Solid formulation of an insecticidal mixture having particularly excellent dispersion properties

Abstract

The present invention relates to solid preparations in the form of granular hydrating agents 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 present invention further relates to methods for producing them and their use for applying the active ingredients contained therein.

Description

Technical Field

[0001] The present invention relates to solid-state formulations (in particular, water-dispersible granules) of tetramic acid derivatives and mixtures of these tetramic acid derivatives that disintegrate particularly efficiently in water and nevertheless have good long-term stability, to methods for producing them, and to their use for applying the active ingredients present.

Background Art

[0002] When producing a WG formulation using formulation aids specified in the prior art, a formulation with undesirable properties is obtained. For example, the proportion of insoluble components or the presence of some active ingredients can have the effect that, after being introduced into water, the granules disintegrate insufficiently (i.e., incompletely or too slowly), or the dissolution is insufficient. The slow disintegration of the granules can have the effect that sediment remains, the nozzles become clogged, or the concentration of the active ingredient in the spraying liquid and the associated efficacy are reduced.

[0003] WO2019197631 describes water-dispersible granules of tetramic acid derivatives and mixtures of these tetramic acid derivatives. However, it does not describe additives that are clearly intended to improve the dissolution properties.

[0004] US2015 / 0164068 describes a storage-stable WG formulation with good efficacy containing active ingredients of various particle sizes and containing 75% by weight of a low-hygroscopic water-soluble carrier in the form of an inorganic salt. The preferred carriers mentioned are ammonium sulfate and potassium sulfate, while potassium hydrogen carbonate is only generally described as a carrier without exemplification in a relatively long list. Furthermore, there is no disclosure of the explicit use of potassium hydrogen carbonate in the examples.

[0005] In contrast to US2015 / 0164068, potassium bicarbonate is clearly present only in small amounts in this compound, and especially when used in combination with further basic salts, it may cause adverse effects on the reaction and storage stability.

[0006] WO2020 / 240394 describes WG formulations that include a "disintegration system". These also include inorganic salts such as bicarbonates. However, in that case, there are no further salts that are potentially decomposable in the formulation, so no adverse effects on storage stability are expected. Furthermore, in its examples, the explicit use of potassium bicarbonate is not disclosed, and instead, standard potassium sulfate is used.

[0007] Furthermore, the general use of bicarbonates when dissolving tablets in combination with an acid (e.g., citric acid) is known.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] Surprisingly, it has been found that the formulations of the present invention have particularly advantageous properties with respect to storage stability and rapid dissolution.

[0010] Surprisingly, it has been found that by adding a specific amount of inorganic carbonate (especially bicarbonate), even in the presence of basic ammonium salts, the granules dissolve more rapidly and better reliably without adversely affecting the storage stability of the granules (especially even at high temperatures).

[0011] Even in the presence of large amounts of salts, and in particular even after storage, having good suspension properties is a further feature of the formulations according to the invention.

[0012] Accordingly, these formulations form the subject of the present invention. The present invention further relates to a process for producing these wettable granular formulations and their use for application.

Means for Solving the Problems

[0013] Accordingly, the present invention provides an insecticidal solid composition in the form of a wettable granule (solid formulation), where this preferably comprises the following: a. As a component, formula (I)

Chemical formula

Chemical formula

Mode for Carrying Out the Invention

[0014] In the present invention, in the formula (for example, formula (I)), the optionally substituted radical can be mono-substituted or multi-substituted unless otherwise indicated, where the substituents in the case of multi-substitution may be the same or different.

[0015] Furthermore, within the preferred ranges shown in the present invention, different levels of preference should be understood to be combinable with each other in a permutation, but in any case, the preferences of the same level, in particular, the most preferred embodiments / most preferred levels of preference in each case, should be combined with each other and are actually disclosed as such combinations.

[0016] The above composition consisting only of essential components (not optional components) should likewise be considered to be disclosed.

[0017] Percentages should be considered as % by weight unless otherwise indicated, where the % by weight of the composition totals 100.

[0018] Unless otherwise defined, in the context of the present invention, "basic" means that the pH of an aqueous solution exceeds 7.

[0019] The formulations according to the invention in aqueous dispersion have a pH exceeding 7.

[0020] In a preferred embodiment, the formulation comprises at least one defoaming agent (i), where the defoaming agent is preferably in solid form, preferably based on silicone oil or wax, and more preferably PDMS adsorbed on a solid support.

[0021] A preferred defoaming agent is Rhodorsil antifoam EP6703 (absorbed polydimethylsiloxane).

