Solid formulation of insecticidal mixtures having particularly good dispersion properties

Abstract

The invention relates to solid formulations in the form of water-dispersible granules of tetramic acid derivatives, and mixtures of these tetramic acid derivatives, which disintegrate particularly well in water and nevertheless have good long-term stability; the invention also relates to a method for producing same and to their use for the application of the contained active ingredients.

Description

[0001] Solid formulation of insecticidal mixtures with particularly good dispersing properties

[0002] The invention relates to solid formulations (in particular water-dispersible granules) of tetramic acid derivatives and mixtures of these tetramic acid derivatives, which decompose particularly well in water and nevertheless have good long-term stability, as well as to a process for their preparation and their use for the application of the active ingredients contained therein.

[0003] The production of WG formulations with the formulation auxiliaries mentioned in the prior art results in formulations with undesirable properties. For example, the proportion of insoluble ingredients or the presence of certain active ingredients can lead to poor disintegration (i.e., incomplete disintegration or dissolution) of the granules after introduction into water. The slow disintegration of the granules can then lead to sediment remaining, nozzle clogging, and / or a reduction in the concentration of the active ingredient in the spray mixture, and thus in its effectiveness.

[0004] WO2019197631 describes water-dispersible granules of tetramic acid derivatives and mixtures of these tetramic acid derivatives. However, no additives are added to explicitly improve the dissolving properties.

[0005] US2015 / 0164068 describes storage-stable WG formulations with good efficacy, containing the active ingredient in various particle sizes and a low-hygroscopic, water-soluble carrier at 75 wt.% in the form of an inorganic salt. Ammonium and potassium sulfate are preferred as carriers, while potassium bicarbonate is merely listed generally as a carrier without an example in a longer list. Furthermore, the explicit use of potassium bicarbonate is not shown in the examples.

[0006] In contrast to US2015 / 0164068, potassium bicarbonate is present in the present compound only in a significantly smaller amount and especially in combination with another basic salt, which can lead to reactions and negative effects on storage stability.

[0007] W02020 / 240394 describes WG formulations that contain a "disintegration system." This also includes inorganic salts, including bicarbonates. However, no other potentially decomposable salts are included in the formulation, so no negative effects on storage stability are expected. Furthermore, the explicit use of potassium bicarbonate is not shown in the examples; instead, the more common potassium sulfate is used.

[0008] Furthermore, the general use of bicarbonates in dissolving tablets in combination with acids, e.g., citric acid, is known. It has now been surprisingly discovered that the present formulations exhibit particularly advantageous properties with regard to storage stability and rapid dissolution.

[0009] Surprisingly, it was found that the addition of a certain amount of inorganic carbonate salt, in particular hydrogen carbonates, ensures that the granules dissolve faster and better without negatively affecting the storage stability of the granules (especially at elevated temperatures), even in the presence of a basic ammonium salt.

[0010] The formulations of the present invention are further characterized by the fact that they have good suspendability even at high salt load, especially after storage.

[0011] These formulations accordingly constitute the subject matter of the present invention. Furthermore, the present invention relates to a process for producing these water-dispersible granules and to their use for application.

[0012] The invention therefore relates to insecticidal solid compositions in the form of water-dispersible granules (solid formulations), preferably containing: a. as component a, tetramic acid derivatives of the formula (I) in which

[0013] W and Y independently represent hydrogen, Cl-C4-alkyl, chlorine, bromine, iodine or fluorine,

[0014] X represents Cl-C4-alkyl, Cl-C4-alkoxy, chlorine, bromine or iodine,

[0015] A, B and the carbon atom to which they are attached represent C3-C6-cycloalkyl which is substituted by an alkylenedioxyl group optionally substituted by C1-C4-alkyl or C1-C4-alkoxy-C1-C2-alkyl, which forms a 5-ring or 6-ring ketal with the carbon atom to which it is attached,

[0016] G stands for hydrogen (a) or for one of the groups stand in which

[0017] E stands for a metal ion or an ammonium ion,

[0018] M stands for oxygen or sulfur,

[0019] RI stands for straight-chain or branched C1-C6 alkyl,

[0020] R2 represents straight-chain or branched C1-C6 alkyl. b. at least one basic salt, c. at least one further inorganic salt from the group of carbonates and bicarbonates, with ammonium being excluded as a cation. Unless explicitly included below, ammonium salts of carbonates and bicarbonates are always excluded as component c) in the present invention. d. at least one dispersant, e. at least one wetting agent, f. at least one filler, g. optionally a structuring agent h. optionally further active ingredients, and i. optionally further customary adjuvants and formulation auxiliaries.

[0021] In the present invention, optionally substituted radicals in formulas, e.g. formula (I), may, unless otherwise stated, be mono- or polysubstituted, where in the case of multiple substitutions the substituents may be the same or different.

[0022] Furthermore, in the preferred ranges mentioned in the present invention, the various preferred levels are to be understood as meaning that they can be combined with one another in a permuted manner. However, in any case, identical preferred levels, and in particular the most preferred embodiment / preferred level in each case, are to be combined with one another and disclosed as such a combination. Likewise, compositions as described above that consist only of the essential components (not optional components) are to be considered disclosed.

