Formulation of insecticidal mixtures containing glycol ether solvents

Abstract

The present invention relates to an insecticidal active ingredient formulation comprising at least one dissolved active ingredient and one active ingredient in solid form, which has good storage stability at high and low temperatures and high active ingredient penetration, a process for producing the same, and its use for the application of the active ingredient present.

Description

[Technical Field]

[0001] The present invention relates to an insecticidal active ingredient formulation comprising at least one dissolved active ingredient and one active ingredient in solid form, which has good storage stability at high and low temperatures and high active ingredient penetration, a process for producing the same, and its use for the application of existing active ingredients. The present invention further relates to an adjuvant combination for an insecticidal active ingredient formulation having at least one dissolved active ingredient and at least one active ingredient in solid form, for improving the penetration of both active ingredients. [Background technology]

[0002] To demonstrate biological effectiveness, systemically active pesticide ingredients, especially systemic insecticides, require formulations that allow the uptake of the active ingredient into the plant / target organism. The best effect can be achieved in that the corresponding active ingredient is diluted in an aqueous solution for use and / or is already in solution, preferably in a concentrate, so that a high active ingredient concentration is always available.

[0003] This is true whenever an active ingredient or active ingredient combination is formulated as an emulsion concentrate (EC) or soluble liquid (SL), where the availability of the dissolved and suspended active ingredients is limited by the solubility equilibrium.

[0004] Furthermore, the biological activity can optionally be further increased by adding suitable adjuvants / penetrating agents.

[0005] As mentioned above, in formulations such as suspension concentrates (SC) and / or oil suspension concentrates (OD), the active ingredient or active ingredient combination is not in a dissolved form but in a solid, particulate form, so these active ingredients in the formulation typically do not have good bioavailability. Here, it is essentially only by adding a suitable adjuvant / penetrating agent that the biological activity can be increased, but this still results in a decrease in biological activity compared to the above-mentioned EC or SL formulations.

[0006] It is known that active pesticide ingredients differ from each other in terms of their physicochemical properties, such as solubility in water, solvent and / or oil, melting point and boiling point, polarity, molar mass, etc. These properties affect the compatibility of active ingredients. Many known active pesticide ingredients, for example, have high melting points, so they can withstand thermal stress, such as that occurring when producing suspension concentrates. In contrast, active ingredients with low melting points can only withstand these production conditions with difficulty, and can only be produced to a very limited extent as storage-stable suspensions, because the active ingredient is expected to soften or melt at relatively high temperatures. However, if the active ingredient is no longer in crystalline form, the physical stability of the formulated product is often significantly reduced, and it no longer has practical utility.

[0007] Furthermore, it is known that organic substances have varying water solubility, which may be pH dependent depending on their chemical properties, for example, via salt formation.

[0008] It is also known that it is often appropriate to combine active pesticide ingredients with each other, for example, to prevent the formation of resistance (for example, by combining different mechanisms of action), or when pests react differently to different active ingredients, or to expand the spectrum of action of the mixture. In the latter case, the mixture of active ingredients can, for example, significantly reduce the effective application rate, thereby enabling specific control of harmful insects without excessively or at all harming beneficial organisms. Another reason for using a mixture of active ingredients may be that the active ingredients have different durations of action (half-lives in plants or soil), so that extremely long-term protection can be achieved with just one treatment.

[0009] Stable suspension concentrates are characterized by physical and chemical storage stability over long periods (12-24 months) and a wide temperature range (0-54° C.), which is necessary so that advantageously only a single formulation with the same active ingredient or active ingredient combination can be used in various climatic regions.

[0010] The storage stability of suspension concentrates is characterized, inter alia, by the fact that containers of these suspension concentrates have little, if any, phase separation over the storage period. Additional parameters for the stability of suspension concentrates include, for example, the stability of the dispersion in the concentrate, which manifests itself in the presence or absence of aggregates in the concentrate.

