HIGHLY LOADED KETOENOL CLASS INSECTICIDE FOR USE IN DRIP AND DRENCH APPLICATIONS

Description

[0001] The present invention relates to solvent-free aqueous suspension concentrates with a high concentration of active ingredients, good biological efficacy, and good rheological stability. The invention is defined in claim 1. The formulations according to the invention are suitable for use in plant protection.

[0002] Active ingredients can, in principle, be formulated in many different ways, but the properties of the active ingredients and the type of formulation can pose problems regarding manufacturability, stability, applicability, and efficacy. Furthermore, certain formulations are more advantageous than others for economic and environmental reasons.

[0003] Water-based formulations generally have the advantage of requiring little or no organic solvents, and the absence of organic solvents can offer ecological benefits.

[0004] On the other hand, there is a general need for highly concentrated formulations of active ingredients because the higher concentration offers numerous advantages. For example, highly concentrated formulations require less packaging than low-concentration formulations. This, in turn, reduces the effort required for production, transport (quantity and frequency), and storage. Furthermore, the preparation of spray solutions used in agriculture is simplified by the smaller quantities of, for example, plant protection products that need to be handled, such as during filling and mixing. In addition, water-based formulations are usually not only more concentrated than organic, solvent-based formulations, but also more environmentally friendly because they are solvent-free. Moreover, highly concentrated formulations allow for more economical use of inert materials or carrier materials.

[0005] At the same time, the increased loading with AI (active ingredient) must not lead to a decrease in the technical stability of the formulation.

[0006] Highly concentrated suspension concentrates (SC) are therefore preferred from an economic and ecological point of view.

[0007] However, some substances, such as the herbicide safener, cannot be added directly to water due to their low and broad melting range and amorphous structure. Therefore, they must first be dissolved or formulated in organic solvents. They are then formulated, for example, as organic dispersions, aqueous emulsions, suspensions, capsule suspensions, or emulsion concentrates, in which the low-melting active ingredient is dissolved or emulsified. A disadvantage of this approach is that the addition of organic solvents does not result in aqueous dispersions, but rather in aqueous emulsions or suspensions, which are significantly less stable during storage and usually have lower concentrations than pure aqueous dispersions.When the technical concentrate is further processed into a water-dispersible granulate, up to 20 wt% of the commonly used mineral oils as solvents (such as Solvesso ®< 200 ND from ExxonMobil) remain in the final product.

[0008] Furthermore, the use of agrochemical formulations for soil application can be advantageous in cases where it is beneficial to avoid exposure of above-ground plant parts to pesticides, or to prevent drift (dispersal of the active ingredient) and exposure of unwanted areas and the fauna and flora living there. The reasons for this may lie in insufficient plant compatibility of the formulation or in incompatibility with other agrochemical products.

[0009] Soil application by drip or drench is particularly advantageous for systemically acting active ingredients, as their effect also unfolds in plant parts that are far away from the root that absorbs the active ingredients.

[0010] Liquid formulations of certain ketoenol insecticides based on organic solvents, which can be used in hydroponics against leaf-eating and / or leaf-sucking insects, are known from WO 2006 / 089633 A2. However, the solvent dimethylformamide described in WO 2006 / 089633 is classified as toxicologically problematic and is potentially toxic to reproduction or teratogenic.

[0011] Furthermore, water-based dispersions of ketoenol insecticides for controlling leaf-dwelling insects are known from WO 2009 / 115262 A1. The described formulations have a maximum loading of 50 g / L (5%), although a higher loading would be desirable from an economic point of view. However, the formulations known from WO 2009 / 115262 A1 are unsuitable for higher loadings.

[0012] EP 1 905 302 A1 discloses a storage-stable aqueous suspension concentrate containing spirotetramate, a polyalkoxytriglyceride as a penetration enhancer in combination with a polyglycerol as an adjuvant, as well as citric acid, xanthan gum, glycerol, surfactants, defoamers and other adjuvants.

[0013] From US 2017 / 166546 A1, aqueous suspension concentrates of spirodiclofen are known which contain, in addition to sodium alkylnaphthalenesulfonate as a dispersant, xanthan gum, propylene glycol and a preservative.

[0014] In WO 2007 / 068428 A2, the enhancement of the efficacy of plant protection products containing inhibitors of fatty acid biosynthesis (e.g., phenyl-substituted cyclic ketoenols) by the addition of ammonium salts and / or phosphonium salts, or by the addition of ammonium or phosphonium salts and penetration enhancers, the corresponding products, methods for their production, and their application in plant protection are described.

[0015] A disadvantage of the formulations known from the prior art (whether suspension concentrates or water-dispersible granules) is that large quantities of organic solvents, which are undesirable for the environment and the user, must be used to dissolve the safener, while the active ingredient loading and biological activity are insufficient.

[0016] There is therefore still a need for new formulations in the form of aqueous dispersions (SC) that offer a high active ingredient load with good environmental compatibility (no or minimal amounts of organic solvents) and good biological activity, as well as good bioavailability of the active ingredients in the soil or during soil application.

[0017] The object of the present invention was therefore to provide aqueous dispersions of certain ketoenol insecticides that exhibit a high active ingredient load, good environmental compatibility, and good biological activity. Preferably, these should be essentially free of organic solvents.

[0018] The present invention therefore relates to aqueous active ingredient dispersions (SC) with the above-mentioned properties as well as a process for the production of aqueous, solvent-free formulations (dispersions) and their application as insecticides.

[0019] Furthermore, it was surprisingly found that the biological activity of the aqueous dispersions according to the invention can be improved with increasing pH value.

