Solid formulation of insecticidal mixtures

Abstract

To provide solid formulations (especially water-dispersible granules) of tetramic acid derivatives and mixtures of these tetramic acid derivatives, which cause only very small amounts of wet sieve residues to be formed during production, which can be efficiently extruded, and which have high suspension stability, excellent suspendability, and high bioavailability of the active ingredient, or excellent penetration through the cuticle.SOLUTION: A solid composition in the form of water-dispersible granules comprises: a. tetramic acid derivative of formula (I); b. at least one basic salt; c. at least one dispersant; d. at least one wetting agent; e. at least one filler; f. at least one structure former; g. optionally a complexing agent; h. optionally further active ingredients; and i. optionally further customary adjuvants and formulation auxiliaries.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to solid formulations (especially water-dispersible granules) of tetramic acid derivatives and mixtures of these tetramic acid derivatives, to a process for their preparation and to their use for applying the active ingredients present. [Background technology]

[0002] The preparation of WG formulations using formulation auxiliaries specified in the prior art results in formulations with undesirable properties. For example, the low melting point of the active ingredient or active ingredient mixture leads to the formation of a large amount of wet sieve residues, which lead to the clogging of the spray nozzle during the later development of the spray liquid. Furthermore, the dispersed active ingredient or ingredients are usually only available in low concentrations in solution, and / or the uptake or penetration of the active ingredient or ingredients into the cuticle is insufficient. Summary of the Invention [Problem to be solved by the invention]

[0003] It has now surprisingly been found that the formulations have particularly advantageous properties, for example that only small amounts of wet sieve residues are formed during their production, which can be efficiently extruded, and that they have particularly high suspension stability, good suspendability, and high bioavailability of the active ingredient or good penetration into the cuticle.

[0004] A further feature of the formulations of the present invention is that they have excellent suspendability, even at high salt loads, especially after storage.

[0005] These formulations therefore form the subject of the present invention.The invention further relates to a process for producing these water-dispersible granules and to their use for application. [Means for solving the problem]

[0006] Thus, the present invention provides an insecticidal solid composition, preferably in the form of a water-dispersible granule (solid formulation), comprising: a. As a component, a tetramic acid derivative of formula (I) [ka] (In the formula, W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine; X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which they are attached are C3-C6-cycloalkyl, optionally substituted by C1-C4-alkyl- or C1-C4-alkoxy-C1-C2-alkyl-substituted alkylenedioxy groups, which together with the carbon atom to which they are attached form a 5- or 6-membered ketal, G is hydrogen (a) or a group [ka] (In the formula, E is a metal ion or an ammonium ion; M is oxygen or sulfur; R1 is a linear or branched C1-C6 alkyl; R2 is a straight or branched C1-C6 alkyl. (one of the b. at least one basic salt; c. at least one dispersant; d. at least one wetting agent; e. at least one filler; f. at least one structure-forming agent; g. optionally, a complexing agent; h. optionally, further active ingredients, and i. Optionally, further conventional adjuvants and formulation aids. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 shows the X-ray diffraction pattern of I-2 (modification A). [Diagram 2] FIG. 2 shows the IR spectrum of the polymorphic form of modification A of I-1.

[0008] In the present invention, in a formula, such as formula (I), unless otherwise stated, optionally substituted groups may be mono- or polysubstituted, and in the case of polysubstitution the substituents may be the same or different.

[0009] Furthermore, within the scope of the preferences stated in the present invention, it is to be understood that the various levels of preference can be combined with one another in permutations, but in each case, the same levels of preference, in particular the most preferred embodiments / levels of preference, should in each case be combined with one another and are actually disclosed as such combinations.

[0010] The above compositions consisting only of essential ingredients (and not optional ingredients) should be considered as disclosed as well.

[0011] Percentages - unless otherwise stated - should be considered as percentages by weight and the weight % of a composition should total 100.

[0012] Unless otherwise defined, "basic" in the context of the present invention means a pH in aqueous solution above pH 7.

[0013] The formulation according to the invention in aqueous dispersion has a pH of >7.

[0014] In a preferred embodiment, the formulation comprises at least one antifoaming agent (i), preferably in solid form, preferably based on a silicone oil or wax, more preferably on PDMS absorbed on a solid carrier.

[0015] A preferred antifoaming agent is Rhodorsil Antimousse EP6703 (an absorbent polydimethylsiloxane) manufactured by Solvay.

[0016] a) Active ingredient In a preferred embodiment, component a) in the composition according to the invention is a compound of formula (I) [ka] The compounds of formula (I) have the following definitions: W is methyl; X is chlorine or methyl; Y is chlorine, bromine or methyl; A, B and the carbon atom to which they are attached are a saturated C6 cycloalkyl substituted with an alkylenedioxy group which together with the carbon atom to which it is attached forms a 5- or 6-membered ketal; G is hydrogen (a) or a group [ka] (In the formula, M is oxygen; E is one metal ion equivalent or an ammonium ion; R 1 is a linear or branched C1-C4 alkyl group; R 2 is a straight-chain or branched C1-C4 alkyl group. (one of It is.

[0017] In a further preferred embodiment, component a) in the composition according to the invention is a compound of formula (I) having [ka]

[0018] In a particularly preferred embodiment, component a) is of the formula [ka] It is a compound of the formula:

[0019] b) Salt Component b) is preferably selected from the group comprising inorganic basic ammonium salts.