[0023] Unless otherwise stated, percentages are to be understood as percentages by weight, with the weight percentages of the compositions adding up to 100.

[0024] Unless otherwise defined, basic in the sense of the present invention means a pH value in aqueous solution with pH>7.

[0025] The formulations according to the invention have a pH of >7 in aqueous dispersion.

[0026] In a preferred embodiment, the formulations contain at least one defoamer (i), preferably solid, preferably based on silicone oil or wax, more preferably a PDMS absorbed on a solid support.

[0027] The preferred defoamer is: Rhodorsil Antimousse EP6703 (absorbed polydimethylsiloxane). a) Active ingredient

[0028] In a preferred embodiment, component a) in the compositions according to the invention is a compound of formula (I) where the compounds of formula (I) have the following definitions:

[0029] W stands for methyl,

[0030] X stands for chlorine or methyl,

[0031] Y stands for chlorine, bromine or methyl,

[0032] A, B and the carbon atom to which they are attached represent saturated C6-cycloalkyl substituted with an alkylenedioxyl group forming a 5-ring or 6-ring ketal with the carbon atom to which it is attached,

[0033] G stands for hydrogen (a) or for one of the groups (c), E (d), in which

[0034] M stands for oxygen,

[0035] E represents a metal ion equivalent or an ammonium ion, Ri represents straight-chain or branched C -C4 alkyl,

[0036] R 2 represents straight-chain or branched C 1 -C4 alkyl.

[0037] In a further preferred embodiment, component a) in the compositions according to the invention is a compound of formula (I) with

[0038] In a particularly preferred embodiment, component a) is a compound of the formula b) basic salt

[0039] Component b) is preferably selected from the group consisting of inorganic basic ammonium salts, excluding carbonates and bicarbonates. For the purposes of the present invention, the basic salt b) is not a carbonate unless expressly stated.

[0040] Further preferred is b) selected from the group comprising diammonium hydrogen phosphate (DAHP). c) another inorganic salt selected from the group comprising inorganic carbonates and hydrogen carbonates, excluding their ammonium salts.

[0041] Further preferably, c) is selected from the group of hydrogen carbonates.

[0042] Sodium and potassium bicarbonate are particularly preferred. d) Dispersants

[0043] Suitable dispersants in the context of the present invention are dispersants of the polycarboxylate type, for example those such as hydrophobically modified comb-like polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin (such as isobutylene or diisobutylene), a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acid and vinyl acetate, a copolymer of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, a copolymer of maleic acid or maleic anhydride and acrylic acid, an N-methyl fatty acid (e.g. Cs-Cis) sarcosinate, a carboxylic acid such as a resin acid or a fatty acid (e.g.Cs-Cis) or a salt of such a carboxylic acid, such as alkali metal or alkaline earth metal salts (preferably Ca, Mg). The above-mentioned copolymers can also be present in the form of their salts, e.g., alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium, or various amines.

[0044] Further preferred are dispersants from the group comprising sodium salts of copolymers of maleic acid and olefins (e.g., Geropon T / 36 / Solvay; Duramax D-305 / Dow); and sodium salts of copolymers of methacrylic acid and styrene (Tersperse 2700 / Indorama; Atlox Metasperse 500S / Croda).

[0045] The dispersant is particularly preferably a sodium salt of copolymers of methacrylic acid and styrene.

[0046] Particularly preferred is the additional addition of stearates, especially magnesium stearate. e) Wetting agents

[0047] Suitable non-ionic surfactants include all substances of this type commonly used in agrochemicals. Preferred surfactants are polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters. Furthermore, alkyl ethoxylates and alkylaryl ethoxylates, which may optionally be phosphated and optionally neutralized with bases, sorbitol ethoxylates being mentioned as examples, and polyoxyalkyleneamine derivatives.

[0048] All substances of this type commonly used in agrochemicals can be considered as anionic surfactants.

[0049] Preferably, anionic surfactants are considered as wetting agents, selected from the group comprising salts of polystyrenesulfonic acids, salts of polyvinylsulfonic acids, salts of naphthalenesulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde as well as salts of ligninsulfonic acid and sodium salts of alkylated naphthalenesulfonates such as (DMorwet EFW), and the sodium salts of dioctylsulfosuccinic acid such as (DAerosol OTB, Geropon ® SDS and block polymer of propylene oxide and ethylene oxide on ethylenediamine, such as ®Synperonic T 905. Particularly preferred wetting agents (e) in the sense of the present invention are selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates such as (DMorwet EFW), and the sodium salts of dioctylsulfosuccinic acid such as ® Aerosol OTB, Geropon ® SDS. .

[0050] 1) Filler

[0051] All substances commonly used for this purpose in agrochemicals can be considered as inert fillers. Preferred are inorganic particles such as silicates and oxides, as well as organic substances such as urea-formaldehyde condensates and celluloses (e.g., Ulmerweiss 6AL, Celite 209, Argirec B21 and B22, Bentone EW, Talcum Luz2, Etiquette Violette). Examples include kaolin, rutile, silicon dioxide, highly dispersed silica, silica gels, natural and synthetic silicates, and talc.