[0020] The invention therefore relates to insecticidal compositions in the form of highly concentrated aqueous suspension concentrates containing: a. at least one ketoenol insecticide, b. at least one dispersant, preferably selected from the group of non-ionic dispersants, c. at least one pH buffer, d. xanthan gum as a rheology modifier, e. at least one antifreeze, f. at least one biocide, g. at least one defoamer, and h. optionally further active ingredients and adjuvants, and i. water, characterized in that a) is a tetramic acid derivative of formula (I). in which W and Y independently represent hydrogen, C1-C4 alkyl, chlorine, bromine, iodine or fluorine, X represents C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which they are bonded represent C3-C6 cycloalkyl, which is substituted by an alkylenedioxyl group, optionally substituted by C1-C4 alkyl or C1-C4 alkoxy-C1-C2 alkyl, forming a 5-ring or 6-ring ketal with the carbon atom to which it is bonded, G represents hydrogen (a) or one of the groups where E represents a metal ion or an ammonium ion, M represents oxygen or sulfur, R1 represents straight-chain or branched C1-C6 alkyl, R2 represents straight-chain or branched C1-C6 alkyl, and where components a) to g) are present in the following concentrations: a) 200-400 g / L b) 40-90 g / L c) 0.9-2.0 g / L d) 3-5 g / L e) 100-150 g / L f) 0.05-1.5 g / L g) 0.05-1.5 g / L.

[0021] In the present invention, in formulas, e.g. formula (I), optionally substituted residues can be singly or multiply substituted unless otherwise specified, wherein in the case of multiple substitutions the substituents can be the same or different.

[0022] Furthermore, in the preferred areas mentioned above in the present invention, the various preferred levels are to be understood in such a way that they can be combined with each other in a permuting manner; in any case, however, identical preferred levels and in particular the most preferred embodiment / preferred level are to be combined with each other and are also disclosed as such a combination.

[0023] Likewise, compositions as described above that consist only of the essential components (not optional components) shall be considered disclosed.

[0024] Unless otherwise stated, percentages are to be understood as weight percentages, with the weight percentages of the compositions adding up to 100.

[0025] Unless otherwise defined, basic in the context of the present invention means a pH value in aqueous solution of pH>7. a) Active ingredient

[0026] In the compositions according to the invention, component a) is a tetramic acid derivative of formula (I) in which W and Y independently represent hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine, X represents C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine, A, Bund represents the carbon atom to which they are bonded, C3-C6-cycloalkyl, which is substituted by an alkylenedioxyl group, optionally substituted by C1-C4-alkyl or C1-C4-alkoxy-C1-C2-alkyl, forming a 5-ring or 6-ring ketal with the carbon atom to which it is bonded, G represents hydrogen (a) or one of the groups, in which E stands for a metal ion or an ammonium ion, M stands for oxygen or sulfur, R 1< stands for straight-chain or branched C 1 -C 6 -alkyl, R 2< stands for straight-chain or branched C 1 -C 6 -alkyl.

[0027] Tetramic acid derivatives of the above-mentioned formula (I) are particularly preferred, in which the substituents have the following meaning: W particularly preferably represents methyl, X particularly preferably represents chlorine or methyl (particularly preferably methyl), Y particularly preferably represents chlorine, bromine or methyl, A, Bund the carbon atom to which they are bonded, particularly preferably represent saturated C 6 cycloalkyl substituted with an alkylenedioxyl group forming a 5-membered or 6-membered ring ketal with the carbon atom to which it is bonded, G particularly preferably represents hydrogen (a) or one of the groups in which M stands for oxygen, E for a metal ion equivalent or an ammonium ion, (especially for sodium or potassium) R 1< particularly preferably stands for straight-chain or branched C 1 -C 4 alkyl, R 2< particularly preferably stands for straight-chain or branched C 1 -C 4 alkyl.

[0028] Tetramic acid derivatives of the above-mentioned formula (I) with G = hydrogen (a) are particularly preferred for use.

[0029] Tetramic acid derivatives of the above-mentioned formula (I) with G = E (d) are also particularly suitable for use.

[0030] Tetramic acid derivatives of the above-mentioned formula (I) are particularly suitable for use, in which the substituents have the following meaning: Example No. W X Y A B known from WO 06 / 089633 ; Example No. I-1 CH 3 CH 3 CH 3 I-1-a-2 I-2 CH 3 CH 3 Cl I-1-a-4 I-3 CH 3 CH 3 Br I-1-a-26 I-4 CH 3 CH 3 CH 3 I-1-a-18 I-5 CH 3 CH 3 Cl I-1-a-14 I-6 CH 3 CH 3 Br I-1-a-19

[0031] In a particularly preferred embodiment, component a) is a compound of the formula

[0032] Compound I-2 is preferably used in its thermodynamically most stable polymorphic structure. This crystal structure and other physical data were determined as follows: Sample preparation: Compound I-2 (C 19 H 22 ClNO 4 / MW = 363.84 g / mol) was crystallized from methanol and dried at room temperature, yielding modification A.

[0033] The modification A of I-2 can be characterized by X-ray powder diffractometry based on the corresponding diffraction diagrams recorded at 25°C and with Cu-Kα 1 radiation (1.5406 Å).