[0020] More preferably, b) is selected from the group comprising ammonium carbonate, ammonium hydrogen carbonate and diammonium hydrogen phosphate (DAHP).

[0021] More preferably, b) is DAHP.

[0022] c) Dispersants Suitable dispersants in the context of the present invention are dispersants of the polycarboxylate type, for example hydrophobically modified comb polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (such as isobutylene or diisobutylene), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylate, copolymers of acrylic acid and vinyl acetate, copolymers of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, copolymers of maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acids (e.g. C8 to C 18 ) sarcosinates, carboxylic acids such as resin acids or fatty acids (e.g., C8-C 18 ) or the salts of such carboxylic acids. The copolymers may also be in the form of their salts, such as alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines.

[0023] 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 / Huntsman; Atlox Metasperse 500S / Croda).

[0024] More preferably, the dispersant is the sodium salt of a copolymer of methacrylic acid and styrene.

[0025] Suitable dispersants, such as Tersperse 2700, are also described in WO2008036865.

[0026] d) Wetting agent Useful nonionic surfactants include all substances of this type that can typically be used in agrochemical compositions, preferably polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, as well as polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters, and also alkyl ethoxylates and alkylaryl ethoxylates, optionally phosphorylated and optionally neutralized with base, such as sorbitol ethoxylates, and polyoxyalkyleneamine derivatives.

[0027] Suitable anionic surfactants include all materials of this type that can typically be used in pesticide compositions.

[0028] Useful wetting agents are preferably anionic surfactants selected from the group comprising salts of polystyrene sulfonic acid, salts of polyvinyl sulfonic acid, salts of naphthalene sulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid and formaldehyde, as well as salts of lignosulfonic acid and sodium salts of alkylated naphthalene sulfonic acids, such as Morwet EFW®, and sodium salts of dioctyl sulfosuccinic acid, such as Aerosol OTB®, and block polymers of propylene oxide and ethylene oxide on ethylenediamine, such as Synperonic T 905®.

[0029] Further preferred dispersants (d) suitable in the context of the present invention are wetting agents selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates, such as Morwet EFW®, and the sodium salts of dioctyl sulfosuccinic acid, such as Aerosol OTB®, more preferably the sodium salts of alkylated naphthalenesulfonates, preferably Morwet EFW®.

[0030] e) Filler Useful inert filler materials are all the substances that can be typically used for this purpose in agrochemical compositions.Also preferred are inorganic particles such as carbonates, silicates and oxides, and organic substances such as urea-formaldehyde condensates and cellulose (e.g. Ulmerweiss 6AL, Celite 209, Argirec B21 and B22, Bentone EW, Luz2 talc, Etiquette Violette).Examples also include kaolin, rutile, silicon dioxide, fine silica, silica gel, and natural and synthetic silicates, and talc.

[0031] The fillers are more preferably selected from the group comprising kaolin, rutile and silicon dioxide, with kaolin being particularly preferred.

[0032] f) Structure-forming agents The formulation according to the present invention may further comprise a structure-forming agent. In particular polyacrylic acid and its salts, and in particular crosslinked polyacrylates, as well as polyurethanes and derivatized polyurethanes and their salts, are suitable for this purpose. Examples of such suitable acrylates are (poly)methacrylates, (poly)methylmethacrylates, polyacrylamides, (poly)ethoxyethylmethacrylates and Pergopak® M. Pergopak® M is a polymethylurea resin manufactured by Albemarle Corporation, Baton Rouge, LA, USA.

[0033] More preferably the structure former is a polymethylurea resin, especially Pergopak®M.

[0034] g) Complexing Agent In the context of the present invention, all customary complexing agents are suitable, but the complexing agent is in particular selected from the group comprising ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and the salts and / or hydrates of the above or combinations thereof.

[0035] A particularly preferred complexing agent is Na4EDTA (tetrasodium ethylenediaminetetraacetate), for example Trilon® B Powder from BASF.

[0036] h) Further active ingredients The formulation may in principle comprise one or more further active agrochemical ingredients, preferably selected from the group of insecticides, herbicides, fungicides and host defense inducers.

[0037] Further preferred active ingredients are one or more selected from the group of insecticides, even more preferably from the group comprising imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron.

[0038] Particularly preferred is one or more further active ingredients selected from the group comprising ethiprole and flupyradifurone.

[0039] i) Adjuvants and formulation aids Useful antifoam agents are all substances which can typically be used for this purpose in agrochemical compositions. Silicone oil-based antifoam agents and magnesium stearate are preferred.

[0040] Polydimethylsiloxanes absorbed onto a solid substrate are particularly preferred. Rhodorsil Antimousse EP 6703 is one example.

[0041] Useful preservatives include all substances that can typically be used for this purpose in pesticide compositions of this type. Examples include Preventol® (Lanxess AG) and Proxel®.

[0042] Useful antioxidants are all substances which can typically be used for this purpose in agrochemical compositions. Butylhydroxytoluene is preferred.

[0043] Useful pigments are all substances that can typically be used for this purpose in agrochemical compositions. Examples include titanium dioxide, black pigments, zinc oxide and blue pigments, and also Permanent Red FGR.