[0011] WO 2011 / 029552 describes alkylpolypropyleneglycol-polyethyleneglycol (e.g. Antarox B / 848)-containing pesticide formulations in which this surfactant class is used as an emulsifier and / or penetrant for the active pesticide ingredient.

[0012] Furthermore, WO 2003 / 000053 describes certain alkyl polypropylene glycol-polyethylene glycols, such as Atlas G5000, as dispersants for organic crop protection products in oil.

[0013] The use of ammonium salts to enhance the activity of active pesticide ingredients is known in the literature.For example, WO 2011 / 131623 (US 2011 / 0281727, Fischer et al.) describes insecticide and / or herbicidal formulations based on heterocyclyl tetramic acid, which have improved efficacy in the presence of ammonium salts.Furthermore, WO 2007 / 068428 describes the activity-enhancing effect of phenyl-substituted cyclic keto-enols in the presence of ammonium salts.WO 2011 / 131623 relates to the combination of a single active ingredient selected from the group of substances of formula [I] with organic or inorganic ammonium salts or phosphonium salts, and its use in aqueous sprays in the presence or absence of a suitable penetrant. Proceeding from the teachings of WO 2011 / 131623, the expert cannot draw any conclusions regarding the physical and chemical stability of formulations with combinations of additional active ingredients or of these mixture formulations. Suitable penetrants are extensively described in paragraphs 1 to 4 and generally claimed in , but only rapeseed oil methyl ester is cited as an example of a vegetable oil derivative and Genapol LRO is cited as an example of an anionic alcohol ether sulfate.

[0014] WO 2011 / 131623 does not describe or suggest a formulation with good penetration of dissolved and non-dissolved active ingredients according to the present invention.

[0015] The oil-based formulation containing ammonium salt is also known in the literature.For example, WO2008 / 151725 describes the adjuvant composition based on oil, in which ammonium salt is in dispersed form.Furthermore, EP2193712 describes the oil-based pesticide formulation, in which ammonium salt is in dispersed form.However, there is no description about the suspension of ammonium salt in water-miscible solvent.

[0016] In summary, however, none of the above cited documents, taken individually or together, suggests that alkyl polypropylene glycol-polyethylene glycols, such as Antarox B / 848, can be used as effective dispersants for inorganic ammonium salts at high loadings in polar water-soluble solvents such as glycol ethers, particularly with suspended and dissolved active ingredients.

[0017] The soluble aqueous concentrate of tetramic acid derivatives is known in the prior art, for example, from WO 2009 / 115262.Due to solubility problems, they cannot be combined with certain crop protection products and formulation components.In addition, these aqueous SL formulations generally have high pH value, which also causes incompatibility with certain base-sensitive crop protection products and formulation components. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] International Publication No. 2011 / 029552 [Patent Document 2] International Publication No. 2003 / 000053 [Patent Document 3] International Publication No. 2011 / 131623 [Patent Document 4] U.S. Patent No. 2011 / 0281727 [Patent Document 5] International Publication No. 2007 / 068428 [Patent Document 6] International Publication No. 2008 / 151725 [Patent Document 7] European Patent No. 2193712 [Patent Document 8] International Publication No. 2009 / 115262 Summary of the Invention [Problem to be solved by the invention]

[0019] The problem addressed was therefore to develop a stable formulation consisting of a combination of a dissolved and a suspended active ingredient, with good bioavailability and penetration capabilities of both active ingredients, and with good storage stability at both high and low temperatures. The active ingredient is preferably an insecticide.

[0020] This problem has been solved by the formulation described below, which contains an active ingredient combination, an ammonium salt, and a glycol ether as a solvent. [Means for solving the problem]

[0021] Thus, the present invention provides an insecticidal composition comprising: a. at least one active ingredient that is solid at room temperature and is preferably insoluble or sparingly soluble in the selected solvent g); ba), at least one active ingredient soluble in an organic solvent, c. at least one ammonium salt; d. at least one dispersant from the class of alkyl propoxylate ethoxylates; e. optionally, one or more surfactants; f. at least one water-insoluble filler; g. at least one solvent from the group of glycol ethers, and h. Additional adjuvants.