[0034] Modification A according to the present invention exhibits at least 3, preferably at least 5, more preferably at least 7, even more preferably at least 10, and most preferably all reflections as shown in Table 2a: Crystallographic investigations on single crystals of modification A showed that the crystal structure is monoclinic. The unit cell has the space group P2 1 / c. Table 1: Crystallographic properties of modification A parameter Modification A Crystal system Monoclinic Room group P2 1 / c a in Å 11.66544(14) b in Å 9.50603(10) c in Å 16.66907(19) α 90 β 110.2045(13) γ 90 Z 4 Density (calculated) 1.393 g / cm³< a, b, c = length of the sides of the unit cell α, β, γ = angle of the unit cell Z = number of molecules in the unit cell Tables 2a / b: Crystallographic data / Reflections [°2Theta] of modification A 2a 2b [°2Theta] Reflexes [°2Theta] Modification A Modification A 11,3 8,0 14,6 10,8 16,0 11,3 20,1 12,2 21,7 14,6 22,7 16,0 23,1 17,6 24,5 18,4 28,2 19,4 29,0 20,1 21,7 22,7 23,1 23,8 24,5 25,9 26,4 28,2 29,0 29,4 30,1 30,6 32,2 36,2 37,4 38,2 39,1

[0035] The polymorphic form of modification A of I-1 can be determined by IR spectroscopy from the corresponding spectrum recorded at 25°C using a diamond ATR instrument at a resolution of 4 cm⁻¹. Modification A of the present invention exhibits at least 3, preferably at least 5, more preferably at least 7, and most preferably all bands as described in Table 2c. Table 2c) IR bands [cm -1< ] Band maxima [cm -1< ] Band maxima [cm -1< ] Modification A 3378 1133 2969 1109 2955 1088 2943 1045 2924 1036 2876 1027 2858 1015 2326 997 1637 980 1592 965 1575 946 1564 936 1470 903 1444 869 1438 856 1428 821 1394 783 1372 769 1344 748 1325 704 1317 691 1297 659 1272 639 1247 625 1194 573 1157 563 553 b) Dispersing agents

[0036] Suitable anionic dispersants b1) such as emulsifiers, surfactants, wetting agents and dispersants are, for example, alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof, such as the salts of alkylsulfonic or alkylphosphoric acids, as well as alkylarylsulfonic or alkylarylphosphoric acids, diphenylsulfonates, alpha-olefin sulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates include sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates include phosphate esters.Examples of carboxylates include alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates. Also suitable are the group of anionic emulsifiers of alkali metal, alkaline earth metal, and ammonium salts of polystyrenesulfonic acids, salts of polyvinylsulfonic acids, salts of alkylnaphthalenesulfonic acids, salts of alkylnaphthalenesulfonic acid-formaldehyde condensation products, and salts of condensation products of naphthalenesulfonic acid, phenolsulfonic acid, and formaldehyde. Examples include calcium dodecylbenzenesulfonate such as Rhodocal® < 70 / B (Solvay), phenylsulfonate CA100 (Clariant), and isopropylammonium dodecylbenzenesulfonates such as Atlox® < 3300B (Croda).

[0037] Other typical examples include Phenylsulfonate CA (Ca-dodecylbenzenesulfonate), Soprophor®< types (possibly esterified derivatives of tristyrylphenol ethoxylates), Emulsogen®< 3510 (alkylated EO / PO copolymer), Emulsogen®< EL 400 (ethoxylated castor oil), Tween®< types (fatty acylated sorbitan ethoxylates), Calsogen®< AR 100 (Ca-dodecylbenzenesulfonate). Preferred are combinations of salts of alkylated aromatic sulfonic acids, such as phenylsulfonate Ca and / or Calsogen®< AR 100, with alkylated copolymers of ethylene and propylene oxide, such as Emulsogen®< 3510. Particularly preferred are combinations of salts of dodecylbenzenesulfonic acid, such as Calsogen®< AR 100, with alkylated copolymers of ethylene and propylene oxide, such as Emulsogen®< 3510.

[0038] Examples of other anionic dispersants b1) from the naphthalenesulfonate group are Galoryl ®< MT 800 (sodium dibutylnaphthalenesulfonic acid), Morwet ®< IP (sodium diisopropylnaphthalenesulfonate) and Nekal ®< BX (alkylnaphthalenesulfonate). Examples of anionic surfactants from the group of condensation products of naphthalenesulfonates with formaldehyde are Galoryl®< DT 201 (naphthalenesulfonic acid hydroxypolymer with formaldehyde and methylphenol sodium salt), Galoryl®< DT 250 (condensation product of phenol and naphthalenesulfonates), Reserve®< C (condensation product of phenol and naphthalenesulfonates), or Morwet®< D-425, Tersperse®< 2020. Preferably, naphthalenesulfonates 1,2-substituted with di-butyl or di-isobutyl are used, such as products like Galoryl®< MT 800 (CFPI-Nufarm) and Nekal®< BX (BASF).

[0039] Other typical surfactants are Soprophor ®< 3D33, Soprophor ®< 4D384, Soprophor ®< BSU, Soprophor ®< CY / 8 (Solvay) and Hoe ®< S3474 and in the form of the Sapogenat ®< T products (Clariant), for example Sapogenat ®< T 100.

