can vary widely. In one embodiment, the weight ratio of the naphthalene sulfonate formaldehyde condensate to the dioctyl sulfosuccinate can be from 1:1 to 10:1, preferably from 3:1 to 10:1, more preferably from 4:1 to 9:1.

[0028] The hydratable granules further contain lignin sulfonate I, in which the sulfonylation is present in the aliphatic portion of the lignin backbone. The hydratable granules also contain lignin sulfonate II, in which the sulfonylation is present in at least the aromatic portion of the lignin backbone.

[0029] Lignin is a complex biopolymer containing both aromatic and aliphatic moieties. It is derived from the reaction of a few precursor molecules, such as phenylpropane, coniferyl alcohol, sinapyl alcohol and para-coumaryl alcohol. These precursor molecules contain aromatic phenyl units as well as hydroxyalkyl and alkoxy moieties, in particular methoxy and hydroxypropyl moieties. Thus, lignin sulfonate I contains sulfonate groups in the aliphatic moieties, such as methoxy and hydroxypropyl groups, in the form of sulfomethoxy and sulfohydroxypropyl groups. On the other hand, lignin sulfonate II contains sulfonate groups at least in the aromatic portion of the lignin backbone, i.e., in the phenyl moiety.

[0030] It is clear to those skilled in the art that due to the rigorous reaction conditions required to produce lignin sulfonates, the sulfonation is never regioselective, but rather results in a mixture of products that contain sulfonate groups at all positions on the lignin backbone, but with differing distribution depending on the synthesis method.

[0031] Thus, Ligninsulfonates I and II will typically contain sulfonate groups in both the aliphatic and aromatic moieties, however Lignosulfonate I will typically have the sulfonate groups predominantly in the aliphatic moiety, e.g. at least 60 mol-%, preferably at least 70 mol-%, more preferably at least 80 wt-%, most preferably at least 90 mol-%, especially at least 95 mol-%.

[0032] On the other hand, lignin sulfonate II can typically contain a more balanced ratio of sulfonate groups in the aliphatic and aromatic moieties, for example, the molar ratio of sulfonate groups in the aliphatic moieties to sulfonate groups in the aromatic moieties of lignin sulfonate II can be 3:1 to 1:3, preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5, for example 1.1:1 to 1:1.1.

[0033] Lignin sulfonates can be characterized by their degree of sulfonation. Lignin sulfonate I typically has a degree of sulfonation of 2 to 5 mol / kilogram, preferably 2.5 to 4 mol / kilogram, more preferably 3 to 4 mol / kilogram, in particular 3 to 3.5 mol / kilogram. Lignin sulfonate II typically has a degree of sulfonation of 2 to 5 mol / kilogram, preferably 2.5 to 4 mol / kilogram, more preferably 3 to 4 mol / kilogram, in particular 3 to 3.5 mol / kilogram.

[0034] The mass average molecular weight (M wThe mass average molar mass of the lignin sulfonate I is typically 1,000 to 5,000 g / mol, preferably 2,000 to 4,000 g / mol, more preferably 3,000 to 4,000 g / mol, and particularly preferably 3,500 to 4,000 g / mol. The mass average molar mass of the lignin sulfonate II is typically 1,000 to 3,000 g / mol, preferably 1,500 to 2,500 g / mol, and more preferably 1,800 to 2,300 g / mol.

[0035] A further method for characterizing lignin sulfonates is the "z+1 molecular average mass" (M z+1 ). The z+1 average molecular weight is controlled by the high molecular weight end of the molecular weight distribution. It can be used to indicate the presence or absence of a high molecular weight fraction in the product, or a general shift in the distribution towards higher molecular weight values. M z+1 is expressed as follows: M z+1 =(ΣN i M i 4 ):(ΣN i M 3 ) where N i is the number of moles of each polymer species, and M i are the molar masses of each species.

[0036] Ligninsulfonates I typically have az+1 average molecular weight of 8,000 to 20,000 g / mol, preferably 10,000 to 15,000 g / mol, more preferably 10,000 to 12,000 g / mol.

[0037] The lignin sulfonate II typically has az+1 average molecular weight of 15,000 to 25,000 g / mol, preferably 16,000 to 20,000 g / mol, more preferably 17,000 to 19,000 g / mol.