[0022] In a preferred embodiment, component e) is essential.

[0023] Furthermore, in preferred embodiments, the composition is essentially free of water. The term "essentially free of water" refers to a composition containing less than 5% water, preferably less than 4% water, and more preferably less than 3% water.

[0024] According to the present invention, it has been found that the corresponding compositions have good penetration-enhancing properties for both the active pesticide ingredients present and high stability, which was surprising considering the different properties of the active ingredients a) and b).

[0025] In the present invention, in a formula, for example, in formula (I), an optionally substituted group may be mono- or polysubstituted, unless otherwise specified, and the substituents in the case of polysubstitution may be the same or different.

[0026] Furthermore, in the preferred ranges stated in the present invention, different preferred levels are to be understood as they can be combined with one another in permutations, but in each case the same preferred levels, in particular the most preferred embodiments / preferred levels in each case, should be combined with one another and are in fact disclosed as such combinations.

[0027] Compositions described herein consisting only of essential ingredients (and not optional ingredients) should also be considered to be disclosed.

[0028] In the context of the present invention, room temperature means a temperature between 20°C and 25°C, unless otherwise specified.

[0029] Components a-h are further defined below. [Brief explanation of the drawings]

[0030] [Figure 1] FIG. 1 shows a modified example A of I-2. [Figure 2] FIG. 2 shows the polymorphic form of variation A of I-1. DETAILED DESCRIPTION OF THE INVENTION

[0031] a. Active ingredients that are solid at room temperature The active ingredient that is solid at room temperature is preferably selected from the group including insecticides, herbicides and fungicides.More preferably, the selected active ingredient is insoluble or slightly soluble in the selected solvent g).Furthermore, the active insecticidal ingredient that is solid at room temperature and insoluble or slightly soluble in the selected solvent g) is preferred.

[0032] In the context of the present invention, poorly soluble or insoluble active ingredients are active ingredients which are solid at room temperature and which preferably have a solubility at 20°C in the selected solvent g) of less than or equal to 5 g / l, more preferably less than or equal to 4 g / l, even more preferably less than or equal to 2.5 g / l, and particularly preferably less than or equal to 1 g / l.

[0033] Even more preferably, the active ingredient is selected from the group comprising diamide insecticides (broflanilide, chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyhalodiamide, flubendiamide, tetrachlorantraniliprole and tetraniliprole), spinosyns (IRAC Group 5), the so-called "mectins" (e.g., abamectin, emamectin benzoate, milbemectin; IRAC Group 6), ethiprole, triflumuron, deltamethrin, thiacloprid, and tetronic and tetramic acid derivatives (IRAC Group 23, including compounds of formula I and II specified below).

[0034] In a preferred embodiment, component a) in the composition according to the invention is tetraniliprole, cyantraniliprole, ethiprole, thiacloprid, spirotetramat, or Keto-enols based on tetramic acids, preferably compounds of formula (I), [ka]

[0035] During the ceremony, W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine; X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which they are attached are C3-C6-cycloalkyl substituted by an alkylenedioxy group, optionally substituted by C1-C4-alkyl- or C1-C4-alkoxy-C1-C2-alkyl, which together with the carbon atom to which they are attached form a 5- or 6-membered ketal, G is hydrogen (a) or one of the following groups: [ka]

[0036] During the ceremony, E is a metal ion or an ammonium ion; M is oxygen or sulfur; R 1 is a linear or branched C1-C6 alkyl; R 2 is a straight-chain or branched C1-C6 alkyl.

[0037] Particularly preferably usable are tetramic acid derivatives of the above formula (I) in which the radicals are defined as follows: W is more preferably methyl; X is more preferably chlorine or methyl (more preferably methyl); Y is more preferably chlorine, bromine or methyl; A, B and the carbon atom to which they are attached are more preferably saturated C6-cycloalkyl substituted by an alkylenedioxy group, which together with the carbon atom to which it is attached forms a 5- or 6-membered ketal, G is more preferably hydrogen (a) or one of the following groups: [ka]

[0038] During the ceremony, M is oxygen, E is one metal ion equivalent or an ammonium ion (specifically, sodium or potassium); R 1 is more preferably a linear or branched C1-C4 alkyl; R 2 is more preferably a straight-chain or branched C1-C4 alkyl.