[0044] In a preferred embodiment, the present invention provides an insecticidal solid composition in the form of a water-dispersible granule comprising: a. Compound of formula (I) [ka] The compounds of formula (I) have the following definitions: W is methyl; X is chlorine or methyl; Y is chlorine, bromine or methyl; A, B and the carbon atom to which they are attached are a saturated C6 cycloalkyl substituted with an alkylenedioxy group which together with the carbon atom to which it is attached forms a 5- or 6-membered ketal; G is hydrogen (a) or a group [ka] (In the formula, M is oxygen; E is one metal ion equivalent or an ammonium ion; R 1 is a linear or branched C1-C4 alkyl group; R 2 is a straight-chain or branched C1-C4 alkyl group. (one of the b. at least one inorganic basic ammonium salt; c. at least one polycarboxylate type dispersant; d. at least one anionic wetting agent; e. at least one inert filler; f. at least one structure-forming agent; g. at least one complexing agent; h. optionally, a further active insecticidal ingredient; i. optionally, an additional adjuvant.

[0045] In a further preferred embodiment, the present invention provides an insecticidal solid composition in the form of a water-dispersible granule comprising: a. A compound of formula (I) selected from the following compounds: [ka]

[0046] b. at least one inorganic basic ammonium salt selected from the group consisting of ammonium carbonate, ammonium bicarbonate and diammonium hydrogen phosphate (DAHP); c. Hydrophobically modified comb polymers including polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins, copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, and modified copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid and methacrylic acid, copolymers of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, copolymers of acrylic acid and methacrylate, copolymers of acrylic acid and vinyl acetate, copolymers of maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acids (e.g., C8-C 18 ) sarcosinates, carboxylic acids such as resin acids or fatty acids (e.g., C8-C 18 ) or the salts of such carboxylic acids, as well as the salts of their copolymers, d. at least one anionic wetting agent selected from the group consisting of the sodium salt of alkylated naphthalene sulfonate and the sodium salt of dioctyl sulfosuccinic acid; e. at least one inert filler selected from the group consisting of carbonates, silicates and oxides, and also urea-formaldehyde condensates and cellulose; f. at least one structure former selected from the group consisting of polyacrylic acid and its salts, crosslinked polyacrylates and polyureas, polyurethanes and derivatized polyureas and polyurethanes; g. at least one complexing agent selected from the group comprising ethylenediaminetetraacetic acid (EDTA), gluconic acid, nitrilotriacetic acid, diethylenediaminepentaacetic acid, and salts and / or hydrates of these compounds; h. optionally, a further active insecticidal ingredient; i. optionally, an additional adjuvant.

[0047] In a particularly preferred embodiment, the present invention provides an insecticidal solid composition in the form of a water-dispersible granule comprising: a. A compound having the formula (I-2) having the following structure: [ka] b. at least one inorganic basic ammonium salt selected from the group consisting of diammonium hydrogen sulfate (DAHP); c. at least one dispersant selected from the group consisting of copolymers of methacrylic acid and styrene, and sodium salts of modified copolymers of methacrylic acid and styrene; d. at least one anionic wetting agent selected from the group consisting of sodium salts of alkylated naphthalene sulfonates; e. at least one inert filler selected from the group consisting of kaolin, rutile and silicon dioxide; f. at least one structure-forming agent selected from the group consisting of polymethylurea resins; g. at least one complexing agent selected from the group comprising EDTA and its salts and hydrates, in particular the tetrasodium salt; h. optionally, a further active insecticidal ingredient; i. optionally, an additional adjuvant.

[0048] In an alternative embodiment, in the above embodiment, a further active insecticidal ingredient (g) is necessarily present, preferably selected from the group comprising imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron; more preferably from the group comprising ethiprole and flupyradifurone.

[0049] In an alternative embodiment, a further adjuvant is present in all of the above embodiments, preferably a silicone oil based antifoam agent, more preferably a polydimethylsiloxane absorbed onto a solid substrate.

[0050] Single formulation: The proportion of active ingredient (component a / compound of formula I / I-2) in a composition according to the invention containing only one active ingredient is Preferably 0.1 to 25% by weight, More preferably, 2 to 10% by weight, More preferably, 4 to 8% by weight It is.

[0051] The proportion of salt (component b) in a composition according to the invention containing only one active ingredient is Preferably 20 to 75% by weight, More preferably, 50 to 68% by weight, More preferably, 60 to 66% by weight It is.

[0052] The proportion of dispersant (component c) in a composition according to the invention containing only one active ingredient is Preferably 1 to 20% by weight, More preferably, 5 to 15% by weight, More preferably, 8 to 12% by weight It is.

[0053] The proportion of the wetting agent (component d) in a composition according to the invention containing only one active ingredient is Preferably 0.5 to 15% by weight, More preferably, 1 to 10% by weight, More preferably, 1.5 to 2.5% by weight It is.

[0054] The proportion of filler (component e) in a composition according to the invention containing only one active ingredient is Preferably, 0.5 to 70% by weight, More preferably, 5 to 25% by weight, More preferably, 10 to 22% by weight It is.

[0055] The proportion of structurant (component f) in a composition according to the invention containing only one active ingredient is Preferably 0.5 to 15% by weight, More preferably, 1 to 10% by weight, More preferably, 3 to 8% by weight It is.

[0056] The proportion of complexing agent (component g) in a composition according to the invention containing only one active ingredient is Preferably 0 to 10% by weight, More preferably, 0.1 to 2% by weight, More preferably, 0.1 to 1% by weight It is.