[0038] The hydratable granules typically contain lignin sulfonate I at a concentration of 2.5-9 wt%, preferably 2.5-8 wt%, more preferably 3-7 wt%, especially 3.5-6 wt%, based on the total weight of the granule. The hydratable granules may contain lignin sulfonate I at a concentration of at least 2 wt%, preferably at least 3.5 wt%, based on the total weight of the granule. The hydratable granules may contain lignin sulfonate I at a concentration of up to 6 wt%, preferably up to 5.5 wt%, based on the total weight of the granule.

[0039] The hydratable granules typically contain lignin sulfonate II at a concentration of 2-6 wt%, preferably 3-5 wt%, more preferably 3.5-4.5 wt%, based on the total weight of the granule. The hydratable granules may contain lignin sulfonate II at a concentration of at least 2.5 wt%, preferably at least 3.8 wt%, based on the total weight of the granule. The hydratable granules may contain lignin sulfonate II at a concentration of up to 7 wt%, preferably up to 4.2 wt%, based on the total weight of the granule.

[0040] The weight ratio of lignin sulfonate I to lignin sulfonate II typically ranges from 1:4 to 4:1, preferably from 1:3 to 3:1, and more preferably from 1:2 to 2:1.

[0041] The hydratable granules typically contain a filler material. Fillers are mineral earths, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; plant-derived products, such as grain flour, bark flour, wood flour, nut shell flour, and mixtures thereof. Preferred fillers are silicates, kaolin, talc, silica gel, and clay. The granules usually contain the filler material in a concentration of 10-40 wt%, preferably 20-40 wt%, more preferably 20-35 wt%, for example 25-35 wt%, based on the total weight of the granule.

[0042] The water-dispersible granules typically contain a pesticidal effective amount of dinpropyridaz. The term "effective amount" refers to an amount of the composition or dinpropyridaz that is sufficient to control invertebrate pests on cultivated plants or in the protection of the material, without causing substantial damage to the treated plants. Such amounts can vary widely and depend on various factors, such as the species of invertebrates to be controlled, the cultivated plants or materials to be treated, and climatic conditions.

[0043] The water-dispersible granules are prepared by known methods, for example as described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Typically, the granules are prepared by contacting components a)-e) in any given order, including optionally contacting with water, and extruding the resulting composition. The amount of water added for extrusion is typically less than 5 wt%, for example 2 wt%. The extruded material can then be cut into granules, which are then dried.

[0044] The water-dispersible granules may contain at least one auxiliary agent. Suitable auxiliary agents are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, moisturizing agents, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, colorants, tackifiers and binders.

[0045] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling mineral oil fractions, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffins, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactate esters, carbonate esters, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

[0046] Suitable surfactants are surface active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof.Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants.Examples of surfactants are listed in McCutcheon's, Vol.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

[0047] Suitable anionic surfactants are the alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphoric acid esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

[0048] Suitable nonionic 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, alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, can be used for the alkoxylation. 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 sorbitan, ethoxylated sorbitan, sucrose esters and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are home-polymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

[0049] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are block polymers of the AB or ABA type, including blocks of polyethylene oxide and polypropylene oxide, or block polymers of the ABC type, including alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

[0050] Suitable adjuvants are compounds that have little or no pesticidal activity of their own, but enhance the biological performance of compound I against the target. Examples are surfactants, mineral or vegetable oils, and other adjuvants. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

[0051] Suitable thickening agents are polysaccharides (eg, xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

[0052] Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinone and benzoisothiazolinone. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable defoamers are silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g. red, blue or green) are pigments of low water-soluble dyes and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin cyanine, azocyanine and phthalocyanine colorants).

[0053] Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0054] The present invention also relates to an aqueous composition obtained by contacting a water-dispersible granule with water. The granule and water are usually homogenized by mixing, grinding, or other techniques known in the art. The aqueous composition typically contains 30-99 wt% water, preferably 50-99 wt%, more preferably 60-95 wt%, and most preferably 70-95 wt% water. Thus, the aqueous composition contains 1-70 wt% water-dispersible granule, preferably 1-50 wt%, more preferably 5-40 wt%, and most preferably 5-30 wt% water, based on the total weight of the aqueous composition. The aqueous composition is usually a dispersion. The dispersion contains at least the dinpropyridaz active ingredient in the form of suspended particles.