[0039] Specifically, the tetramic acid derivatives of the above formula (I) in which G=hydrogen (a) can be used.

[0040] Likewise, tetramic acid derivatives of formula (I) above, in which G=E(d), can also be used in particular.

[0041] Particularly preferably usable are tetramic acid derivatives of the above formula (I) in which the radicals are defined as follows: [ka] [Table 1]

[0042] In a particularly preferred embodiment, component a) is a compound of the following formula: [ka]

[0043] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorph, the crystal structure of which and additional physical data were determined as follows: Sample preparation: Compound I-2(C 19 H 22 ClNO4 / MW=363.84 g / mol) was crystallized from methanol and dried at room temperature to give Modification A.

[0044] Modification A of I-2 can be characterized by X-ray powder diffraction based on the corresponding diffractogram recorded at 25° C. with Cu-Kα 1 radiation (1.5406 Å) (FIG. 1).

[0045] Variant A according to the invention exhibits at least 3, preferably at least 5, more preferably at least 7, even more preferably at least 10, and most preferably all, reflections as shown in FIG. 1: The variant A according to the invention is also characterized by the X-ray diffraction pattern shown in FIG.

[0046] Crystallographic testing on a single crystal of Modification A showed that the crystal structure was monoclinic. The unit cell had the P21 / c space group. [Table 2] [Table 3]

[0047] The polymorphic form of variant A of I-1 is 4 cm -1 The bands can be determined by IR spectroscopy using the corresponding spectrum recorded at 25°C using a diamond ATR instrument with a resolution of 100 .ANG. (FIG. 2). Variant A of the present invention exhibits at least three, preferably at least five, more preferably at least seven, and even more preferably all bands as shown in FIG. 2 and listed in Table 2c. [Table 4]

[0048] In an alternative embodiment, component a) comprises a tetramic acid of formula (II): [ka]

[0049] During the ceremony, 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, V 1 is hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, nitro or cyano, V 2 is hydrogen, halogen, C1-C6-alkyl or C1-C6-alkoxy, V 3 is hydrogen or halogen, A, B and the carbon atom to which they are attached are saturated C5-C6-cycloalkyl, one ring member of which is replaced by oxygen, optionally monosubstituted by C1-C8-alkyl, C1-C8-alkoxy or C1-C6-alkyloxy-C1-C6-alkyl, G is hydrogen (a) or one of the following groups: [ka]

[0050] During the ceremony, E is a metal ion or an ammonium ion; L is oxygen or sulfur; M is oxygen or sulfur; R 1 is a linear or branched C1-C6 alkyl; R 2 is a straight-chain or branched C1-C6 alkyl.

[0051] Particularly preferably usable are tetramic acid derivatives of the above formula (I) in which the radicals are defined as follows: W is more preferably hydrogen or methyl; X is more preferably chlorine or methyl; Y is more preferably hydrogen; V 1 is more preferably fluorine or chlorine (specifically, fluorine or chlorine at the 4-position), V 2 is more preferably hydrogen or fluorine (specifically, fluorine at the 3-position), V 3 is more preferably hydrogen or fluorine (specifically, fluorine at the 5-position), A, B and the carbon atom to which they are attached are more preferably saturated C6-cycloalkyl in which one ring member is replaced by oxygen, G is more preferably hydrogen (a) or one of the following groups: [ka]

[0052] During the ceremony, E is more preferably one metal ion equivalent or an ammonium ion (e.g., sodium or potassium); R 1 is more preferably a linear or branched C1-C4 alkyl; R 2 is more preferably a straight-chain or branched C1-C4 alkyl.

[0053] Specifically, the tetramic acid derivatives of the above formula (I) in which G=hydrogen (a) can be used.