[0022] (a) Active ingredient In a preferred embodiment, component (a) in the composition according to the invention has the formula (I)

Chemical formula

Chemical formula

[0023] In a further preferred embodiment, component (a) in the composition according to the invention has the formula (I)

Chemical formula

Chemical formula

[0024] In a particularly preferred embodiment, component (a) has the formula

Chemical formula

[0025] (b) Basic salt Component (b) is preferably selected from the group comprising inorganic basic ammonium salts, excluding carbonates and hydrogencarbonates. In the context of the present invention, the basic salt (b) is not a carbonate, unless otherwise expressly stated.

[0026] More preferably, (b) is selected from the group comprising diammonium hydrogen phosphate (DAHP).

[0027] (c) Further inorganic salts (excluding ammonium salts thereof) selected from the group consisting of inorganic carbonates and hydrogen carbonates More preferably, (c) is selected from the group of hydrocarbon acid salts.

[0028] Particularly preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

[0029] (d) Dispersant Suitable dispersants in connection with the present invention are polycarboxylate type dispersants, such as hydrophobically modified comb-like polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or maleic anhydride and olefin (e.g., isobutylene or diisobutylene) copolymers, acrylic acid and itaconic acid copolymers, methacrylic acid and itaconic acid copolymers, maleic acid or maleic anhydride and styrene copolymers, acrylic acid and methacrylic acid copolymers, acrylic acid and methacrylate copolymers, acrylic acid and vinyl acetate copolymers, styrene and methacrylic acid copolymers, modified copolymers of styrene and methacrylic acid, maleic acid or maleic anhydride and acrylic acid copolymers, 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 salts of such carboxylic acids, such as alkali metal salts or alkaline earth metal salts (preferably, Ca, Mg). The above copolymers can further 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.

[0030] More preferably, the dispersant is selected from the group consisting of sodium salts of maleic acid and olefin copolymers (e.g., Geropon T / 36 / Solvay; Duramax D-305 / Dow); and sodium salts of methacrylic acid and styrene copolymers (Tersperse 2700 / Indorama; Atlox Metasperse 500S / Croda).

[0031] More preferably, the dispersant is the sodium salt of a methacrylic acid and styrene copolymer.

[0032] Particularly preferably, stearate (especially, magnesium stearate) is additionally added.

[0033] (e) Wetting agent Useful non-ionic surfactants include all substances of this kind that can be normally used in pesticide 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, and further, polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol and polyvinyl pyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters, and alkyl ethoxylates and alkyl aryl ethoxylates, etc. can be mentioned. Here, these may be phosphorylated and may be neutralized with a base. Here, for example, sorbitol ethoxylate can be mentioned. Further, polyoxyalkylene amine derivatives can also be mentioned.

[0034] Suitable anionic surfactants include all substances of this kind that can be normally used in pesticide compositions.

[0035] Useful wetting agents are preferably anionic surfactants selected from the group including 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, and 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, Geropon® SDS, and block polymers on ethylenediamine of propylene oxide and ethylene oxide, such as Synperonic® T 905.

[0036] More preferably, suitable wetting agents (e) in relation to the present invention are selected from the group consisting of sodium salts of alkylated naphthalene sulfonates, such as Morwet® EFW, and sodium salts of dioctyl sulfosuccinate, such as Aerosol® OTB, Geropon® SDS.

[0037] (f) Bulking agent Useful inert fillers are all substances that can normally be used for this purpose in pesticide compositions. Preferred are inorganic particles such as silicates and oxides, and furthermore 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 include kaolin, rutile, silicon dioxide, micronized silica, silica gel, and natural and synthetic silicates, and furthermore talc and the like.

[0038] The filler is more preferably selected from the group containing kaolin, rutile and silicon dioxide. Particularly preferred is kaolin.

[0039] (g) Structure-forming agent The formulations according to the invention can further contain structuring agents. Particularly suitable for this purpose are polyacrylic acid and its salts, in particular crosslinked polyacrylates, and polyurethanes and derivatized polyurethanes and their salts are also suitable. Examples of such suitable acrylates are (poly)methacrylate, (poly)methyl methacrylate, polyacrylamide, (poly)ethoxyethyl methacrylate, and polymethyl urea resins, such as Pergopak® M.

[0040] The structuring agent is more preferably a polymethyl urea resin.

[0041] (h) Further active ingredient The formulation can, in principle, contain one or more further pesticidal active ingredients, preferably one or more further pesticidal active ingredients selected from the group consisting of insecticides, herbicides, fungicides and host defense inducers.