[0055] The present invention also relates to a method of treating plant propagation material comprising the step of contacting the plant propagation material with the aqueous composition.

[0056] The water-dispersible granules can be used for the purpose of treating plant propagation material, in particular seeds. The compositions, after 2-10-fold dilution, result in active substance concentrations of 0.01-60% by weight, preferably 0.1-40% by weight, in the ready-to-use preparation. Application can be carried out before or during sowing. Methods for applying ginpropyridaz and its compositions, respectively, to plant propagation material, in particular seeds, include methods of dressing, covering, pelleting, dusting, immersion and furrow application of the propagation material. Preferably, aqueous compositions containing ginpropyridaz are applied to the plant propagation material in such a way that germination is not induced, for example by dressing, pelleting, covering and dusting the seeds.

[0057] The present invention also relates to a method for combating or controlling invertebrate pests, the method comprising the step of contacting said pests or their food supply, habitat or breeding grounds with a pesticidal effective amount of a water dispersible granule or aqueous composition.

[0058] The contact can be achieved by spraying, irrigation, furrow application, dredging, and other techniques known to those skilled in the art.Invertebrate pests refer to a wide range of pests, particularly arachnids and arthropods.

[0059] When used in plant protection, the application rates of ginpropyridaz are, depending on the type of effect desired, between 0.001 and 2 kg / ha, preferably between 0.005 and 2 kg / ha, more preferably between 0.05 and 0.9 kg / ha, in particular between 0.1 and 0.75 kg / ha.

[0060] In the treatment of plant propagation material such as seeds, for example by dusting, coating or irrigating the seeds, an amount of dinpropylidazide of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g, most preferably from 5 to 100 g per 100 kilograms of plant propagation material (preferably seeds) is generally required.

[0061] When used in the protection of materials or stored products, the application rate of ginpropyridaz depends on the type of application area and the desired effect. Customary application rates in the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0062] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and further pest control agents (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substance or to the composition containing it as a premix or, if appropriate, not added until just before use (tank mix). These agents can be mixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0063] The user usually applies the aqueous composition according to the invention from a predosage device, a backpack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the aqueous composition is made up with water, a buffer, and / or further auxiliaries to the desired application concentration, thus obtaining a ready-to-use spray solution or an aqueous composition according to the invention. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray solution are applied per hectare of agriculturally utilized area.

[0064] Advantages: Water-dispersible granules are characterized by good dispersibility in water, the formation of stable homogeneous aqueous compositions upon dilution with water, and a low degree of dust formation. The following examples are illustrative of the invention. EXAMPLES

[0065] The following ingredients were used to prepare the pest control compositions of each example. Disintegrant: Ligninsulfonate, sulfonated with aliphatic side groups, weight average molecular weight 3700 Da, degree of sulfonation 3.3 (mol / kg), Na2SO3 content 9.4 wt%. Dispersant: Lignin sulfonate, sulfonated with aliphatic and aromatic side groups, weight average molecular weight 2000 Da, degree of sulfonation 3.4 (mol / kg), Na2SO3 content 3 wt%. Wetting agent: 10~20wt% sodium dioctyl sulfosuccinate, 80~90% sodium alkylnaphthalene sulfonate, formaldehyde condensate. Filler: Kaolin clay.

[0066] Example 1 A dispersible granule formulation was prepared having the ingredients summarized in Tables 1 and 2.

[0067] [Table 1]

[0068] The formulations were prepared by mixing the dry ingredients together, hammer milling the resulting composition to a powder, and homogenizing the mixture. The hammer milled mixture was then air milled until the active ingredient reached a D(0.5) particle size of between 2.5-4.5 um. The air milled mixture was then blended with just enough water to consolidate the mixture and pass it through an extruder to form granules. Finally, the granules were dried in a fluidized air bed dryer to a moisture content of approximately 1%.

[0069] The resulting water-dispersible granules were then analyzed for their dispersibility in water. For this purpose, the granules were added in an amount of 2 grams to a cylinder of 29.6 mm diameter containing 100 ml of water. The cylinder was left to stand for 2 minutes, then it was repeatedly inverted upside down and the number of inversions was counted. The cylinder containing the aqueous composition was then incubated at 20-25°C for 2 hours, for which the amount of sediment was measured. Finally, the cylinder containing the aqueous composition was incubated at 20-25°C for a total of 24 hours, and the number of inversions to recover a homogeneous composition was counted. The results of these tests are shown in Table 2 below.