[0040] Suitable nonionic dispersants (b2) such as emulsifiers, wetting agents, surfactants, and dispersants are common surface-native substances found in formulations of agrochemical active ingredients. Examples include ethoxylated nonylphenols, reaction products of linear or branched alcohols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, and end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g.,Butoxypolyethylenepropylene glycols), reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, furthermore fatty acid esters, fatty acid polyglycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyrylphenol ethoxylate with an average of 16 ethylene oxide units per molecule, furthermore ethoxylated and propoxylated arylalkylphenols as well as sulfated or phosphatized arylalkylphenol ethoxylates or -ethoxy- and -propoxylates. Tristyrylphenol alkoxylates and fatty acid polyglycol ether esters are particularly preferred. Tristyrylphenol ethoxylates, tristyrylphenol ethoxy-propoxylates and castor oil polyglycol ether esters, each individually or in mixtures, are especially preferred. In addition, additives such as surfactants or fatty acid esters may be used to improve biological efficacy.Suitable non-ionic emulsifiers b2) are, for example, Soprophor ®< 796 / P, Lucramul ®< CO30, Lucramul ®< HOT, Lucramul ®< PSI 100, Lucramul PS 29 or Synperonic ®< T304.

[0041] Suitable non-ionic dispersants (b2) may also be selected from the group containing polyvinylpyrrolidone (PVP), polyvinyl alcohol, PVP-dimethylaminoethyl methacrylate copolymer, butylated PVP, vinyl chloride-vinyl acetate copolymer, and partially hydrolyzed vinyl acetate, phenolic resins, modified cellulose types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol), or modified cellulose. Polyvinylpyrrolidone types are preferred, and low molecular weight types such as Luviskol® K30 or Sokalan® K30 are particularly preferred.

[0042] Other non-ionic emulsifiers b2) from the group of di- and tri-block copolymers of alkylene oxides include, for example, compounds based on ethylene and propylene oxides, with average molar masses between 200 and 10000, preferably 1000 to 4000 g / mol, wherein the mass fraction of the polyethoxylated block varies between 10 and 80%, such as Synperonic®< PE series (Uniqema), Pluronic®< PE series (BASF), VOP®< 32- or Genapol®< PF series (Clariant).

[0043] Particularly preferred are non-ionic dispersants, especially non-ionic dispersants based on tristyrylphenol polyethylene glycol ethers, e.g. Lucramul PS 29, and polyethylene oxide modified poly(methyl methacrylate) methacrylic acids, e.g. Atlox ®< 4913. c) pH buffer

[0044] Suitable pH buffers include commercially available pH buffers such as citrate, phosphate, and acetate. pH buffers with a pH ≤ 7 (measured in aqueous solution with a hydrogen electrode) are preferred.

[0045] Preferably, pH buffers based on citrate and phosphate are used. d) Rheology modifiers

[0046] Xanthan gum is used as a rheology modifier (c). Typical examples include Rhodopol® (Solvay), Kelzan® (Kelco Corp.), and Satiaxane® (Cargill). e) Antifreeze

[0047] Suitable antifreeze agents are those from the group of ureas, diols and polyols, such as ethylene glycol and propylene glycol, glycerin, preferably propylene glycol or glycerin, particularly preferably glycerin. f) Biocides

[0048] Preferably biocides based on isothiazolinones are used, preferably selected from the group consisting of benzisothiazolinone, chloromethylisothiazolinone, methylisothiazolinone and mixtures thereof.

[0049] Biocides based on 1,2-benzisothiazolin-3-one and chloromethylisothiazolinone are particularly preferred.

[0050] Suitable biocides include products such as Acticide ®< MBS (Biocide, Thor Chemie), CIT, MIT or BIT, such as Proxel ®< GXL (BIT), Acticide ®< SPX (MIT, CIT), Kathon CGI. g) Defoamer

[0051] Suitable defoamers are surface-active compounds based on silicone or silane, such as the Tegopren®< products (Goldschmidt), the SE®< products (Wacker), as well as the Bevaloid®< (Kemira), Rhodorsil®< (Solvay) and Silcolapse®< products (Blustar Silicones). SE®< (Wacker), Rhodorsil®< and Silcolapse®< products are preferred, and silicone-based defoamers, e.g., products such as Silcolapse®< 5020, are particularly preferred. h) optionally other active ingredients and adjuvants

[0052] The compositions according to the invention may optionally contain further formulation aids (h), e.g., optionally substances from the groups of antioxidants, dyes and / or inert fillers, penetration enhancers, as well as further, preferably insecticidal, active ingredients.

[0053] Suitable antioxidants include all substances commonly used for this purpose in agrochemicals. Butylhydroxytoluene is preferred.

[0054] Suitable dyes include all substances commonly used for this purpose in agrochemicals. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, and Permanent Red FGR.

[0055] In this context, polyalkoxytriglycerides, for example, are suitable penetration enhancers. Polyalkoxytriglycerides can be produced by the alkoxylation of triglycerides. The alkoxylation of triglycerides leads to mixtures in which 1 to 3 of the side chains are alkoxylated. Alkoxylation can be categorized as ethoxylation, propoxylation, butoxylation, or a mixture of these processes. The length of the unmodified side chains can vary independently of the other side chains in the same molecule, ranging from 9 to 24, preferably from 12 to 22, and most preferably from 14 to 20 carbon atoms. These aliphatic side chains can be straight or branched.

[0056] Further insecticidal active ingredient (f) are preferably selected from the group consisting of imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamide, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor and triflumurone; particularly preferably from the group consisting of ethiprole and flupyradifurone.

[0057] The proportion of active ingredient (component a / compounds of formula I / I-2) in the compositions according to the invention is 200-400 g / L.

[0058] The proportion of dispersing agent (component b) in the compositions according to the invention is 40 - 90 g / L.

[0059] The proportion of pH buffer (component c) in the compositions according to the invention is 0.9 - 2 g / L.

[0060] The proportion of rheology modifier (component d) in the compositions according to the invention is 3 - 5 g / L.

[0061] The proportion of antifreeze (component e) in the compositions according to the invention is 100 - 150 g / L.