[0057] The proportion of further adjuvants (component i), if present, in the composition according to the invention is: Preferably 0 to 10% by weight, More preferably, 0 to 8% by weight More preferably, 0 to 5% by weight It is.

[0058] If component i) is in any alternative embodiment present, for example as an antifoaming agent, its proportion in the solid formulation according to the invention is between 0.1 and 5% by weight.

[0059] A preferred embodiment of the present invention comprises the component a) 0.1 to 25% by weight, b) 20 to 75% by weight; c) 1 to 20% by weight; d) 0.5 to 15% by weight; e) 0.5 to 70% by weight; f) 0.5 to 15% by weight; g) 0 to 10% by weight A composition comprising:

[0060] A further preferred embodiment of the present invention comprises the component a) 2 to 10% by weight; b) 50 to 68% by weight; c) 5 to 15% by weight; d) 1 to 10% by weight; e) 5 to 25% by weight; f) 1 to 10% by weight; g) 0.1 to 2% by weight A composition comprising:

[0061] An even more preferred embodiment of the present invention comprises the component a) 4 to 8% by weight; b) 60 to 66% by weight; c) 8 to 12% by weight; d) 1.5 to 2.5% by weight; e) 10 to 22% by weight; f) 3 to 8% by weight; g) 0.1 to 1% by weight A composition comprising:

[0062] In an alternative embodiment where component i) is always present, a) 4~8% by weight b)60~66% by weight c)8~12% by weight d)1.5~2.5wt% e) 10~22% by weight f) 3~8% by weight g)0.1~1wt% i)0.1~5% by weight A solid composition containing

[0063] Mixed preparations: The proportion of the active ingredient (component a / compound of formula I / I-2) in the composition according to the present invention is Preferably 1 to 10% by weight, More preferably, 1 to 7% by weight, More preferably, 1.5 to 5% by weight It is.

[0064] The proportion of salt (component b) in the composition according to the invention is Preferably 20 to 75% by weight, More preferably, 30 to 60% by weight, More preferably, 30 to 50% by weight It is.

[0065] The proportion of dispersant (component c) in the composition according to the invention is Preferably 1 to 20% by weight, More preferably, 5 to 15% by weight, More preferably, 8 to 12% by weight It is.

[0066] The proportion of the wetting agent (component d) in the composition according to the invention is Preferably 0.5 to 15% by weight, More preferably, 1 to 10% by weight, More preferably, 1.5 to 2.5% by weight It is.

[0067] The proportion of filler (component e) in the composition according to the invention is Preferably, 0.5 to 70% by weight, More preferably, 5 to 25% by weight, More preferably, 10 to 22% by weight It is.

[0068] The proportion of structuring agent (component f) in the composition according to the invention is Preferably 0.5 to 15% by weight, More preferably, 1 to 10% by weight, More preferably, 3 to 8% by weight It is.

[0069] The proportion of complexing agent (component g) in the composition according to the invention is Preferably 0 to 10% by weight, More preferably, 0.1 to 2% by weight, More preferably, 0.1 to 1% by weight It is.

[0070] The proportion of active ingredient (component h), if present, in the composition according to the invention is Preferably, 1 to 60% by weight, More preferably, 10 to 40% by weight, More preferably, 10 to 35% by weight It is.

[0071] The proportion of further adjuvants (component i), if present, in the composition according to the invention is: Preferably 0 to 10% by weight, More preferably, 0 to 8% by weight More preferably, 0 to 5% by weight It is.

[0072] If component i) is in any alternative embodiment present, for example as an antifoaming agent, its proportion in the solid formulation according to the invention is between 0.1 and 5% by weight.

[0073] The tetramic acid derivatives of the above formula (I) in which G=hydrogen (a) can be particularly preferably used in the above composition.

[0074] Tetramic acid derivatives of the above formula (I) in which G=E(d) can likewise be most preferably used.

[0075] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure, the crystal structure of which and further physical data were determined as follows: Sample preparation: Compound I-2(C 19 H 22 Modification A was obtained by crystallization of ClNO4 / MW=363.84 g / mol) from methanol and drying at room temperature.

[0076] Modification A of I-2 can be characterized by X-ray powder diffraction based on the corresponding diffractogram recorded at 25 °C using Cu-Kα1 radiation (1.5406 Å) (Figure 1).

[0077] Modification A according to the invention exhibits at least 3, preferably at least 5, more preferably at least 7, even more preferably at least 10 and most preferably all the reflections as shown in Figure 1 and in table 2a). Table 2b) shows all the measured reflections of modification A. Modification A according to the invention is further characterized by the X-ray diffraction diagram shown in FIG.

[0078] Crystallographic studies of a single crystal of modification A showed that the crystal structure is monoclinic. The unit cell has the P21 / c space group.

[0079] [Table 1]

[0080] [Table 2]

[0081] The polymorphic form of modification A of I-1 is 4 cm -1The IR spectrum can be determined by IR spectroscopy from the corresponding spectrum recorded at 25° C. using a Diamond ATR instrument with a resolution of 1000 nm (FIG. 2). Modification A of the present invention exhibits at least 3, preferably at least 5, even more preferably at least 7, and more preferably all of the bands as seen in FIG. 2 and listed in table 2c.

[0082] [Table 3]

[0083] In addition to modification A above, compound I-2 may exist in further polymorphic forms and also pseudopolymorphous forms (hydrates, solvates, etc.).