[0042] More preferably, the active ingredient is one or more selected from the group of insecticides, and even more preferably, imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metflumizone, methoxyphenozide, milbemectin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron.

[0043] Particularly preferred are one or more further active ingredients selected from the group consisting of ethiprole, spinetoram, abamectin and flupyradifurone.

[0044] (i) Adjuvant and formulation aid Useful foam suppressants are all substances that can normally be used for this purpose in pesticidal compositions. Preferred are silicone oil-based defoamers and magnesium stearate.

[0045] Preferably, it is further a solid defoamer, or a defoamer adsorbed or absorbed on a support.

[0046] Particularly preferred is polydimethylsiloxane absorbed on a solid substrate. An example thereof is Rhodorsil antifoam EP 6703.

[0047] Useful preservatives include all substances that can usually be used for this purpose in this type of pesticide composition. For example, isothiazolinone (e.g., Preventol® (manufactured by Lanxess AG)) and 1,2-benzisothiazolin-3-one (e.g., Proxel®), etc.

[0048] Useful antioxidants are all substances that can usually be used for this purpose in the pesticide composition. Butylhydroxytoluene is preferred.

[0049] Useful dyes are all substances that can usually be used for this purpose in the pesticide composition. For example, titanium dioxide, pigment black, zinc oxide, and blue pigments, and furthermore, Permanent Red FGR, etc.

[0050] In a preferred embodiment, the present invention a. Formula (I)

Chemical formula

Chemical formula

[0051] In a further preferred embodiment, the present invention a. the following compound:

Chemical formula

[0052] In a particularly preferred embodiment, the present invention is a. The following structure:

Chemical formula

[0053] In an alternative embodiment, in the above embodiment, the further pesticidal active ingredient (g) must be present and is preferably selected from the group consisting of imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyphenozide, milbemectin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron; more preferably selected from the group consisting of ethiprole, spinetoram, abamectin and flupyradifurone.

[0054] In an alternative embodiment, in the above embodiment and also in the embodiments specified below, the further adjuvant (i) [preferably an antifoaming agent based on silicone oil, more preferably polydimethylsiloxane absorbed on a solid substrate] is essential.

[0055] Single formulation: The proportion of the active ingredient (ingredient (a) / compound represented by formula (I) / (I-2)) in the composition according to the invention having only one kind of active ingredient is preferably 0.5 - 25% by weight; more preferably 1 - 18% by weight; and even more preferably 2 - 12% by weight.

[0056] The proportion of the salt (ingredient (b)) in the composition according to the invention having only one kind of active ingredient is preferably 20 - 75% by weight; more preferably 25 - 68% by weight; and even more preferably 30 - 66% by weight.

[0057] The proportion of the inorganic salt (component (c)) in the composition according to the invention having only one type of active ingredient is preferably 1-10% by weight; more preferably 1.5-9% by weight; and even more preferably 2-7% by weight.

[0058] The proportion of the dispersant (component (d)) in the composition according to the invention having only one type of active ingredient is preferably 1-20% by weight; more preferably 5-15% by weight; and even more preferably 8-12% by weight.

[0059] The proportion of the wetting agent (component (e)) in the composition according to the invention having only one type of active ingredient is preferably 0.5-15% by weight; more preferably 1-10% by weight; and even more preferably 1.5-2.5% by weight.

[0060] The proportion of the extender (component (f)) in the composition according to the invention having only one type of active ingredient is preferably 0.5-30% by weight; more preferably 5-25% by weight; and even more preferably 10-22% by weight.

[0061] The proportion of the structure-forming agent (component (g)) in the composition according to the invention having only one type of active ingredient is preferably 0.5-15% by weight; more preferably 1-10% by weight; and even more preferably 3-8% by weight.

[0062] The proportion of the further adjuvant (component (i)) - when present - in the composition according to the invention is Preferably, it is 0-10% by weight; More preferably, it is 0-8% by weight; and, Even more preferably, it is 0-5% by weight.

[0063] In the above alternative embodiment, when component (i) is essential, for example as an antifoaming agent, its proportion in the solid preparation according to the present invention is 0.1-5% by weight.

[0064] A preferred embodiment of the present invention is a composition comprising the following components: (a) 0.5-25% by weight; (b) 20-75% by weight; (c) 1-10% by weight; (d) 1-20% by weight; (e) 0.5-15% by weight; (f) 0.5-30% by weight; (g) 0.5-15% by weight.