[0054] Likewise, tetramic acid derivatives of formula (I) above, in which G=E(d), can also be used in particular.

[0055] Particularly preferably usable are tetramic acid derivatives of the above formula (II) in which the groups are defined as follows: [Table 5]

[0056] In a particularly preferred alternative embodiment, a) is: [ka]

[0057] b. Soluble active ingredient The soluble active ingredient is preferably selected from the group consisting of insecticides, herbicides and fungicides. More preferably, the selected active ingredient has good or sufficient solubility in the selected solvent g), the solubility at 20°C being preferably at least 10 g / l, more preferably at least 20 g / l, even more preferably at least 30 g / l, and even more preferably at least 40 g / l.

[0058] The soluble active ingredient is preferably selected from the group of insecticides.Even more preferably, the active ingredient is nAChR agonists (IRAC group 4, such as imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, sulfoxaflor, nitenpyram and flupyradifurone), flonicamid, and additional insecticides as described in WO 2007 / 115644, such as 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one. furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluorovinyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, or in WO 2009 / 118025, for example, 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0059] More preferably, the active ingredient b) is selected from imidacloprid, clothianidin, flupyradifurone, flonicamid and acetamiprid.

[0060] Most preferably, the active ingredient b) is flupyradifurone.

[0061] In another embodiment, the active ingredient b) is flonicamid.

[0062] In yet another embodiment, the active ingredient b) is acetamiprid.

[0063] C. ammonium salts The ammonium salt is preferably selected from the group comprising water-soluble inorganic ammonium salts.

[0064] More preferably, c) is selected from the group comprising ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate (AMS), ammonium hydrogen carbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0065] More preferably, c) is DAHP and AMS.

[0066] d. Dispersant Component d) is preferably selected from the group comprising alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a), [ka]

[0067] In the formula, R is a C1 to C4 fragment, preferably a C3 to C4 fragment, and more preferably a C4 fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably consisting of 15 to 35 PO units, and more preferably consisting of 20 to 30 PO units; B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units (Formula III-c) with 0-10 propylene glycol (PO) units, preferably consisting of 20-40 EO units with 0-8 PO units, more preferably consisting of 30-40 EO units with 0-5 PO units. [ka]

[0068] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are as follows: [Table 6]

[0069] and compounds of general formula (IIId) RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId) wherein the individual groups and indices have the following definitions: R and R' are independently hydrogen, a linear C1- to C5-alkyl group or a branched C3- or C4-alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; wherein one group n or m has the meaning of 2 and the other group n or m has the meaning of 3).

[0070] In the context of the present invention, a straight-chain C1- to C5-alkyl group is understood to mean a methyl, ethyl, n-propyl, n-butyl or n-pentyl group.

[0071] In the context of the present invention, a branched C3- to C4-alkyl group is understood to mean an isopropyl, isobutyl or tert-butyl group.

[0072] In a preferred embodiment, the R and R' groups are independently selected from the group consisting of methyl, n-butyl, and hydrogen.

[0073] In an even more preferred embodiment, the R and R' groups are independently selected from the group consisting of n-butyl and hydrogen.

[0074] Regarding the arrangement of polyethylene units and polypropylene units, (a) m may take the value 2 and n may take the value 3, (b) Alternatively, m may take the value 3 and n may take the value 2.

[0075] Configuration (b) where m=3 and n=2 is preferred.

[0076] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of formula (IIId), in which m is 3, n is 2, x is 5 to 80; y is 5 to 80; R is n-butyl or hydrogen, and R' is hydrogen.