[0084] The application rates of the formulations according to the invention can vary within relatively wide ranges. This is guided by the respective active ingredients and their content in the composition.

[0085] With the aid of the compositions according to the invention, the insecticidal active ingredient mixtures can be disposed in a particularly advantageous manner on the plants and / or their habitat.

[0086] The compositions according to the invention can be used to treat all plants and plant parts. Plants in this context are understood to include all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants that can be obtained by traditional breeding and optimization methods, or by biotechnology and genetic engineering methods, or a combination of these methods, including transgenic plants and plant cultivars that can or cannot be protected by plant breeder's rights. Plant parts should be understood to mean all parts and organs of plants above and below ground, such as shoots, leaves, flowers and roots, including, for example, leaves, needles, stalks, stems, flowers, fruiting bodies, fruits and seeds, as well as tubers, roots and rhizomes. Plant parts also include harvested materials and vegetative and reproductive propagation materials, such as cuttings, tubers, rhizomes, shoots and seeds.

[0087] Preferably, the compounds of formula (I) are used in the formulations according to the invention by spray application, but also after drench, immersion or drip application, against animal pests of the following pest families: From the family of the aphids (Pemphigidae): Eriosoma spp., Pemphigus spp., for crops such as citrus fruits, pome fruits, stone fruits, leafy vegetables, root and tuberous vegetables and ornamental plants are preferred.

[0088] From the grape lice (Phylloxeridae) family: Phylloxera species on grapes, nuts and citrus are preferred.

[0089] From the family of psyllids (Psyllidae): for example Psylla spp., Paratrioza spp., Tenalaphara spp., Diaphorina spp., Trioza spp. from crops such as pome fruits, stone fruits, citrus fruits, vegetables, potatoes, tropical crops are preferred.

[0090] From the family of scale insects (Coccidae): for example Ceroplastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., Coccus spp. from perennial crops such as citrus fruits, pome fruits, stone fruits, olives, grapes, coffee, tea, tropical crops, ornamental plants, vegetables, etc. are preferred.

[0091] From the family of scale insects (Diaspididae): e.g. Quadraspidiotus spp., Aonidiella spp., Lepidosaphes spp., Aspidiotus spp., Aspis spp., Diaspis spp., Parlatoria spp., Pseudaulacaspis spp., Unaspis spp., on crops such as citrus fruits, pome fruits, stone fruits, almonds, pistachios, nuts, olives, tea, ornamental plants, grapes, tropical crops, etc. spp.), Pinnaspis spp., and Selenaspidus spp. are preferred.

[0092] From the family of scale insects (Ortheziidae): Orthezia spp. from citrus, pome and stone fruits are preferred.

[0093] From the family of mealybugs (Pseudococcidae): Pericerga, Pseudococcus spp., Planococcus spp., Dysmicoccus spp. are preferred for crops such as, for example, citrus fruits, stone and pome fruits, tea, grapes, vegetables, ornamental plants and tropical crops.

[0094] From the family of whiteflies (Aleyrodidae): Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes spp., Dialeurodes spp., Parabemisia myricae are further preferred in crops such as vegetables, potatoes, melons, potatoes, tobacco, soft fruits, citrus fruits, ornamentals, cotton, soybeans and tropical crops.

[0095] Additionally, from the aphid family (Aphididae): Myzus spp. in tobacco, stone fruits, soft fruits, fruit vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamentals, and spices; Pea aphid (Acyrthosiphon onobrychis) on vegetables, Aphis spp. in tobacco, citrus fruits, pome fruits, stone fruits, melons, strawberries, soft fruits, fruit vegetables, leafy vegetables, tubers, stem and root vegetables, ornamental plants, potatoes, pumpkins, spices; Strawberry rose aphid (Rhodobium porosum), Lettuce aphid (Nasonovia ribisnigri) on leafy vegetables, Macrosiphum spp. in ornamental plants, potatoes, leafy and fruit vegetables, strawberries, Hop's Phorodon humuli, Radish aphid (Brevicoryne brassicae) on leafy vegetables; Toxoptera spp. in citrus fruits, stone fruits, almonds, nuts, and spices; Aulacorthum spp. in citrus fruits, potatoes, fruit and leafy vegetables; Vegetable Anuraphis cardui, Sunflower Brachycaudus helycrisii, Pea aphid (Acyrthosiphon onobrychis) on vegetables is preferred.

[0096] Also from the family of thrips (Thripidae): for example Anaphothrips spp., Baliothrips spp., Caliothrips spp., Frankliniella spp., Heliothrips spp., Hercinothrips spp., Rhipiphorothrips spp., Scirtothrips spp., Kakothrips spp., from crops such as fruit, cotton, grapes, tea, nuts, tropical crops, ornamentals, conifers, tobacco, spices, vegetables, soft fruits, melons, citrus and potatoes. spp.), Selenothrips spp. and Thrips spp. are preferred.

[0097] Furthermore, from the families of the leaf miner flies (Agromyzidae) and root maggot flies (Anthomyiidae): for example Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., Pegomyia spp. from crops such as vegetables, melons, potatoes, nuts, ornamental plants, etc. are preferred.