[0065] A more preferred embodiment of the present invention is a composition comprising the following components: (a) 1-18% by weight; (b) 25-68% by weight; (c) 1.5-9% by weight; (d) 5-15% by weight; (e) 1-10% by weight; (f) 5-25% by weight; (g) 1-10% by weight.

[0066] An even more preferred embodiment of the present invention is a composition comprising the following components: (a) 2-12% by weight; (b) 30-66% by weight; (c) 2-7% by weight; (d) 8-12% by weight; (e) 1.5-2.5% by weight; (f) 10-22% by weight; (g) 3-8% by weight.

[0067] In an alternative embodiment where component (i) is essential, preferably a solid composition comprising the following components: (a) 2-12% by weight; (b) 30-66% by weight; (c) 2-7% by weight; (d) 8-12% by weight; (e) 1.5-2.5% by weight; (f) 10-22% by weight; (g) 3-8% by weight; (i) 0.1-5% by weight.

[0068] Mixed formulation: In the composition according to the invention, the proportion of further active ingredient (component (h)) - when present - is preferably 1-30% by weight; more preferably 1-25% by weight; and even more preferably 1.5-20% by weight.

[0069] In an alternative embodiment where component (h) and component (i) are essential, preferably a solid composition comprising the following components: (a) 2-12% by weight; (b) 30-66% by weight; (c) 2-7% by weight; (d) 8-12% by weight; (e) 1.5-2.5% by weight; (f) 10-22% by weight; (g) 3-8% by weight; (h) 1.5-20% by weight; (i) 0.1-5% by weight.

[0070] Particularly preferably usable in the composition is a tetramic acid derivative represented by the formula (I) [wherein, G = hydrogen (a)].

[0071] Similarly, most preferably usable is a tetramic acid derivative represented by the above formula (I) [wherein, G = E (d)].

[0072] Compound (I-2) is preferably used in the form of its most thermodynamically stable polymorphic structure. This crystal structure and further physical data were confirmed as follows.

[0073] Preparation of samples: Compound (I-2) (C 19 H 22 ClNO4 / MW = 363.84 g / mol) was crystallized from methanol and dried at room temperature to obtain Modification A.

[0074] Modification A of (I-2) can be characterized by powder X-ray diffraction based on the corresponding diffraction pattern recorded at 25 °C with Cu-Kα1 radiation (1.5406 Å) (Figure 1).

[0075] Modification A according to the present invention exhibits at least 3 reflections, preferably at least 5 reflections, more preferably at least 7 reflections, even more preferably at least 10 reflections, and most preferably all reflections, as shown in Figure 1 and Table 2(a). Table (2b) shows all the measured reflections of Modification A.

[0076] Modification A according to the present invention is further characterized by the X-ray diffraction pattern shown in Figure I.

[0077] Crystallographic studies on single crystals of Modification A showed that the crystal structure is monoclinic. The unit cell is in the P21 / c space group.

[0078] [Table 1]

[0079] [Table 2]

[0080] The polymorphic form of Polymorph A of (I-1) was measured using a diamond ATR apparatus at 4 cm-1 It can be determined by IR spectroscopy from the corresponding spectra recorded at 25 °C with a resolution of -1 (Figure 2). As can be seen in Figure 2, the polymorph A of the present invention exhibits at least 3 bands, preferably at least 5 bands, more preferably at least 7 bands, and particularly preferably all bands, and is described in Table 2c.

[0081] [Table 3]

[0082] In addition to the above polymorph A, compound (I-2) can exist in further polymorphic forms and can also exist in pseudopolymorphic forms (such as hydrates, solvates, etc.).

[0083] The application dose of the formulation of the present invention can be varied within a relatively wide range. It depends on each active ingredient and its content in the composition.

[0084] Using the composition of the present invention, the insecticidal active ingredient mixture can be deployed on plants and / or their habitats in a particularly advantageous manner.

[0085] The compositions of the present invention can be used to treat all plants and parts of plants. In the context of the present invention, "plant" is understood to include all plants and plant populations such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants). Crop plants can be obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or by a combination of these methods. Such crop plants include transgenic plants, and also plant varieties that can or cannot be protected by plant breeder's rights. The part of a plant is understood to mean all above-ground and underground parts and all organs of the plant, such as shoots, leaves, flowers and roots, and examples that can be mentioned here are leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, and further tubers, roots and rhizomes. The parts of a plant further include harvests, as well as vegetative and generative propagation material, such as cuttings, tubers, rhizomes, slips and seeds, etc.

[0086] Preferably, the compound represented by formula (I) is used by spraying application in the formulation according to the present invention against pests of the following families of pests, and further used after irrigation application, dipping application or dripping application.