[0062] The proportion of biocide (component f) in the compositions according to the invention is 0.05 - 1.5 g / L.

[0063] The proportion of defoamer (component g) in the compositions according to the invention is 0.05 - 1.5 g / L.

[0064] The proportion of the other active ingredients and adjuvants (component h) - if included - in the compositions according to the invention is preferably 0.01 - 5 g / L.

[0065] In the formulations according to the invention, water is added to 1 L as described above and below.

[0066] In the embodiments mentioned above, as well as in all compositions according to the invention mentioned in the present application, the pH value of the aqueous suspension concentrates is preferably 3 - 9, more preferably 4 - 8, and particularly preferably 5 to 7.

[0067] In a preferred embodiment, the insecticidal composition according to the invention contains: a. Compounds of formula (I) where W stands for methyl, X for chlorine or methyl, Y for chlorine, bromine or methyl, A, Bund the carbon atom to which they are bonded, stand for saturated C6 cycloalkyl substituted with an alkylenedioxyl group forming a 5-ring or 6-ring ketal with the carbon atom to which it is bonded, G for hydrogen (a) or for one of the groups, in which M stands for oxygen, E for a metal ion equivalent or an ammonium ion, R1< for straight-chain or branched C1-C4 alkyl, R2< for straight-chain or branched C1-C4 alkyl, b. at least one non-ionic dispersant selected from the group consisting of tristyrylphenol alkoxylates and fatty acid polyglycol ether esters, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. xanthan gum as a rheology modifier, e. at least one antifreeze selected from the group consisting of ureas, diols, and polyols, f. at least one biocide from the group of isothiazolinones, g. at least one defoamer from the group of silicone- or silane-based defoamers, h. optionally, further active ingredients and adjuvants.

[0068] In a further preferred embodiment, the insecticidal composition according to the invention comprises: a. a compound of formula (I) selected from the following compounds W X Y A B CH 3 CH 3 CH 3 CH 3 CH 3 Cl CH 3 CH 3 Br CH 3 CH 3 CH 3 CH 3 CH 3 Cl CH 3 CH 3 Br b. at least one non-ionic dispersant selected from the group of tristyrylphenol alkoxylates, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. Xanthan gum as a rheology modifier, e. at least one antifreeze selected from the group consisting of diols and polyols, f. at least one biocide from the group consisting of benzisothiazolinone, chloromethylisothiazolinone and methylisothiazolinone, g. at least one defoamer from the group of silicone-based defoamers, h. optionally other active ingredients and adjuvants.

[0069] In a particularly preferred embodiment, the insecticidal composition according to the invention contains: a. the combination of formula (I-2) with the following structure: b. at least one non-ionic dispersant selected from the group of tristyrylphenol alkoxylates, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. xanthan gum as a rheology modifier, e. at least one antifreeze selected from the group consisting of ethylene glycol, propylene glycol, and glycerol, preferably propylene glycol and glycerol, and particularly preferably glycerol, f. benzisothiazolinone as a biocide, g. at least one defoamer from the group of silicone-based defoamers, h. optionally further active ingredients and adjuvants.

[0070] The amount of the formulations according to the invention used can be varied within a wide range. It depends on the respective active ingredients and their content in the compositions.

[0071] With the help of the compositions according to the invention, the insecticidal active ingredient mixtures can be applied to plants and / or their habitat in a particularly advantageous manner.

[0072] The compositions according to the invention can be used to treat all plants and plant parts. Here, "plants" refers to all plants and plant populations, such as desirable and undesired wild plants or cultivated plants (including naturally occurring cultivated plants). Cultivated plants can be plants obtained through conventional breeding and optimization methods, or through biotechnological and genetic engineering methods, or combinations thereof, including transgenic plants and plant varieties that are or are not protected by plant variety rights. "Plant parts" refers to all aboveground and belowground parts and organs of plants, such as shoots, leaves, flowers, and roots, with examples including leaves, needles, stems, trunks, flowers, fruiting bodies, fruits, and seeds, as well as roots, tubers, and rhizomes.Plant parts also include harvested crops as well as vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

[0073] The compounds of formula (I or II) are preferably used after drenching, dipping, or drip application against animal pests from the following pest families: Preferably from the family of blister aphids (Pemphigidae): Eriosoma spp., Pemphigus spp., in crops such as citrus, pome fruit, stone fruit, leafy vegetables, root and tuber vegetables and ornamental plants.

[0074] Preferred species from the family of root aphids (Phylloxeridae) are: Phylloxera spp. in wine, nuts, citrus.

[0075] Preferred species from the family Psyllidae (psyllids): Psylla spp., Paratrioza spp., Tenalaphara spp., Diaphorina spp., Trioza spp., in crops such as pome fruit, stone fruit, citrus, vegetables, potatoes, in tropical crops.

[0076] Preferred species from the family Coccidae (soft scale insects): Ceroplastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., Coccus spp., in perennial crops such as citrus, pome fruit, stone fruit, olives, wine, coffee, tea, tropical crops, ornamental plants, vegetables.

[0077] Preferred species from the family Diaspididae (armored scale insects): Quadraspidiotus spp., Aonidiella spp., Lepidosaphes spp., Aspidiotus spp., Aspis spp., Diaspis spp., Parlatoria spp., Pseudaulacaspis spp., Unaspis spp., Pinnaspis spp., Selenaspidus spp., in crops such as citrus, pome fruit, stone fruit, almonds, pistachios, nuts, olives, tea, ornamental plants, wine, tropical crops.