[0077] e. Suitable surfactants e) in the context of the present invention are selected from the group comprising: e1) Polycarboxylate surfactants, such as hydrophobically modified comb polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (such as isobutylene or diisobutylene), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylate, copolymers of acrylic acid and vinyl acetate, copolymers of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acids (for example C8-C 18 )-sarcosinate, carboxylic acid, for example, resin acid or fatty acid (e.g., C8-C 18 ), or copolymers with salts of such carboxylic acids. The copolymers may also be in the form of their salts, such as alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines. For example, examples of the above include Geropon T / 36, Geropon TA / 72, Tersperse 2700, Atlox Metasperse 550 S, Geropon Ultrasperse, Narlex D-72, Versa TL3 and Agrilan 789 Dry; e2) surfactants selected from the group consisting of salts of sulfated formaldehyde condensation products with alkylaromatics, such as MORWET D-425 (available from Akzo Nobel); OPARYL DT 120, OPARYL DT 201, OPARYL DT 530 (available from Bozzetto); TERSPERSE 2020 (available from Huntsman), and salts of sulfated formaldehyde condensation products with ditolyl ethers (for example, BAYKANOL SL available from Levaco), and salts of sulfated formaldehyde condensation products with cyclohexanone (for example, LUCRAMUL DAC 210 available from Levaco), and e3) surfactants selected from the group of lignosulfonates and their salts, preferably Borresperse NA, Borresperse 3A, Ultrazine NA, Ufoxane 3A, Vanisperse CB, Marasperse AG, MARASPERSE N 22, MARASPERSE C 21, MARASPERSE CBOS-4, WAFEX CA122 and Borresperse CA from Borregaard; KRAFTSPERSE EDF-350, KRAFTSPERSE 25M, KRAFTSPERSE EDF-450, REAX 100M, REAX 83A, REAX 85A, REAX 88A, REAX 88B, REAX 907, REAX 910, POLYFON H, POLYFON O and POLYFON T from Ingevity; AGRINOL DN from Tembec a surfactant selected from the group of lignosulfonates and salts thereof consisting of 19 and Agrinol C12, and e4) surfactants selected from the group consisting of sulfated alkylarylsulfonates and their salts, such as alkylarylsulfonates and their salts, for example, AEROSOL OS (manufactured by Solvay); AGNIQUE ANS 3DNP-U, AGNIQUE ANS 4DNP, AGNIQUE NSC 2NP-U, NEKAL BX DRY (manufactured by BASF); MORWET B, MORWET DB, MORWET EFW, MORWET IP (manufactured by Akzo Nobel); OPARYL MT 704, OPARYL MT 800, OPARYL MT 804 (manufactured by Bozzetto); RHODACAL BX 78, SUPRAGIL WP (manufactured by Solvay); SURFOM HRB (manufactured by Oxiteno), and the like; e5) surfactants from the group di- / tristyrylphenol ethoxylate phosphates and their salts, DISPERSOGEN LFH, DISPERSOGEN TP 160 (Clariant); LUCRAMUL PPS 16, LUCRAMUL PPS K 16 (Levaco); PHOSPHOLAN PHB 14 (Akzo Nobel); SOPROPHOR 3 D 33, SOPROPHOR TS 20-F, SOPROPHOR FL, SOPROPHOR FLK (Solvay); STEPFAC TSP-PE, STEPFAC TSP PE-K (Stepan); SURFOM 1323 SC, SURFOM 1325 SC (Oxiteno); TERSPERSE 2222 (Huntsman); and alcohol ethoxylate phosphates, for example EMPIPHOS 03 D (Akzo Nobel); MULTITROPE Surfactants from the group: 1214, Crodafos series, Atphos 3226 (manufactured by Croda); PHOSPHOLAN PE 169 (manufactured by Akzo Nobel); RHODAFAC RS-410, RHODAFAC RS-710, RHODAFAC TD 20 F (manufactured by Solvay); SERVOXYL VPDZ 20 / 100 (manufactured by Elementis); STEPFAC 8180 (manufactured by Stepan); CRAFOL AP261 (manufactured by BASF); GERONOL CF / AR (manufactured by Clariant).

[0078] More preferably, suitable surfactants are selected from the group comprising surfactants e1), e2), e3) and e4).

[0079] More preferably, suitable surfactants are selected from the group comprising surfactants e1), e2) and e3).

[0080] Even more preferably, suitable surfactants are selected from the group comprising surfactants e1) and e2).

[0081] Even more preferably, suitable surfactants are selected from the group comprising surfactants e1).