[0087] Preferred are the following of the family Pemphigidae: for example, Eriosoma spp., Pemphigus spp. in crops such as citrus fruits, pomaceous fruits, stone fruits, leafy vegetables, root vegetables and tuber vegetables and ornamental plants.

[0088] Preferred are the following of the family Phylloxeridae: Phylloxera spp. in grapevines, nuts, citrus fruits.

[0089] Preferred are the following of the Psyllidae: for example, Psylla spp., Paratrioza spp., Tenalaphara spp., Diaphorina spp., Trioza spp. in crops such as pomaceous fruits, stone fruits, citrus fruits, vegetables, potatoes, tropical crops, etc.

[0090] Preferred are the following of the Coccidae: for example, Ceroplastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., Coccus spp. in perennial crops such as citrus fruits, pomaceous fruits, stone fruits, olive, grapevine, coffee, tea, tropical crops, ornamental plants, vegetables, etc.

[0091] Preferred are the following of the Diaspididae: for example, 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 fruits, pomaceous fruits, stone fruits, almond, pistachio, nuts, olive, tea, ornamental plants, grapevine, tropical crops, etc.

[0092] Preferred are the following of the family Ortheziidae: Orthezia spp. in citrus fruits, pomaceous fruits, and stone fruits.

[0093] Preferred are the following of the family Pseudococcidae: For example, Pericerga, Pseudococcus spp., Planococcus spp., Dysmicoccus spp. in crops such as citrus fruits, stone fruits and pomaceous fruits, tea, grapevines, vegetables, ornamental plants, and tropical crops.

[0094] Preferred are further the following of the family Aleyrodidae: For example, Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes spp., Dialeurodes spp., Parabemisia myricae in crops such as vegetables, melons, potatoes, tobacco, small fruit trees, citrus fruits, ornamental plants, cotton, soybeans, and tropical crops.

[0095] Further preferred are the following of the family Aphidae: Myzus spp. in tobacco, stone fruits, small fruit trees, fruit vegetables, leaf vegetables, tuber vegetables, and root vegetables, melons, potatoes, ornamental plants, and spices; Acyrthosiphon onobrychis in vegetables; Aphis spp. in tobacco, citrus fruits, pomaceous fruits, stone fruits, melons, strawberries, small fruit trees, fruiting vegetables, leafy vegetables, tuber vegetables, stem vegetables and root vegetables, ornamental plants, potatoes, pumpkins, and spices; Rhodobium porosum in strawberries; Nasonovia ribisnigri in leafy vegetables; Macrosiphum spp. in ornamental plants, potatoes, leafy vegetables, fruiting vegetables, and strawberries; Phorodon humuli in hops; Brevicoryne brassicae in leafy vegetables; Toxoptera spp. in citrus fruits, stone fruits, almonds, nuts, and spices; Aulacorthum spp. in citrus fruits, potatoes, fruiting vegetables, and leafy vegetables; Anuraphis cardui in vegetables; Brachycaudus helycrisii in sunflowers; Acyrthosiphon onobrychis in vegetables.

[0096] Similarly preferred are the following of the Thripidae: for example, 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 fruits, cotton, grapevines, tea, nuts, tropical crops, ornamental plants, conifers, tobacco, spices, vegetables, small fruit trees, melons, citrus fruits, and potatoes.

[0097] Further preferred are the following of the Agromyzidae and Anthomyiidae: for example, Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., and Pegomyia spp. in crops such as vegetables, melons, potatoes, nuts, and ornamental plants.

[0098] Preferred are the following of the families Cicadellidae and Delphacidae: for example, Circulifer spp., Dalbus spp., Empoasca spp., Erythroneura spp., Homalodisca spp., Iodioscopus spp., Laodelphax spp., Nephotettix spp., Nilaparvata spp., Oncometopia spp., Sogatella spp. in crops such as citrus fruits, fruits, grapevines, potatoes, vegetables, ornamental plants, conifers, melons, small fruit trees, tea, nuts, rice and tropical crops.

[0099] Preferred are the following of the family Gracillariidae: for example, Caloptilia spp., Gracillaria spp., Lithocolletis spp., Leucoptera spp., Phtorimaea spp., Phyllocnistis spp. in crops such as pomaceous fruits, stone fruits, grapevines, nuts, citrus fruits, conifers, potatoes, coffee.

[0100] Preferred are the following of the Cecidomyiidae: for example, Contarinia spp., Dasineura spp., Diplosis spp., Prodiplosis spp., Thecodiplosis spp., Sitodiplosis spp., Haplodiplosis spp. in crops such as citrus fruits, pomaceous fruits, stone fruits, vegetables, potatoes, spices, small fruit trees, conifers, hops.