[0052] More preferably, the filler is selected from the group comprising kaolin, rutile, and silicon dioxide. Kaolin is particularly preferred. g) Structural agent

[0053] The formulations according to the invention may further comprise a structuring agent. Polyacrylic acid and its salts, and especially crosslinked polyacrylates, as well as polyurethanes and derivatized polyurethanes and their salts, are particularly suitable for this purpose. Examples of such suitable acrylates are: (poly)methacrylate, (poly)methyl methacrylate, polyacrylamide,

[0054] (Poly)ethoxyethyl methacrylate, as well as polymethylurea resins, e.g. Pergopak®M.

[0055] The structure-forming agent is particularly preferably a polymethylurea resin. h) Other active ingredients

[0056] The formulation may in principle contain one or more further agrochemical active ingredients, preferably selected from the group of insecticides, herbicides, fungicides and host defense inducers.

[0057] Further preferred are one or more active ingredients selected from the group of insecticides, even more preferably from the group comprising imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifuron, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron;

[0058] Particularly preferred are one or more further active ingredients selected from the group comprising ethiprole, spinetoram, abamectin, and flupyradifurone. i) Adjuvants and formulation aids.

[0059] All substances commonly used for this purpose in agrochemicals can be considered as antifoams. Silicone oil-based defoamers and magnesium stearate are preferred.

[0060] Further preferred are solid defoamers or defoamers applied or absorbed onto a carrier.

[0061] Polydimethylsiloxane absorbed onto a solid substrate is particularly preferred. An example is Rhodorsil Antimousse EP 6703.

[0062] All substances commonly used for this purpose in agrochemicals of this type can be used as preservatives. Examples include isothiazolinone (e.g., Preventol® (Lanxess AG)) and 1,2-benzisothiazolin-3-one (e.g., Proxel®).

[0063] All substances commonly used for this purpose in agrochemicals can be considered as antioxidants. Butylhydroxytoluene is preferred.

[0064] All substances commonly used for this purpose in agrochemicals can be used as dyes. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, and permanent red FGR.

[0065] In a preferred embodiment, the invention relates to an insecticidal solid composition in the form of water-dispersible granules containing: a. Compounds of formula (I) where the compounds of formula (I) have the following definitions:

[0066] W stands for methyl,

[0067] X stands for chlorine or methyl,

[0068] Y represents chlorine, bromine or methyl, A, B and the carbon atom to which they are attached represent saturated C6-cycloalkyl substituted with an alkylenedioxyl group forming a 5-ring or 6-ring ketal with the carbon atom to which it is attached,

[0069] G stands for hydrogen (a) or for one of the groups in which

[0070] M stands for oxygen,

[0071] E stands for a metal ion equivalent or an ammonium ion,

[0072] Ri stands for straight-chain or branched C | -C4 -alkyl, b. at least one inorganic basic ammonium salt, c. another inorganic salt selected from the group of carbonates and hydrogen carbonates. d. at least one dispersant of the polycarboxylate type, e. at least one anionic wetting agent, f. at least one inert filler, g. optionally a structuring agent, h. optionally further insecticidal active ingredients, i. optionally further adjuvants.

[0073] In a further preferred embodiment, the subject of the invention is an insecticidal solid composition in the form of water-dispersible granules containing: a. Compound of formula (I) selected from the following compounds b. at least one inorganic basic ammonium salt selected from the group comprising diammonium hydrogen phosphate (DAHP), c. at least one inorganic bicarbonate salt whose cation is not ammonium, d.at least one polycarboxylate-type dispersant selected from the group consisting of hydrophobically modified comb-like polymers, comprising polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin, a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, and modified copolymers of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acid and vinyl acetate, a copolymer of maleic acid or maleic anhydride and acrylic acid, an N-methyl fatty acid (e.g., C-Cix) sarcosinate, a carboxylic acid such as a resin acid, or a fatty acid (e.g.,Cs-Cis) or a salt of such a carboxylic acid, as well as the salts of these copolymers, e. at least one anionic wetting agent selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates and the sodium salts of dioctylsulfosuccinic acid, f. at least one inert filler selected from the group comprising carbonates, silicates and oxides, as well as urea-formaldehyde condensates and celluloses, g. optionally a structuring agent selected from the group comprising polyacrylic acid and its salts, cross-linked polyacrylates as well as polyureas, polyurethanes and derivatized polyureas and polyurethanes, h. optionally further insecticidal active ingredients, i. optionally further adjuvants.

[0074] In a particularly preferred embodiment, the invention relates to an insecticidal solid composition in the form of water-dispersible granules containing: a. Compound of formula (1-2) having the following structure: b. at least one inorganic basic ammonium salt selected from the group comprising diammonium hydrogen phosphate (DAHP), c. at least one inorganic bicarbonate salt selected from the group comprising sodium and potassium bicarbonate, d. at least one dispersant selected from the group comprising sodium salts of copolymers of methacrylic acid and styrene and modified copolymers of methacrylic acid and styrene, e. at least one anionic wetting agent selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates and the sodium salts of dioctylsulfosuccinic acid, f. at least one inert filler selected from the group comprising kaolin, rutile and silicon dioxide, g. optionally a structuring agent selected from the group comprising polymethylurea resins, h. optionally further insecticidal active ingredients, i. optionally further adjuvants.