[0078] Preferred species include Orthezia spp. from the family of tube scale insects (Ortheziidae) found in citrus, pome fruit, and stone fruit.

[0079] Preferred species from the mealybug and scale insect family (Pseudococccidae) are: Pericerga, Pseudococcus spp., Planococcus spp., Dysmicoccus spp., in crops such as citrus, stone and pome fruit, tea, wine, vegetables, ornamental plants and tropical crops.

[0080] Also preferred are species from the family of whiteflies (Aleyrodidae): Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes spp., Dialeurodes spp., Parabemisia myricae in crops such as vegetables, melons, potatoes, tobacco, berries, citrus, ornamental plants, cotton, soy and tropical crops.

[0081] Also preferred are members of the Aphidae family: Myzus spp. in tobacco, stone fruit, berries, fruiting vegetables, leafy vegetables, tuber and root vegetables, melons, potatoes, ornamental plants, spices,

[0082] Acyrthosiphon onobrychis in vegetables Aphis spp. in tobacco, citrus, pome fruit, stone fruit, melons, strawberries, berries, fruiting vegetables, leafy vegetables, tuber, stalk and root vegetables, ornamental plants, potatoes, pumpkins, spices; Rhodobium porosum in strawberries; Nasonovia ribisnigri in leafy vegetables; Macrosiphum spp. in ornamental plants, potatoes, leafy and fruiting vegetables, strawberries; Phorodon humuli in hops; Brevicoryne brassicae in leafy vegetables; Toxoptera spp. in citrus, stone fruit, almonds, nuts, spices; Aulacorthum spp. in citrus, potatoes, fruiting and leafy vegetables; Anuraphis cardui in vegetables; Brachycaudus helycrisii in sunflowers; Acyrthosiphon onobrychis in vegetables.

[0083] Also preferred are species from the Thrips family (Thripidae): Anaphothrips spp., Baliothrips spp., Caliothrips spp., Frankliniella spp., Heliothrips spp., Hercinothrips spp., Rhipiphorothrips spp., Scirtothrips spp., Kakothrips spp., Selenothrips spp. and Thrips spp., in crops such as fruit, cotton, wine, tea, nuts, tropical crops, ornamental plants, conifers, tobacco, spices, vegetables, berries, melons, citrus and potatoes.

[0084] Also preferred are flies from the families of leaf miners (Agromyzidae) and flower flies (Anthomyiidae): Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., Pegomyia spp. in crops such as vegetables, melons, potatoes, nuts, ornamental plants.

[0085] Preferred species include cicadas (Cicadellidae) and horned cicadas (Delphacidae); Circulifer spp., Dalbus spp., Empoasca spp., Erythroneura spp., Homalodisca spp., Iodioscopus spp., Laodelphax spp., Nephotettix spp., Nilaparvata spp., Oncometopia spp., Sogatella spp., found in crops such as citrus, fruit, wine, potatoes, vegetables, ornamental plants, conifers, melons, berries, tea, nuts, rice and tropical crops.

[0086] Preferred species from the family Gracillariidae (mining moths): Caloptilia spp., Gracillaria spp., Lithocolletis spp., Leucoptera spp., Phtorimaea spp., Phyllocnistis spp. in crops such as pome fruit, stone fruit, wine, nuts, citrus, conifers, potatoes, coffee.

[0087] Preferred targets are species from the gall midge family (Cecodomyiidae): Contarinia spp., Dasineura spp., Diplosis spp., Prodiplosis spp., Thecodiplosis spp., Sitodiplosis spp., Haplodiplosis spp. in crops such as citrus, pome fruit, stone fruit, vegetables, potatoes, spices, berries, conifers, hops.

[0088] Also preferred are species from the fruit fly family (Tephritidae): Anastrepha spp., Ceratitis spp., Dacus spp., Rhagoletis spp. in crops such as vegetables, berries, melons, pome and stone fruits, ornamental plants, potatoes, wine, tropical crops, citrus, olives.

[0089] Also preferred are mites from the families of spider mites (Tetranychidae) and gall mites (Eriophydae): Tetranychus spp., Panonychus spp., Aculops spp. in crops such as vegetables, potatoes, ornamental plants, citrus, wine, conifers.

[0090] The treatment of plants and plant parts with the compositions according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by drenching, dipping, spraying, evaporating, fogging, scattering, brushing and, in the case of propagation material, especially seeds, furthermore by single or multi-layer coating.

[0091] The active ingredient is preferably applied by pouring it onto the soil. Alternatively, it can be applied by drip application or dip application.

[0092] Preferably, the plant to be treated is selected from the group consisting of cotton, soybean, tobacco, vegetables, spices, ornamental plants, conifers, citrus plants, fruit, tropical crops, nuts and wine.

[0093] Preferably, the composition according to the invention is effective against pests from the families of blister aphids, root aphids, psyllids, soft scale insects, armored scale insects, tube scale insects, mealybugs, woolly aphids, moth whiteflies, tube aphids, thrips, leafhoppers, horned leafhoppers, leaf miners, gall midges, fruit flies, leaf miners, spider mites, and gall mites.

[0094] The suspension concentrates according to the invention are produced by mixing the components together in the desired proportions. The order in which the components are mixed is arbitrary. Advantageously, the solid components are used in a finely ground state. However, it is also possible to subject the suspension resulting from the mixing of the components first to coarse and then to fine grinding, so that the average particle size is below 20 µm. Suspension concentrates in which the solid particles have an average particle size between 1 and 10 µm are preferred (determined by laser diffraction, e.g., with a Malvern Mastersizer 2000 or 3000, whereby the sample is diluted in pH 4 buffer until the dispersion reaches a suitable turbidity. The data are processed using Fraunhofer diffraction or Mie theory).