[0101] Similarly, preferred are the following of the Tephritidae: for example, Anastrepha spp., Ceratitis spp., Dacus spp., Rhagoletis spp. in crops such as vegetables, small fruit trees, melons, pomaceous fruits and stone fruits, ornamental plants, potatoes, grapevines, tropical crops, citrus fruits, olives.

[0102] Furthermore, preferred are mites of the Tetranychidae and Eriophyidae: for example, Tetranychus spp., Panonychus spp., Aculops spp. in crops such as vegetables, potatoes, ornamental plants, citrus fruits, grapevines, conifers.

[0103] The treatment of plants and plant parts according to the composition of the present invention is carried out directly by conventional treatment methods, for example, by irrigation, dipping, spraying, vaporization, fogging, scattering, coating, etc., or by allowing the composition to act on the surroundings, environment or storage space of the plants and plant parts, and in the case of propagation material, especially in the case of seeds, it is also carried out by applying one or more coatings.

[0104] The active ingredient is preferably applied by spraying. Alternatively, the active ingredient is applied by irrigation, dripping or dipping.

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

[0106] Preferably, the composition according to the invention acts against pests of the families Tineidae, Phylloxeridae, Psyllidae, Coccidae, Margarodidae, Monophlebidae, Eriococcidae, Aphididae, Thripidae, Aleyrodidae, Cicadellidae, Delphacidae, Agromyzidae, Drosophilidae, Muscidae, Gracillariidae, Tetranychidae, Tarsonemidae.

[0107] It has also been found that the composition according to the invention can be produced by wetting a powder mixture consisting of the active ingredient(s) and formulation auxiliaries, then granulating using low-pressure extrusion, and then drying the wet granules. The related equipment for wetting, extrusion and drying is known to those skilled in the art. It should be particularly ensured that the temperature to which the product is exposed during the manufacturing process is kept below 60 °C, preferably below 50 °C, at all process stages.

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

[0109] The treatment of plants and parts of plants according to the composition of the invention is carried out directly by customary treatment methods, such as dipping, spraying, vaporizing, fogging, scattering, coating, etc., or by acting on the combination around the plants and parts of plants, the environment or the storage space, and also, in the case of propagation material, in particular seeds, by applying one or more coatings.

[0110] The following examples will describe the subject matter of the present invention without limitation.

Example

[0111] Examples 1. Production and physical properties of samples 1 kg of a mixture of compound (I-2), optionally a second active ingredient, diammonium hydrogen phosphate (DAHP), (optionally) a second inorganic salt, Morwet EFW, Pergopak M, Kaolin W, a dispersion aid, optionally further magnesium stearate and an antifoaming agent was ground in a Hosokawa 100 AS 4” air jet mill (injected air 5.5 bar, grinding air 4.5 bar, throughput 100 g / min) by a method known to those skilled in the art, moistened with water (about 14% by weight), and extruded using a Fuji Paudal dome-type extruder (die size 1 mm) to obtain a WG. It was further dried in a fluidized bed dryer.

[0112]

Table 4

[0113]

Table 5

[0114]

Table 6

[0115] Measurement of pH (by method CIPAC MT 75.3): The pH is measured using a standard pH glass electrode in a 1% dispersion in which the granules are dispersed in deionized water at 23°C.

[0116] Measurement of suspension (by method CIPAC MT 184.1): Disperse a 1% suspension in water (CIPAC C) in a 250 mL volumetric cylinder. Equilibrate the mixture for 30 minutes. Then, remove the upper 9 / 10 of the suspension. Dry the remaining 1 / 10 and measure the residue (precipitate) by gravimetry. The suspensibility is defined as follows:

Number

[0117] Therefore, a value of 100% corresponds to all insoluble components being uniformly distributed throughout the sample volume.

[0118] Measurement of wet sieve residue (by method CIPAC MT 185): Charge 25 g of granules into 250 mL of water in a beaker. After 1 minute, stir the mixture with a magnetic stirrer for 5 minutes. Then, transfer the dispersion and washing water to the corresponding sieve to wash the beaker. Then, rinse the sieve with cold water until there is no obvious change in the residue on the sieve (up to 10 minutes). After drip-drying the sieve, quantitatively transfer the residue to an evaporating dish containing deionized water and dry it, and measure the residue by gravimetry.