[0075] In an alternative embodiment, the above-mentioned embodiments necessarily contain a further insecticidal active ingredient (g), preferably from the group comprising imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron; particularly preferably from the group comprising ethiprole, spinetoram, abamectin and flupyradifurone.

[0076] In an alternative embodiment, in the embodiments mentioned above and also in the following, a further adjuvant i), preferably a silicone oil-based defoamer, more preferably polydimethylsiloxane absorbed on a solid substrate, is necessarily present.

[0077] Solo formulations:

[0078] The proportion of the active ingredient (component a / compounds of formula I / 1-2) in the compositions according to the invention with only one active ingredient is preferably 0.5 - 25 wt.%, more preferably 1 - 18 wt.%, and particularly preferably 2 - 12 wt.%.

[0079] The proportion of the salt (component b) in the compositions according to the invention with only one active ingredient is preferably 20 - 75 wt.%, more preferably 25 - 68 wt.%, and particularly preferably 30 - 66 wt.%.

[0080] The proportion of the inorganic salt (component c) in the compositions according to the invention with only one active ingredient is preferably 1 - 10 wt.%, more preferably 1.5 - 9 wt.%, and particularly preferably 2 - 7 wt.%

[0081] The proportion of the dispersant (component d) in the compositions according to the invention with only one active ingredient is preferably 1 - 20 wt.%, more preferably 5 - 15 wt.%, and particularly preferably 8 - 12 wt.%.

[0082] The proportion of the wetting agent (component e) in the compositions according to the invention with only one active ingredient is preferably 0.5 - 15 wt.%, more preferably 1 - 10 wt.%, and particularly preferably 1.5 - 2.5 wt.%.

[0083] The proportion of the filler (component f) in the compositions according to the invention with only one active ingredient is preferably 0.5 - 30 wt.%, more preferably 5 - 25 wt.%, and particularly preferably 10 - 22 wt.%.

[0084] The proportion of the structuring agent (component g) in the compositions according to the invention with only one active ingredient is preferably 0.5 - 15 wt.%, more preferably 1 - 10 wt.%, and particularly preferably 3 - 8 wt.%.

[0085] The proportion of further adjuvants (component i) - if present - in the compositions according to the invention is preferably 0 - 10 wt.%, more preferably 0 - 8 wt.%, and particularly preferably 0 - 5 wt.%.

[0086] If component i) is necessarily included according to the alternative embodiment, e.g. as a defoamer, its proportion in the solid formulations according to the invention is 0.1 - 5 wt.%.

[0087] A preferred embodiment of the invention are compositions containing components a) 0.5 - 25 wt.% b) 20 - 75 wt.% c) 1 - 10 wt.% d) 1 - 20 wt.% e) 0.5 - 15 wt.% f) 0.5 - 30 wt.% g) 0.5 - 15 wt.%

[0088] A further preferred embodiment of the invention are compositions comprising components a) 1 - 18 wt.% b) 25 - 68 wt.% c) 1.5 - 9 wt.% d) 5 - 15 wt.% e) 1 - 10 wt.% f) 5 - 25 wt.% g) 1 - 10 wt.%

[0089] An even more preferred embodiment of the invention are compositions comprising components a) 2-12 wt.% b) 30-66 wt.% c) 2-7 wt.% d) 8-12 wt.% e) 1.5-2.5 wt.% f) 10-22 wt.% g) 3-8 wt.%.

[0090] According to an alternative embodiment in which component i) is mandatorily present, a solid composition is preferably comprising components in a) 2 - 12 wt.% b) 30 - 66 wt.% c) 2 - 7 wt.% d) 8 - 12 wt.% e) 1.5 - 2.5 wt.% f) 10 - 22 wt.% g) 3 - 8 wt.% i) 0.1 - 5 wt.%.

[0091] Mixture formulations:

[0092] The proportion of the further active ingredients (component h) - if contained - in the compositions according to the invention is preferably 1 - 30 wt.%, more preferably 1 - 25 wt.%, and particularly preferably 1.5 - 20 wt.%.

[0093] According to an alternative embodiment, in which components h) and i) are necessarily included, a solid composition is preferably containing components in a) 2 - 12 wt.% b) 30 - 66 wt.% c) 2 - 7 wt.% d) 8 - 12 wt.% e) 1.5 - 2.5 wt.%

[0094] 1) 10 - 22% by weight g) 3 - 8% by weight h) 1.5 - 20% by weight i) 0.1 - 5% by weight.

[0095] Particularly preferred for use in the above-mentioned compositions are tetramic acid derivatives of the above-mentioned formula (I) with G = hydrogen (a).

[0096] Tetramic acid derivatives of the above-mentioned formula (I) with G = E (d) are also particularly preferred.