[0095] The temperatures can be varied within a certain range when carrying out the method according to the invention. Generally, work is carried out at temperatures between 10°C and 60°C, preferably between 15°C and 40°C.

[0096] Conventional mixing and grinding equipment used for the production of agrochemical formulations can be used to carry out the process according to the invention.

[0097] In the method according to the invention, the water preferably has a temperature between 0°C and 40°C, preferably between 5°C and 20°C.

[0098] Also part of the present invention are water-dispersible suspension concentrates (SC) obtainable according to the inventive method.

[0099] Grinding can be carried out according to methods known in the prior art, e.g. by wet grinding of the components in bead mills (such as discontinuous bead mills or continuous bead mills), or colloid mills (such as tooth colloid mills).

[0100] With the suspension concentrates according to the invention, improved biological efficacy and bioavailability can be achieved with the same application rate when applied to the soil. Advantageously, the suspension concentrates according to the invention exhibit excellent plant compatibility and a reduced tendency to cause phytotoxic damage.

[0101] Surprisingly, the suspension concentrates according to the invention exhibit excellent dispersing and stabilizing properties after further dilution with liquids, preferably water, with improved biological activity.

[0102] In addition, the suspension concentrates result in formulations that are stable over long periods of storage and technically sound in application, with improved rheological properties.

[0103] The invention is further explained by the examples without thereby limiting it. Examples: Materials used:

[0104] The terms used in the following examples have the following meanings: Citric acid polybasic organic acid Rhodopol ®< 23 Xanthan Derivative (Solvay) Silfoam® < SRE Silicone defoamer (Wacker) SAG 1572 Silicone defoamer (Momentive) Glycerin antifreeze Proxel® < GXL Preservatives (biocide, Proxel) Kathon CG / ICP Preservative (Biocide, Rohm and Haas) Lucramul PS29 Tristyrylphenol ethoxylate (dispersant, Levaco) Lucramul PS54 Tristyrylphenol ethoxylate (dispersant, Levaco) Atlox 4913 Ethoxylate-polymethacrylate graft copolymer (dispersant, Croda) Production examples

[0105] To produce a suspension concentrate, all liquid components are first mixed together. Next, the solids are added and stirred until a homogeneous suspension is obtained. This homogeneous suspension is then subjected to coarse and then fine grinding, resulting in a suspension in which 90% of the solid particles have a particle size below 5 µm. Finally, the thickener, pre-solution, antifreeze, and water are added while stirring at room temperature. This yields a homogeneous suspension concentrate.

[0106] The following examples illustrate the invention without limiting it in any way. All values ​​are given in g / L. Table 5: Rheological properties (Comparative) example Elastic Modulus (Pa) @ Strain (Measured @0.1 Hz) Phase Angle(°) @ Strain (Measured @0.1 Hz) Yield Stress (Pa) Dynamic Viscosity @ Yield Rhinestone (Pa*s) 1-1 (comparison) 0.3 Pa @ 0.1 50° 0.1 0.5 1-2 (comparison) 0.3 Pa @0.5 50° 0.1 0.4 1-3 (Comparison) 0.6 Pa @0.1 45° 0.1 0.5 1-4 (Comparison) 0.6 Pa @0.1 45° 0.1 0.5 1-5 (comparison) 1 Pa @0.1 40° 0.1 1 1-6 (Comparison) 5 Pa @0.01 30° 0.02 10 1-7 (Comparison) 12 Pa @0.002 15° 0.05 50 2-1 8 Pa @0.2 25° 2 12 2-2 5 Pa @0.1 25° 1 10 2-3 15 Pa @0.1 25° 2 13 2-4 35 Pa @0.005 20° 3 30 2-5 80 Pa @0.003 15° 0.2 400 2-6 8 Pa @3 20° 3 29 2-7 8 Pa @3 20° 3 30 2-8 8 @0.1 25° 3 20

[0107] As Table 5 shows, the formulations according to the invention exhibit improved rheological properties with a reduced tendency to sediment and clump. This results from both the higher modulus of elasticity of the formulations according to the invention and the smaller phase angle.

[0108] Accordingly, the formulations according to the invention exhibit a higher yield stress and a higher dynamic viscosity at the yield point than the formulations known from the prior art. Technical characterization and storage stability

[0109] The dispersions do not lose their rheological properties when stored above 2W@RT / 30°C / 54°C (Table 2)

[0110] Furthermore, the representative formulation example 2-8 does not lose its technical properties (AI concentration, particle size, syneresis) after storage (Table 7)

[0111] Unless otherwise defined, W means weeks and T means days within the scope of the present invention. Biological activity after drip application

[0112] Drip application in greenhouse testing: Cotton plants are planted in flowerpots containing 1 liter of sandy loam soil (58.5% sand, 12.9% clay, 28.5% loam, 1.6% humus, pH 6.8). After 7 days, 1 mg of the active ingredient in the specified formulation is dissolved in 60 mL of water and dripped into the potting soil over a period of 15 minutes using a dipper approximately 1 cm from the base of the plant. The plants are kept in a greenhouse at 25 °C with sufficient lighting. After another seven days (during which watering is performed as needed, without overflowing the pot), a mixed population of Aphis gossypiiInfected. 7 days after infection, mortality (dead animals compared to a fully effective standard and to an untreated control) is evaluated.