[0098] From the families of leafhoppers (Cicadellidae) and planthoppers (Delphacidae): for example Circulifer spp., Dalbus spp., Empoasca spp., Erythroneura spp., Homalodisca spp., Iodioscopus spp., Laodelphax spp., Nephotettix spp., Nilaparvata spp. on crops such as citrus, berries, grapes, potatoes, vegetables, ornamental plants, conifers, melons, soft fruits, tea, nuts, rice and tropical crops. spp.), Oncometopia spp., and Sogatella spp. are preferred.

[0099] From the Leaf Miner Moths (Gracillariidae) family: Preference is given to Caloptilia spp., Gracilaria spp., Lithocolletis spp., Leucoptera spp., Phtorimaea spp., Phyllocnistis spp. in crops such as pome fruits, stone fruits, grapes, nuts, citrus fruits, conifers, potatoes, coffee, etc.

[0100] From the family Cecidomyiidae (Cecidomyiidae): Preferred are Contarinia spp., Dasineura spp., Diplosis spp., Prodiplosis spp., Thecodiplosis spp., Sitodiplosis spp., Haplodiplosis spp. in crops such as citrus, pome fruits, stone fruits, vegetables, potatoes, spices, soft fruits, conifers, and hops.

[0101] Similarly, from the family of fruit flies (Tephritidae): Preference is given to Anastrepha spp., Ceratitis spp., Dacus spp., Rhagoletis spp. in crops such as vegetables, soft fruits, melons, pome and stone fruits, ornamental plants, potatoes, grapes, tropical crops, citrus fruits, olives, etc.

[0102] Additionally, from the families of spider mites (Tetranychidae) and eriophyid mites (Eriophydae): Preferred are Tetranychus spp., Panonychus spp., Aculops spp. on crops such as vegetables, potatoes, ornamental plants, citrus fruits, grapes, and conifers.

[0103] The treatment according to the invention of plants and plant parts with the compositions according to the invention is carried out by customary treatment methods, such as irrigation, immersion, spraying, evaporation, misting, dusting, spreading, in the case of sowing material, in particular seeds, by applying one or more coats, either directly or by allowing the combination to act on the surroundings, the environment or the storage space.

[0104] The active ingredients are preferably applied by spray application. Alternatively, the active ingredients are applied by drench, drip or immersion application.

[0105] Preferably, the plants to be treated are selected from the group consisting of cotton, soybeans, tobacco, vegetables, spices, ornamentals, conifers, citrus plants, fruits, tropical crops, nuts and vines.

[0106] Preferably, the compositions according to the invention act against pests from the families of: bollworm, grape lice, psyllid, scale, round scale, leaf scale, mealybug, whitefly, aphids, thrips, leafhoppers, planthoppers, leaf miner flies, gall flies, fruit flies, leaf miner moths, spider mites and eriophyid mites.

[0107] It has also been found that the composition according to the invention can be produced by moistening a powdery mixture of one or more active ingredients and formulation auxiliaries, then granulating by low pressure extrusion, and then drying the moist granules. The equipment involved in moistening, extrusion and drying is known to those skilled in the art. During the production, it should be particularly ensured that the temperature to which the product is exposed is kept below 60°C, preferably below 50°C, in all process steps.

[0108] This method also forms part of the subject matter of the present invention.

[0109] The treatment according to the invention of plants and plant parts with the compositions according to the invention is carried out by customary treatment methods, such as immersion, spraying, evaporation, misting, dusting, spreading, in the case of sowing material, in particular seeds, by applying one or more coats, either directly or by allowing the combination to act on the surroundings, the environment or the storage space.

[0110] The following examples illustrate the subject matter of the invention without limiting it.

[0111] Working Example 1. Suspension 1.a) Suspension of single formulations In order to achieve good suspension at high salt concentrations in the formulation, the following dispersing aids were tested as follows: A 20 g mixture of 0.96 g compound I-2, 13 g diammonium hydrogen phosphate (DAHP), 0.4 g Morwet EFW (wetting agent), 1 g Pergopak M, 0.1 g Trilon B Powder, 2.54 g Kaolin W, and 2 g dispersing aid was milled in an IKA A 10 analytical mill (20,000 rpm) for 2 minutes and tested for gravimetric suspendability.

[0112] [Table 4]

[0113] Determination of Suspension A 1% suspension in water (CIPAC C) is dispersed in a 250 ml graduated cylinder. The mixture is allowed to equilibrate for 30 minutes. The top 9 / 10 of the suspension is then removed. The remaining 1 / 10 is dried and the residue is determined gravimetrically. The suspension is 10 / 9*100*(sample amount [g]*proportion ai [%] / 100-residue [g]) / (sample amount [g]*proportion ai [%] / 100) Define it as:

[0114] Thus, a value of 100% corresponds to a homogenous distribution of all insoluble components throughout the sample volume.

[0115] A good visual rating means no sediment or clumps.

[0116] 1.b) Suspension and stability of single and mixed formulations Suspension studies on single and mixed formulations after storage at elevated temperatures.

[0117] 1 kg of a mixture of compound I-2 (different in Example 12), optionally a second active ingredient, diammonium hydrogen phosphate (DAHP), Morwet EFW, Pergopak M, optionally Trilon B Powder, Kaolin W, dispersing aid and antifoaming agent is ground in a Hosokawa 100 AS 4'' air jet mill (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g / min) in a manner known to those skilled in the art, moistened with water (about 14% by weight), extruded using a Fuji Paudal dome extruder (die size 0.8 mm) to obtain WG and further dried in a fluidized bed dryer.