[0070] [Table 2]

[0071] The results showed that the WG formulations tested performed best when they contained at least 2.5 wt% but less than 10% disintegrant, with optimal results obtained at a concentration of approximately 5 wt%.

[0072] Example 2 A dispersible granule formulation was prepared having the ingredients summarized in Tables 3 and 4.

[0073] [Table 3]

[0074] The formulation was prepared by the method described in Example 1. The formulation was then evaluated for dispersibility as described in Example 1. In addition, dust generation was analyzed with a Heubach Dustmeter. Granules were added in an amount of 50 grams to the dustmeter with a rotation speed of 30 UPM, air flow of 201 / min, volume of 600 liters, and time of 1800 seconds. The dust collected by the dustmeter was then weighed.

[0075] The results are shown in Table 4.

[0076] [Table 4]

[0077] The results indicate that the formulation requires both a dispersant and a wetting agent for acceptable non-dusting performance.

[0078] Example 3: A dispersible granule formulation was prepared having the ingredients summarized in Tables 5 and 6.

[0079] [Table 5]

[0080] The formulations were prepared by the method described in Example 1. The formulations were then evaluated for dispersibility and dustiness as described in Examples 1 and 2. The results are shown in Table 6.

[0081] [Table 6]

[0082] Example 4: A dispersible granule formulation was prepared having the ingredients summarized in Tables 7 and 8.

[0083] [Table 7]

[0084] The formulations were prepared by the method described in Example 1. The formulations were then evaluated for dispersibility and dustiness as described in Examples 1 and 2. The results are shown in Table 8.

[0085] [Table 8]

Claims

1. a) Zimpropyridaz; b) Dioctyl sulfosuccinate; c) Alkylnaphthalenesulfonate formaldehyde condensate; d) Lignosulfonate I in which sulfonation is present in the aliphatic part of the lignin skeleton; e) Lignosulfonate II in which sulfonation is present in at least the aromatic part of the lignin skeleton A wettable granule containing the same.

2. The granule according to claim 1, wherein the concentration of the zimpropyridaz is at least 25 wt% based on the total weight of the granule.

3. The granule according to claim 1 or 2, wherein the concentration of the dioctyl sulfosuccinate is 0.15 to 0.6 wt% based on the total weight of the granule.

4. The granule according to claim 1 or 2, wherein the concentration of the alkylnaphthalenesulfonate formaldehyde condensate is 1.2 to 2.5 wt% based on the total weight of the granule.

5. The granule according to claim 1 or 2, wherein the weight ratio of component c) to component b) is 3:1 to 10:

1.

6. The granule according to claim 1 or 2, wherein the concentration of the lignosulfonate I is 2.5 to 8 wt% based on the total weight of the granule.

7. The granule according to claim 1 or 2, wherein the concentration of the lignosulfonate II is 3 to 5 wt% based on the total weight of the granule.

8. The granule according to claim 1 or 2, wherein the weight ratio of the lignosulfonate I to the lignosulfonate II is 1:2 to 2:

1.

9. The granule according to claim 1 or 2, wherein the lignosulfonate II contains sulfonate groups in both the aliphatic part and the aromatic part of the lignin skeleton.

10. The granule according to claim 1 or 2, wherein the lignosulfonate I contains 3 to 4 moles / kg of sulfonate groups.

11. The granule according to claim 1 or 2, wherein the lignosulfonate II contains 3 to 4 moles / kg of sulfonate groups.

12. The granule according to claim 1 or 2, wherein the lignosulfonate II has a z+1 average molecular weight of 15,000 to 25,000 g / mol.

13. A process for producing the hydratable granule according to claim 1, comprising the steps of contacting the components a) to e) with water, optionally, in any given order, and extruding the resulting composition.

14. An aqueous composition obtained by contacting the hydratable granule according to claim 1 or 2 with water.

15. A method for treating the plant propagation material, comprising the step of contacting the plant propagation material with the composition according to claim 14.

16. A method for controlling or eradicating invertebrate pests, the method comprising contacting the pests or their food supply, habitat or breeding ground with a pest control effective amount of the hydratable granule according to claim 1 or the composition according to claim 13.