[0097] Compound 1-2 is preferably used in its thermodynamically most stable polymorphic structure. This crystal structure and other physical data were determined as follows:

[0098] Sample preparation:

[0099] Compound 1-2 (C19H22CINO4 / MW = 363.84 g / mol) was crystallized from methanol and dried at room temperature to give modification A.

[0100] The modification A of 1-2 can be characterized by X-ray powder diffraction based on the corresponding diffraction patterns recorded at 25°C and with Cu-Koc 1 radiation (1.5406 Å) (FIGURE 1).

[0101] The modification A according to the present invention shows at least 3, preferably at least 5, more preferably at least 7, even more preferably at least 10, and most preferably all reflections as shown in FIGURE 1 and Table 2a). Table 2b) shows all measured reflections of the modification A:

[0102] Modification A according to the present invention is further characterized by the X-ray diffraction pattern shown in Figure I.

[0103] Crystallographic studies on single crystals of modification A showed that the crystal structure is monoclinic. The unit cell has the space group P2i / c. Table 2: Crystallographic properties of modification A a, b, c = length of the sides of the unit cell a, ß, y = angle of the unit cell Z = number of molecules in the unit cell

[0104] corresponding spectrum recorded at 25°C using a diamond ATR device at a resolution of 4 cm' 1 (FIGURE 2). Modification A of the present invention shows at least 3, preferably at least 5, more preferably at least 7, and most preferably all bands as seen in Figure 2 and described in Table 2c. Table 2c) IR bands [cm' 1 ]

[0105] In addition to the modification A described above, compound 1-2 can exist in other polymorphic forms, including pseudopolymorphic forms (hydrates, solvates, etc.). The application rate of the formulations according to the invention can be varied within a wide range. It depends on the respective active ingredients and their content in the compositions.

[0106] With the aid of the compositions according to the invention, the insecticidal active ingredient mixtures can be applied to plants and / or their habitat in a particularly advantageous manner.

[0107] All plants and plant parts can be treated with the compositions according to the invention. Plants are understood to mean all plants and plant populations, such as desirable and undesirable wild plants or cultivated plants (including naturally occurring cultivated plants). Cultivated plants can be plants that can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods, or combinations of these methods, including transgenic plants and including plant varieties that may or may not be protected by plant variety rights. Plant parts are understood to mean all above-ground and below-ground parts and organs of the plants, such as shoots, leaves, flowers, and roots, with examples including leaves, needles, stems, trunks, flowers, fruiting bodies, fruits, and seeds, as well as roots, tubers, and rhizomes.Plant parts also include harvested material as well as vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

[0108] The compounds of formula (I) are preferably used in the formulations according to the invention by spray application, but also after drenching, dipping or by drip application against animal pests from the following pest families:

[0109] Preferred members of the blister aphid family (Pemphigidae) are Eriosoma spp., Pemphigus spp., in crops such as citrus, pome fruit, stone fruit, leafy vegetables, root and tuber vegetables and ornamental plants.

[0110] Preferred members of the root aphid family (Phylloxeridae) are Phylloxera spp. in wine, nuts, and citrus.

[0111] Preferred members of the Psyllidae family are: Psylla spp., Paratrioza spp., Tenalaphara spp., Diaphorina spp., Trioza spp., in crops such as pome fruit, stone fruit, citrus, vegetables, potatoes, in tropical crops.

[0112] Preferred members of the Coccidae family are: Ceropiastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., Coccus spp., in perennial crops such as citrus, pome fruit, stone fruit, olives, wine, coffee, tea, tropical crops, ornamental plants, vegetables.

[0113] Preferred from the family of scale insects (Diaspididae): Quadraspidiotus spp., Aonidiella spp., Lepidosaphes spp., Aspidiotus spp., Aspis spp., Diaspis spp., Parlatoria spp., Pseudaulacaspis spp., Unaspis spp., Pinnaspis spp., Selenaspidus spp., in crops such as citrus, pome fruit, stone fruit, almonds, pistachios, nuts, olives, tea, ornamental plants, wine, tropical crops.

[0114] Preferred members of the scale insect family (Ortheziidae) are Orthezia spp. in citrus, pome fruit, and stone fruit.

[0115] Preferred members of the mealybug and mealybug family (Pseudococcidae) are Pericerga, Pseudococcus spp., Pianococcus spp., Dysmicoccus spp., in crops such as citrus, stone and pome fruit, tea, wine, vegetables, ornamental plants and tropical crops.

[0116] Also preferred from the family of whitefly (Aleyrodidae): Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes spp., Dialeurodes spp., Parabemisia myricae in crops such as vegetables, melons, potatoes, tobacco, berries, citrus, ornamental plants, cotton, soy and tropical crops.