[0113] Drench application in greenhouse testing: Cotton plants are planted in flowerpots containing 1 liter of sandy loam soil (58.5% sand, 12.9% clay, 28.5% loam, 1.6% humus, pH 6.8). After 7 days, 2 mg of the active ingredient in the specified formulation is added to 60 mL of the potting soil all at once, poured around the base of the plant. The plants are kept in a greenhouse at 25 °C with sufficient light. After another seven days (during which watering is done as needed, without overflowing the pot), a mixed population of Aphis gossypii Infected. 7 days after infection, mortality (dead animals compared to a fully effective standard and to an untreated control) is evaluated. Table 8 Application method Example wording Concentration AI pH spray solution Biological control drip 2-8 1 mg AI / L Soil pH 5 55% pH 7 65% Drench 2-8 2 mg AI / L Soil pH 5 85% pH 7 93% Testing and storage procedures:

[0114] All tests were performed according to the CIPAC methods commonly used in plant protection (CIPAC = Collaborative International Pesticides Analytical Council; www.cipac.org). Long-term storage was carried out according to CIPAC MT 46.3 at room temperature / 54°C for 2 weeks. The following terms have the following meanings: Unless otherwise specified, 1% in water (CIPAC D, 342 ppm water hardness) at 23°C is tested. 0T = Test result after zero days of storage; 2W RT / 54 = Test result of the accelerated storage test (2 weeks room temperature / 54°C) to verify the long-term stability of a formulation product; D90 / 50 = Active ingredient particle size (laser scattering 90% / 50% of all volume particles); D90 / 50 2WRT / 54 = Active ingredient particle size after storage test (2 weeks room temperature / 54°C); An increase in the values ​​indicates crystal growth, whereby an increase by a factor of 2 is usually still acceptable; more than a factor of 4 is unacceptable; Sediment = Values ​​> 10% indicate strong sediment formation.

Claims

1. Composition comprising: a. at least one ketoenol insecticide, b. at least one dispersant, preferably selected from the group of the nonionic dispersants, c. at least one pH buffer, d. xanthan as rheology modifier, e. at least one antifreeze, f. at least one biocide, g. at least one defoamer, and h. optionally further active ingredients and adjuvants, and i. water, characterized in that a) is a tetramic acid derivative of the formula (I) in which 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 bonded are C3-C6-cycloalkyl substituted by an optionally C1-C4-alkyl- or C1-C4-alkoxy-C1-C2-alkyl-substituted alkylenedioxy group that forms a 5-membered or 6-membered ketal together with the carbon atom to which it is bonded, G is hydrogen (a) or is one of the groups in which E is a metal ion or an ammonium ion, M is oxygen or sulfur, R1 is straight-chain or branched C1-C6-alkyl, R2 is straight-chain or branched C1-C6-alkyl, and where components a) to g) are present as follows: a) 200-400 g / L b) 40-90 g / L c) 0.9-2.0 g / L d) 3-5 g / L e) 100-150 g / L f) 0.05-1.5 g / L g) 0.05-1.5 g / L2. Composition according to Claim 1, characterized in that component a) in the compositions according to the invention is a compound of the formula (I) with WXYABCH3CH3CH3 CH3CH3Cl CH3CH3Br CH3CH3CH3 CH3CH3Cl CH3CH3Br 3. Composition according to one or more of the preceding claims, characterized in that component a) is a compound of the formula (I-2) 4. Composition according to one or more of the preceding claims, characterized in that component b) is a nonionic dispersant based on tristyrylphenol polyethylene glycol ethers.

5. Composition according to any of the preceding claims, characterized in that component c) is a citrate- or phosphate-based pH buffer.

6. Composition according to one or more of the preceding claims, characterized in that component e) is an antifreeze selected from the group consisting of ureas, diols and polyols.

7. Composition according to one or more of the preceding claims, characterized in that component f) is a biocide selected from the group of the isothiazolinones.

8. Composition according to one or more of the preceding claims, characterized in that component g) is a silicone-based defoamer.

9. Composition according to Claim 1, comprising a. compounds of the formula (I) where the compounds of the 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 bonded are saturated C6-cycloalkyl substituted by an alkylenedioxy group that forms a 5-membered or 6-membered ketal together with the carbon atom to which it is bonded, G is hydrogen (a) or is one of the groups in which M is oxygen, E is one metal ion equivalent or an ammonium ion, R1 is straight-chain or branched C1-C4-alkyl, R2 is straight-chain or branched C1-C4-alkyl, b. at least one nonionic dispersant selected from the group consisting of tristyrylphenol alkoxylates and fatty acid polyglycol ether esters, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. xanthan as rheology modifier, e. at least one antifreeze selected from the group consisting of ureas, diols and polyols, f. at least one biocide from the group of isothiazolinones, g. at least one defoamer from the group of the silicone- or silane-based defoamers, h. optionally further active ingredients and adjuvants.

10. Composition according to one or more of Claims 1 to 9, comprising a. the compound of the formula (I-2) having the following structure: b. at least one nonionic dispersant selected from the group of the tristyrylphenol alkoxylates, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. xanthan as rheology modifier, e. at least one antifreeze selected from the group consisting of ethylene glycol and propylene glycol, glycerol, preferably propylene glycol or glycerol, more preferably glycerol, f. at least one biocide from the group consisting of benzisothiazolinone, g. at least one defoamer from the group of the silicone-based defoamers, h. optionally further active ingredients and adjuvants.

11. Product characterized by a content of a composition according to one or more of Claims 1 to 10.

12. Non-therapeutic use of a composition according to one or more of Claims 1 to 10 for controlling insects.