[0119] 2. Usage examples * The productivity test for the press slurry for spray application was carried out using an induction hopper under the following boundary conditions: Tank capacity: 400 L * Amount of water: 100 L * Amount of granules: 2.5 kg

[0120] While circulating water with a pump, quickly introduce 2.5 kg of the product into the induction hopper and circulate it with the pump for another 10 minutes. After 5 minutes and 10 minutes, inspect the residue in the induction hopper, the filter at the water intake, and the residue of the undispersed product in the tank.

[0121]

Table 7

[0122] Materials used Geropon® TA / 72 is a sodium polycarboxylate salt, Geropon® SDS is sodium dioctyl sulfosuccinate, and Geropon® L-Wet max is a blend (supplier: Solvay).

[0123] Kaolin W is an aluminum hydrosilicate (supplier: Erbsloh Lohrheim GmbH & Co. KG, Lohrheim, Germany).

[0124] Tersperse® 2700 is a sodium naphthalene sulfonate-formaldehyde condensate (supplier: Indorama Ventures, The Woodlands, Texas, USA).

[0125] Rhodorsil Antifoam EP 6703® is absorbed polydimethylsiloxane (supplier: Solvay).

[0126] Morwet EFW is a sodium alkylnaphthalene sulfonate (supplier: Nouryon, Stenungsund, Sweden).

[0127] Pergopak® M is a polymethyl urea resin (supplier: Huber Martinswerk, Bergheim, Germany).

[0128] Atlox Metasperse TM 550S is a modified styrene-acrylic polymer (supplier: Croda, Great Britain).

[0129] Trilon® B powder is tetrasodium ethylenediaminetetraacetate (supplier: BTC Europe GmbH, Monheim, Germany).

[0130] Full pyraziflumid is a crop protection active substance (Supplier: Bayer Crop Science).

[0131] Abamectin is a crop protection active substance (Supplier: Syngenta).

[0132] Spinetoram is a crop protection active substance (Supplier: Corteva).

Brief Description of the Drawings

[0133]

Figure 1

Figure 2

Claims

1. A solid composition in the form of a granulated aqueous formulation, comprising: a. A tetramic acid derivative represented by formula (I): 【Chemical 1】 〔wherein, W and Y are, independently, hydrogen, C １ -C ４ -alkyl, chlorine, bromine, iodine or fluorine; X is C １ -C ４ -alkyl, C １ -C ４ -alkoxy, chlorine, bromine or iodine; A, B, and the carbon atoms to which they are attached are C １ -C ４ -alkyl- or C １ -C ４ -alkoxy-C １ -C ２ -alkyl-substituted alkylene dioxyl group-substituted C ３ -C ６ -cycloalkyl (wherein the alkylene dioxyl group forms a 5- or 6-membered ketal together with the carbon atom to which it is attached); G is hydrogen (a) or one of the following groups: 【Chemical 2】 [wherein, E is a metal ion or an ammonium ion; M is oxygen or sulfur; R １ is a straight-chain or branched C １ -C ６ -alkyl; R ２ is a linear or branched C １ -C ６ -alkyl] ]; b. At least one basic salt; c. At least one additional inorganic salt selected from the group consisting of carbonates and bicarbonates; d. At least one dispersant; e. At least one wetting agent; f. At least one bulking agent; g. At least one structurant; h. Optionally, further active ingredients; i. Optionally, further conventional adjuvants and formulation aids; 〕.

2. The composition according to claim 1, characterized in that it contains the following component: (h) At least one further active ingredient.

3. The composition according to claim 1 or 2, characterized in that component (a) in the composition of the present invention is a compound represented by formula (I): 〔wherein, 〕. 【Chemical Formula 3】

4. 【Chemical 4】 【Chem.】 The composition according to claim 1 or 2, characterized in that component (a) is a compound represented by the formula: 〔wherein, 〕.

5. 【Chemical Formula 5】 The composition according to any one of the preceding claims, characterized in that component (b) is diammonium hydrogen phosphate (DAHP).

6. The composition according to any one of the preceding claims, characterized in that component (c) is selected from the group consisting of sodium bicarbonate and potassium bicarbonate.

7. The composition according to any one of the preceding claims, characterized in that component (d) is a dispersant selected from the group consisting of the sodium salt of a copolymer of maleic acid and an olefin, the sodium salt of a copolymer of methacrylic acid and styrene, and a modified copolymer of methacrylic acid and styrene, more preferably a dispersant selected from the group consisting of the sodium salt of a copolymer of methacrylic acid and styrene and a modified copolymer of methacrylic acid and styrene.