[0117] Also preferred from the family of tube lice (Aphidae) are:

[0118] Myzus spp. in tobacco, stone fruits, berries, fruit vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamental plants, spices,

[0119] Acyrthosiphon onobrychis in vegetables,

[0120] Aphis spp. in tobacco, citrus, pome fruit, stone fruit, melons, strawberries, berries, fruit vegetables, leafy vegetables, tubers, stalks and root vegetables, ornamental plants, potatoes, pumpkins, spices,

[0121] Rhodobium porosum in strawberries,

[0122] Nasonovia ribisnigri in leafy vegetables,

[0123] Macrosiphum spp. in ornamental plants, potatoes, leaf and fruit vegetables, strawberries,

[0124] Phorodon humuli in hops,

[0125] Brevicoryne brassicae in leafy vegetables,

[0126] Toxoptera spp.in citrus, stone fruit, almonds, nuts, spices,

[0127] Aulacorthum spp. in citrus, potatoes, fruit and leafy vegetables,

[0128] Anuraphis cardui in vegetables,

[0129] Brachycaudus helycrisii in sunflowers,

[0130] Acyrthosiphon onobrychis in vegetables. Also preferred from the thrips family (Thripidae): Anaphothrips spp., Baliothrips spp., Caliothrips spp., Frankliniella spp., Heliothrips spp., Hercinothrips spp., Rhipiphorothrips spp., Scirtothrips spp., Kakothrips spp., Selenothrips spp., and Thrips spp., in crops such as fruit, cotton, vines, tea, nuts, tropical crops, ornamental plants, conifers, tobacco, spices, vegetables, berries, melons, citrus fruits, and potatoes.

[0131] Also preferred from the families of leaf miners (Agromyzidae) and flower flies (Anthomyiidae): Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., Pegomyia spp. in crops such as vegetables, melons, potatoes, nuts, ornamental plants.

[0132] Preferred insects from the families of leafhoppers (Cicadellidae) and hornhoppers (Delphacidae) are Circulifer spp., Dalbus spp., Empoasca spp., Erythroneura spp., Homalodisca spp., lodioscopus spp., Laodelphax spp., Nephotettix spp., Nilaparvata spp., Oncometopia spp., Sogatella spp., in crops such as citrus, fruit, wine, potatoes, vegetables, ornamental plants, conifers, melons, berries, tea, nuts, rice and tropical crops.

[0133] Preferred from the family of leaf miners (Gracillariidae) are:

[0134] Caloptilia spp., Gracillaria spp., Lithocolletis spp., Leucoptera spp., Phtorimaea spp., Phyllocnistis spp. in crops such as pome fruits, stone fruits, vines, nuts, citrus, conifers, potatoes, and coffee.

[0135] Preferred from the family of gall midges (Cecodomyiidae) are:

[0136] Contarinia spp., Dasineura spp., Diplosis spp., Prodiplosis spp., Thecodiplosis spp., Sitodiplosis spp., Haplodiplosis spp. in crops such as citrus, pome fruit, stone fruit, vegetables, potatoes, spices, soft fruit, conifers, hops.

[0137] Also preferred from the fruit fly family (Tephritidae) are:

[0138] Anastrepha spp., Ceratitis spp., Dacus spp., Rhagoletis spp. in crops such as vegetables, soft fruits, melons, stone and pome fruits, ornamental plants, potatoes, vines, tropical crops, citrus fruits, and olives.

[0139] Also preferred are mites from the families of spider mites (Tetrany chidae) and gall mites (Eriophydae):

[0140] Tetranychus spp., Panonychus spp., Aculops spp. in crops such as vegetables, potatoes, ornamental plants, citrus, vines, and conifers.

[0141] The treatment of plants and plant parts according to the invention with the compositions according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by watering (drenching), dipping, spraying, evaporating, atomizing, scattering, painting and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.

[0142] The active ingredient is preferably applied by spraying. Alternatively, the active ingredient can be applied by drenching, drip application, or dipping.

[0143] Preferably, the plant to be treated is selected from the group consisting of cotton, soybean, tobacco, vegetables, spices, ornamental plants, conifers, citrus plants, fruit, tropical crops, nuts and vines.

[0144] The composition according to the invention is preferably effective against pests from the families of bladder aphids, root aphids, aphids, scale insects, lidded scale insects, tube aphids, mealybugs, mealybugs, whitefly, tube aphids, thrips, leafhoppers, hornhoppers, leaf miners, gall midges, fruit flies, leaf miners, spider mites, gall mites.

[0145] It has also been found that the compositions according to the invention can be produced by moistening a powdered mixture consisting of the active ingredients and the formulation auxiliaries, subsequently granulating them by low-pressure extrusion, and then drying the moist granules. Relevant equipment for moistening, extrusion, and drying is known to those skilled in the art. During production, particular care must be taken to keep the temperatures to which the product is exposed below 60°C during all process steps, and preferably below 50°C.

[0146] This method is also the subject of the invention.

[0147] The treatment of plants and plant parts according to the invention with the compositions according to the invention is carried out directly or by exposure to their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, evaporating, nebulizing, scattering, painting and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.

[0148] The following examples illustrate the subject matter of the invention without limiting it. Examples

[0149] 1 Sample preparation and physical behavior 1 kg of a mixture of compound 1-2 optionally a second active ingredient, diammonium hydrogen phosphate

[0150] (DAHP), (if necessary) a second inorganic salt, Morwet EFW, Pergopak M, kaolin W, dispersing agent, if necessary additionally magnesium stearate and defoamer were ground in a 4" air jet mill Hosokawa 100 AS (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g / min) as known to the person skilled in the art, moistened with water (approx. 14 wt.%) and extruded on a Fuji Paudal Dome extruder (die size 1 mm) to a WG and dried in a fluidized bed dryer.