[0118] [Table 5]

[0119] 2.Manufacturability 2.a) Granulation method experiment Preparation of WG by extrusion as a suitable granulation method due to lower thermal stress.

[0120] a) A mixture of compound I-2, second active ingredient, diammonium hydrogen phosphate (DAHP), Morwet EFW, Pergopak M, Trilon B Powder, Kaolin W and dispersing aid is milled in a Hosokawa 100 AS 4'' air jet mill (injector air 5.5 bar, milling air 4.5 bar, throughput 100 g / min) in a manner known to the skilled person, moistened with water (about 14 wt%), extruded using a Fuji Paudal dome extruder (die size 1 mm) to obtain WG and further dried in a fluid bed dryer.

[0121] b) A mixture of compound I-2, DAHP, Geropon T36, Geropon SDS, Trilon B Powder and Reax 88A is dispersed in water to obtain a 50% slurry, milled in a bead mill and then dried by spray drying (Niro SD 6.3 spray dryer) or by a fluid bed granulator (Niro Aeromatic MP1) in a manner known to those skilled in the art.

[0122] [Table 6]

[0123] Spray drying or the fluidized bed reduces the pH of the spray solution too much (below 7).

[0124] 2.b) Optimization of extrudability of WG A mixture of compound I-2, second active ingredient, Morwet EFW, Pergopak M, optionally Trilon B Powder, Tersperse 2700, DAHP and optionally Kaolin W is ground in a Hosokawa 100 AS 4'' air jet mill (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g / min) in a manner known to those skilled in the art, moistened with water (about 14 wt%), extruded using a Fuji Paudal dome extruder (die size 0.8 or 1 mm) to obtain WG and further dried in a fluid bed dryer.

[0125] [Table 7]

[0126] As is evident from Comparative Examples 20 and 21, if the amount of filler is insufficient or the amount of salt is too high, no extrudates or extrudates of sufficient quality can be obtained.

[0127] Example 22 shows that in the case of active ingredient combinations, the optimum content of filler must be adjusted.

[0128] 3) Solubility of the active ingredient An attempt to increase the availability of the active ingredient in the spray solution by improving its solubility as a function of the amount of salt.

[0129] Six samples of sample 19 (see Example 2b) were dispersed in 50 g of water to achieve a concentration of 0.12 or 0.24 g / l of active ingredient. The mixtures were stirred and in each case after 30 minutes, 2 hours and 5 hours, centrifuged thoroughly and the percentage of dissolved active ingredient in the supernatant was determined by HPLC.

[0130] [Table 8]

[0131] Only with the formulation according to the invention is there virtually complete solubility of the active ingredient in the spray liquid.

[0132] 4) Bioavailability Measurement of plant penetration This test measured the penetration of active ingredients through enzymatically isolated cuticles of apple tree leaves.

[0133] Fully developed leaves removed from Golden Delicious apple trees were used. The cuticle was -First, leaf discs, marked with dye on the underside and punched out, were filled with a pectinase solution (0.2%-2%) buffered to pH 3-4 by vacuum infiltration; Sodium azide is then added, The leaf discs thus treated are then left until the original leaf structure has dissolved and the acellular cuticle has detached. It was isolated by

[0134] Afterwards, only the cuticles of the upper leaf side, free of stomata and hairs, were used for further procedures. These were repeatedly washed alternately with water and pH 7 buffer. The resulting clean cuticles were finally applied to a Teflon® sheet, smoothed and dried under a gentle air stream.

[0135] In a next step, the cuticle membrane thus obtained was placed in a stainless steel diffusion cell (=transport chamber) for membrane transport studies. For this purpose, the cuticle was placed, using tweezers, in the center of the edge of a diffusion cell greased with silicone grease and sealed with a ring also greased. The positioning was chosen so that the outer morphology of the cuticle was facing outwards, i.e. towards the air, and the original inner side faced the inside of the diffusion cell.

[0136] The diffusion cells were filled with a 30% ethylene glycol / water solution. To measure penetration, 10 μl of each of the following spray solutions was applied to the outside of the cuticle: The spray solutions were made up of local tap water with moderate water hardness.

[0137] After applying the spray solution, the water was evaporated, the chambers were inverted and they were placed in a thermostatic chamber where the temperature above the cuticle and the air humidity could be controlled via a gentle airflow over the sprayed film with the cuticle (20°C, 60% rh). Aliquots were taken at regular intervals by an autosampler and the active ingredient content was measured by HPLC.

[0138] The experimental results are shown in the table below. The values ​​reported are the average of 8 to 10 measurements.

[0139] Sample 1 and a comparison sample (sample 25) containing the same concentration of ammonium dihydrogen phosphate (ADHP) rather than DAHP were analyzed.

[0140] [Table 9]

[0141] Below pH 7, the penetration / bioavailability of the active ingredient is no longer sufficient or is significantly reduced, as shown by sample 25. The pH, and therefore the use of basic salts, has a significant effect on AI penetration.

[0142] Materials used Kraftsperse® EDF-350, DD-5, Kraftsperse® DD-8, Kraftsperse® DW-8, Kraftsperse® EDF-450, Reax® 88B and Reax® 907 are lignosulfonates made by Ingevity, North Charleston, SC, USA.

[0143] Geropon® TA / 72, T / 36 are sodium salts of polycarboxylic acids manufactured by Solvay.