8. The composition according to any one of the preceding claims, characterized in that component (e) is selected from the group consisting of the sodium salt of alkylated naphthalene sulfonate and the sodium salt of dioctyl sulfosuccinate, more preferably selected from the group consisting of the sodium salt of alkylated naphthalene sulfonate.

9. ​ ​ The composition according to one or more of the preceding claims, wherein component (f) is selected from the group consisting of kaolin, rutile and silicon dioxide, and more preferably is kaolin.

10. The composition according to one or more of the preceding claims, wherein component (g) is selected from the group containing polymethyl urea resin.

11. Component (h) is selected from the group consisting of imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyphenozide, milbemectin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron; more preferably, it is selected from the group consisting of ethiprole, spinetoram, abamectin and flupyradifurone. The composition according to one or more of the preceding claims.

12. a. Formula (I) 【Chemical Formula 6】 〔Here, the compound represented by formula (I) has 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 saturated C6-cycloalkyl substituted with an alkylenedioxyl group (wherein the alkylenedioxyl group forms a 5- or 6-membered ketal together with the carbon atom to which it is attached); G is hydrogen (a), or the following group 【Chemical Formula 7】 〔Here, M is oxygen; E is one metal ion equivalent or ammonium ion; R １ is a linear or branched C １ -C ４ -alkyl; R ２ is a linear or branched C １ -C ４ -alkyl]] and is one of them〕 The compound represented by; b. At least one inorganic basic salt; c. At least one inorganic salt selected from the group containing sodium bicarbonate and potassium bicarbonate; d. At least one dispersant of the polycarboxylate type; e. At least one anionic wetting agent; f. At least one inert extender; g. At least one structurant; h. Optionally, a further insecticidal active ingredient; i. Optionally, a further adjuvant; The composition according to one or more of the preceding claims, comprising [

13. ] The following compound: 【Chemical Formula 8】 A compound represented by formula (I), selected from b. At least one inorganic basic ammonium salt selected from the group comprising diammonium hydrogen phosphate (DAHP); c. At least one further inorganic salt selected from the group of carbonates and hydrogen carbonates; d. At least one dispersant of the polycarboxylate type selected from the following group: hydrophobically modified comb-like polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or a copolymer of maleic acid or maleic anhydride and 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, a copolymer of methacrylic acid and styrene, a modified copolymer of methacrylic acid and styrene, a copolymer of maleic acid or maleic anhydride and acrylic acid, N-methyl fatty acid (e.g., C ８ -C １８ ), -sarcosinate, carboxylic acids, such as resin acids or fatty acids (e.g., C ８ -C １８ ), or salts of such carboxylic acids, and salts of these copolymers; e. At least one anionic wetting agent selected from the group consisting of sodium salts of alkylated naphthalene sulfonates and sodium dioctyl sulfosuccinate; f. At least one inert extender selected from the group comprising carbonates, silicates and oxides, and further urea-formaldehyde condensates and cellulose; g. At least one structure former selected from the group comprising polyacrylic acid and its salts, crosslinked polyacrylates, and polyureas, polyurethanes and derivatized polyureas and polyurethanes; h. Optionally, a further insecticidal active ingredient; i. Optionally, a further adjuvant; The composition according to one or more of the preceding claims, comprising [

14. ] The following structure: 【Chemical Formula 9】 A compound represented by formula (I-2), having 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 sodium salts of alkylated naphthalene sulfonates; f. At least one inert extender selected from the group comprising kaolin, rutile and silicon dioxide; g. At least one structure former selected from the group comprising polymethyl urea resin; h. Optionally, a further insecticidal active ingredient; i. Optionally, a further adjuvant; The composition according to one or more of the preceding claims, comprising [

15. ] Components (a) to (g) are as follows: (a) 2-12% by weight; (b) 30-66% by weight; (c) 2-7% by weight; (d) 8-12% by weight; (e) 1.5-2.5% by weight; (f) 10-22% by weight; (g) 3-8% by weight; The composition according to one or more of the preceding claims, characterized by being present as such.

16. Component (h) is as follows (h) 1.5 - 20% by weight The composition according to one or more of the preceding claims, characterized by additionally being present as such.

17. Component (i) is as follows (i) 0.1 - 5% by weight The composition according to one or more of the preceding claims, characterized by being present as such.

18. A process for producing the composition according to one or more of the preceding claims, characterized in that the composition is brought about by mixing the components and then extruding them.

19. Use of the composition according to one or more of claims 1 to 17 for applying the present pesticidal active ingredient to plants and / or their habitats.

20. A product, characterized by containing the composition according to one or more of claims 1 to 17.

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

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