[0151] Examples Composition

[0152] Examples of warehouse data

[0153] Examples Composition

[0154] 5 Determination of the pH value (according to method CIPAC MT 75.3): The pH value is measured with a standard pH glass electrode in a 1% dispersion of the granules in demineralized water at 23 °C.

[0155] Determination of suspendability (according to method CIPAC MT 184.1):

[0156] A 1% suspension in water (CIPAC C) is dispersed in a 250 mL measuring cylinder. The mixture is equilibrated for 30 minutes. The top 9 / 10 of the suspension is then removed. The remaining 1 / 10 is dried, and the residue (sediment) is determined gravimetrically. Suspendability is defined as:

[0157] 10 / 9 * 100 * (sample amount [g]*proportion ai [% J / l 00 - residue [g]) / (sample amount [g]*proportion ai [% ] / l 00)

[0158] Thus, a value of 100% corresponds to a uniform distribution of all insoluble components throughout the sample volume.

[0159] Determination of wet sieve residue (according to method CIPAC MT 185):

[0160] 25 g of granules are placed in 250 mL of water in a beaker. After one minute, the mixture is stirred for 5 minutes using a magnetic stirrer. The dispersion and the wash water for cleaning the beaker are then transferred to the appropriate sieve. The sieve is then rinsed with cold water until no further change in the residue on the sieve is visible (max. 10 min). After draining the sieve, the residue is quantitatively transferred to an evaporating dish with demineralized water, allowed to dry, and the residue is determined gravimetrically.

[0161] 2. Application examples:

[0162] • The manufacturability test of a pre-slurry for spray applications was carried out with a dispensing hopper under the following conditions: Tank volume: 400 L

[0163] • Water volume: 100 L

[0164] • Granule quantity: 2.5 kg

[0165] While the water was pumped in a circular flow, the 2.5 kg of product was quickly added to the induction hopper and pumped around for another 10 minutes. After 5 and 10 minutes, the residue in the induction hopper, the filter in the intake system, and the residue of undispersed product in the tank were inspected.

[0166] Materials used

[0167] Geropon ® TA / 72 is a polycarboxylic acid sodium salt, Geropon ® SDS is a dioctyl sodium 5 sulfosuccinate, Geropon ® L-Wet max is a blend from Solvay.

[0168] Kaolin W is an aluminum hydrosilicate from Erbslöh Lohrheim GmbH & Co. KG, Lohrheim, Germany.

[0169] Tersperse ® 2700 is a naphthalenesulfonic acid-formaldehyde condensate, sodium salt from Indorama Ventures, The Woodlands, Texas, USA.

[0170] 10 Rhodorsil Antimousse EP 6703 ® is an absorbed polydimethylsiloxane, Solvay.

[0171] Morwet EFW is an alkyl naphthalene sulfonate sodium salt from Nouryon, Stemungsund, Sweden.

[0172] Pergopak ® M is a polymethyl urea resin from Huber Martinswerk, Bergheim, Germany.

[0173] 15 Atlox MetasperseTM 550S is a modified styrene-acrylic polymer manufactured by Croda, UK.

[0174] Trilon ® B powder is a tetrasodium ethylenediaminetetraacetate from BTC Europe GmbH, Monheim, Germany.

[0175] 20 Flupyradifurone is a crop protection active ingredient from Bayer Crop Science.

[0176] Abamectin is a crop protection agent from Syngenta.

[0177] Spinetoram is a crop protection active ingredient from Corteva.

Claims

1. Solid compositions in the form of water-dispersible granules containing: a. Tetramic acid derivatives of formula (I) W and Y independently represent hydrogen, Cl-C4-alkyl, chlorine, bromine, iodine or fluorine, X represents C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which they are attached represent C3-C6-cycloalkyl which is substituted by an alkylenedioxyl group optionally substituted by C1-C4-alkyl or C1-C4-alkoxy-C1-C2-alkyl, which forms a 5-ring or 6-ring ketal with the carbon atom to which it is attached, G stands for hydrogen (a) or for one of the groups E stands for a metal ion or an ammonium ion, M stands for oxygen or sulfur, RI stands for straight-chain or branched Cl-C6-alkyl, R2 represents straight-chain or branched C1-C6 alkyl. b. at least one basic salt, c. at least one further inorganic salt from the group of carbonates and bicarbonates, d. at least one dispersant, e. at least one wetting agent, f. at least one filler, g. at least one structuring agent, h. optionally further active ingredients, i. optionally further conventional adjuvants and formulation aids.

2. The composition according to claim 1, characterized in that at least one further active ingredient is present as component h).

3. Composition according to claim 1 or 2, characterized in that component a) in the compositions according to the invention is a compound of formula (I) with 4. Composition according to claim 1 or 2, characterized in that component a) is a Compound of the formula is.

5. Composition according to one or more of the preceding claims, characterized in that component b) is diammonium hydrogen phosphate (DAHP).

6. Composition according to one of the preceding claims, characterized in that component c) is selected from the group comprising sodium bicarbonate and potassium bicarbonate.