[0144] Oparyl® MT 804 is dibutylnaphthalene sulfonic acid sodium salt manufactured by Giovanni Bozzetto SpA, Filago, Italy.

[0145] Oparyl® DT 530 is a naphthalenesulfonic acid-formaldehyde condensate, sodium salt, manufactured by Giovanni Bozzetto SpA, Filago, Italy. Pergopak® M is a polymethylurea resin manufactured by Albemarle Corporation, Baton Rouge, LA, USA.

[0146] Rhodorsil® EP 6703 is a polydimethylsiloxane on starch manufactured by Rhodia, Boulogne, France.

[0147] Celite® 209 S is a diatomaceous earth manufactured by Lehmann & Voss, Hamburg, Germany.

[0148] Luzenac 2 talc is a magnesium hydrosilicate manufactured by Luzenac Europe, Paris, France.

[0149] Kaolin W is an aluminum hydrosilicate manufactured by Erbsloh Lohrheim GmbH & Co. KG, Lohrheim, Germany.

[0150] Borresperse® Na and Ufoxane® 3 A are lignosulfonates manufactured by Borregaard, Sarpsborg, Norway.

[0151] Morwet® D 425 is a naphthalenesulfonic acid-formaldehyde condensate, sodium salt, manufactured by Akzo Nobel, Stenungsund, Sweden.

[0152] Tersperse®a is a naphthalenesulfonic acid-formaldehyde condensate, sodium salt, made by Huntsman, The Woodlands, Texas, USA.

[0153] Baykanol® SL is an alkylaryl sulfonate manufactured by Lanxess, Leverkusen, Germany.

[0154] Rhodorsil Antimousse EP 6703® is an absorbed polydimethylsiloxane manufactured by Solvay.

Claims

1. a. 0.1 to 25% by weight of a tetramic acid derivative of formula (I) 【Chemistry 1】 (In the formula, Y is chlorine, bromine, iodine or fluorine; W and X are independently C1-C4 alkyl; A, B and the carbon atom to which they are attached are a C5-C6-cycloalkyl substituted by an alkylenedioxy group, which together with the carbon atom to which they are attached form a 5- or 6-membered ketal; G is hydrogen; b. 20-68% by weight of at least one basic salt selected from the group consisting of ammonium carbonate, ammonium bicarbonate, and diammonium hydrogen phosphate (DAHP); c. 1-20% by weight of at least one polycarboxylate type dispersant selected from the group consisting of polyacrylic acid, polymethacrylic acid, polymaleic acid, hydrophobically modified comb polymers including polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins, copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylates, copolymers of acrylic acid and vinyl acetate, copolymers of methacrylic acid and styrene, modified copolymers of methacrylic acid and styrene, copolymers of maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acid (e.g., C8-C18) sarcosinates, carboxylic acids, such as resin acids or fatty acids (e.g., C8-C18) or salts of such carboxylic acids, and salts of these copolymers; d. 0.5-15% by weight of at least one wetting agent selected from the group consisting of the sodium salt of alkylated naphthalene sulfonate and the sodium salt of dioctyl sulfosuccinic acid, more preferably the sodium salt of alkylated naphthalene sulfonate; e. 16.2% or more and less than 22% by weight of at least one filler that is a silicate; f. 0.5 to 15 wt. % of at least one structure former selected from the group consisting of crosslinked polyureas and polyurethanes, and derivatized polyureas and polyurethanes; g. optionally, a complexing agent; h. flupyradifurone as a further active ingredient, and i. Optionally, further adjuvants selected from the group of antifoaming agents, preservatives, antioxidants, and dyes. Including, A solid composition in the form of water-dispersible granules.

2. A composition according to claim 1, characterized in that component a) in the composition according to the invention comprises a compound of formula (I) having the following: 【Chemistry 2】

3. Component a) is of the formula 【Chemistry 3】 The composition according to claim 1, characterized in that it is a compound of the formula:

4. A composition described in any one of claims 1 to 3, characterized in that component b) is DAHP.

5. A composition described in any one of claims 1 to 4, characterized in that component c) is a dispersant selected from the group comprising the sodium salt of a copolymer of maleic acid and an olefin, and the sodium salt of a copolymer of methacrylic acid and styrene, modified copolymers of methacrylic acid and styrene, more preferably the sodium salt of a copolymer of methacrylic acid and styrene and modified copolymers of methacrylic acid and styrene.

6. A composition according to claim 1, characterized in that component e) is kaolin.

7. The composition according to claim 1, wherein component f) is selected from the group comprising polymethylurea resins.

8. A composition according to claim 1, characterized in that component g) is Na 4 EDTA.

9. The composition according to claim 1, wherein components a to g are present in the following amounts: a) 4-8% by weight b) 60-66% by weight c) 8-12% by weight d) 1.5-2.5% by weight e) 10-22% by weight f) 3-8% by weight g) 0.1-1% by weight.

10. The composition according to claim 1, further comprising component h) present in the following amount: h) 10-35% by weight.

11. The composition according to claim 1, wherein component i) is present in the following amount: i) 0.1-5% by weight.

12. A method for producing a composition according to any one of claims 1 to 11, characterized in that the composition is produced by mixing the components and then extruding.

13. Use of a composition according to any one of claims 1 to 11 for applying to plants and / or their habitats the active pesticide ingredients present.

14. Use of a composition according to any one of claims 1 to 11 for controlling insects.

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