7. Composition according to one or more of the preceding claims, characterized in that component d) is a dispersant selected from the group comprising sodium salts of copolymers of maleic acid and olefins and sodium salts of copolymers of methacrylic acid and styrene, modified copolymers of methacrylic acid and styrene, particularly preferably sodium salts of copolymers of methacrylic acid and styrene and modified copolymers of methacrylic acid and styrene.

8. Composition according to one or more of the preceding claims, characterized in that component e) is selected from the group comprising sodium salts of alkylated naphthalenesulfonates and the sodium salts of dioctylsulfosuccinic acid, particularly preferably sodium salts of alkylated naphthalenesulfonates.

9. Composition according to one or more of the preceding claims, characterized in that component 1) is selected from the group comprising kaolin, rutile and silicon dioxide, particularly preferably kaolin.

10. Composition according to one or more of the preceding claims, characterized in that component g) is selected from the group comprising polymethylurea resins.

11. Composition according to one or more of the preceding claims, characterized in that component h) is selected from the group consisting Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron; particularly preferably from the group comprising ethiprole, spinetoram, abamectin and flupyradifurone.

12. Composition according to one or more of the preceding claims containing a. Compounds of formula (I) where the compounds of formula (I) have the following definitions: W stands for methyl, X stands for chlorine or methyl, Y stands for chlorine, bromine or methyl, A, B and the carbon atom to which they are attached represent saturated C6-cycloalkyl substituted with an alkylenedioxyl group forming a 5-ring or 6-ring ketal with the carbon atom to which it is attached, G stands for hydrogen (a) or for one of the groups in which M stands for oxygen, E stands for a metal ion equivalent or an ammonium ion, Ri represents straight-chain or branched C | -Cq-alkyl, R^ represents straight-chain or branched Cj-Cq-alkyl. b. at least one inorganic basic salt, c. at least one inorganic salt selected from the group comprising sodium bicarbonate and potassium bicarbonate. d. at least one polycarboxylate-type dispersant, e. at least one anionic wetting agent, f. at least one inert filler, g. at least one structuring agent, h. optionally further insecticidal active ingredients, i. optionally further adjuvants.

13. Composition according to one or more of the preceding claims2 containing a compound of formula (I) selected from the following compounds b. at least one inorganic basic ammonium salt selected from the group comprising diammonium hydrogen phosphate (DAHP), c. at least one further inorganic salt from the group of carbonates and hydrogen carbonates, d. at least one polycarboxylate-type dispersant selected from the group consisting of hydrophobically modified comb-like polymers, comprising polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin, a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acid and vinyl acetate, copolymers of methacrylic acid and styrene, modified copolymers of methacrylic acid and styrene, a copolymer of maleic acid or maleic anhydride and acrylic acid, an N-methyl fatty acid (e.g. C8-C18) sarcosinate, a carboxylic acid such as a resin acid or a fatty acid (e.g.Cs-Cis) or a salt of such a carboxylic acid, as well as the salts of these copolymers, e. at least one anionic wetting agent selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates and the sodium salts of dioctylsulfosuccinic acid, f. at least one inert filler selected from the group comprising carbonates, silicates and oxides, as well as urea-formaldehyde condensates and celluloses, g. at least one structure former selected from the group comprising polyacrylic acid and salts thereof, cross-linked polyacrylates as well as polyureas, polyurethanes and derivatized polyureas and polyurethanes, h. optionally further insecticidal active ingredients, i. optionally further adjuvants.

14. Composition according to one or more of the preceding claims containing the compound of formula (1-2) having the following structure: (I) b. at least one inorganic basic ammonium salt selected from the group comprising diammonium hydrogen phosphate (DAHP), c. at least one inorganic salt selected from the group comprising sodium hydrogen carbonate and potassium hydrogen carbonate, d. at least one dispersant selected from the group comprising sodium salts of copolymers of methacrylic acid and styrene, e. at least one anionic wetting agent selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates, f. at least one inert filler selected from the group comprising kaolin, rutile and silicon dioxide, g. at least one structuring agent selected from the group comprising polymethylurea resins, h. optionally further insecticidal active ingredients, i. optionally further adjuvants.

15. Composition according to one or more of the preceding claims, characterized in that components a - g are present in a) 2 - 12 wt.% b) 30 - 66 wt.% c) 2 - 7 wt.% d) 8 - 12 wt.% e) 1.5 - 2.5 wt.% f) 10 - 22 wt.% g) 3 - 8 wt.%.

16. Composition according to one or more of the preceding claims, characterized in that component h) is additionally contained in h) 1.5-20 wt.% 17. Composition according to one or more of the preceding claims, characterized in that component i) is contained in i) 0.1-5 wt.% 18. A process for producing a composition according to one or more of the preceding claims, characterized in that the composition is produced by mixing the components and subsequent extrusion.

19. Use of a composition according to one or more of claims 1 to 17 for applying the agrochemical active ingredients contained therein to plants and / or their habitat.

20. Agent characterized by a content of a composition according to one or more of claims 1 to 17.

21. Use of a composition according to one or more of claims 1 to 17 for controlling insects.

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