[0082] Very particular preference is given to surfactants of group e1) which include sodium salts of copolymers of maleic acid and olefins (e.g. Geropon T / 36 / Solvay; Duramax D-305 / Dow); and sodium salts of copolymers of methacrylic acid and styrene (Tersperse 2700 / Huntsman; Atlox Metasperse 500S / Croda); in particular sodium salts of copolymers of maleic acid and olefins (e.g. Geropon T / 36).

[0083] Suitable surfactants, such as Tersperse 2700, are also described in WO2008036865.

[0084] The above surfactants can be used individually or in combination, with preference being given to a combination of a surfactant selected from the group of sodium salts of copolymers of maleic acid and olefins with salts of sulfated formaldehyde condensation products with alkylaromatics and lignosulfonates and their salts.

[0085] f. Water-insoluble fillers Suitable fillers are preferably selected from the group comprising: f1) modified natural silicates, such as chemically modified bentonite, hectorite, attapulgite, montmorillonite, smectite or other silicate minerals, such as Bentone® (Elementis), Attagel® (BASF), Agsorb® (Oil-Dri Corporation), Pangel B (Tolsa) or Hectorite® (Akzo Nobel), f2) synthetic silicates and fumed silicas, for example silicates from the Sipernat®, Aerosil® or Durosil® series (Degussa), CAB-O-SIL® series (Cabot) or Van Gel series (RT Vanderbilt), and f3) Fillers based on synthetic polymers, for example thickeners from the Thixin® or Thixatrol® series (Elementis).

[0086] Fillers of group f2 are more preferred.

[0087] Fumed silicas as fillers f) are particularly preferred, for example the Aerosil, Aerosil R and Cab-O-Sil products, and attapulgite, both alone and in mixtures.

[0088] g. Solvent The solvent g) is selected from a compound or a mixture of compounds represented by formula 4, wherein: [ka]

[0089] y=1~9 A, B = independently of each other H or linear C1-C4 alkyl; M=H or C1-C2-alkyl.

[0090] It refers to all definitions of g) in the present invention, except for 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0091] In a further preferred embodiment, g) is selected from a compound or mixture of compounds represented by formula 4, wherein: y=1~5 A, B = independently of each other H or linear C1-C4 alkyl; M=H; or g) is selected from a compound or mixture of compounds represented by formula 4, wherein: y=1~5 A, B = independently of each other H or linear C1-C4 alkyl; M=C1-C2-alkyl; However, this does not include 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0092] Even more preferably, g) is selected from compounds represented by formula 4, wherein: y=1~3 A, B = H or methyl independently of each other; M = methyl; However, this does not include 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0093] Most preferably, g) is selected from the group comprising dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol.

[0094] In a preferred embodiment, the solvent g) according to the present invention can occur in a mixture. The mixture of any one of g) can be present in a ratio ranging from 1:50 to 50:1, preferably in a ratio ranging from 1:25 to 25:1, more preferably in a ratio ranging from 1:10 to 10:1, for example, 1:10, 1:8, 1:6, 1:5, 1:2, 1:1, 2:1, 5:1, 6:1, 8:1 or 10:1. Yet another preferred embodiment comprises a mixture of any one of g) in a ratio ranging from 1:8 to 1:1, or in a ratio ranging from 1:1 to 8:1. Examples of solvents g) include Dowanol glycol ether products from Dow, or different grades of polyethylene glycol ethers (e.g. ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol monobenzyl ether), Alternatively, different grades of polypropylene glycol ethers (for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monobenzyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, and tripropylene glycol monobenzyl ether) may be used.

[0095] h. Additional adjuvants The compositions according to the invention may optionally contain additional adjuvants h), for example substances from the group of the emulsifiers, wetting agents, antifoaming agents, preservatives, dyes, stabilizers and antioxidants.

[0096] Useful emulsifiers include all conventional nonionogenic, anionic, cationic, and zwitterionic substances with surfactant properties typically used in agricultural chemical products, including fatty acids, fatty acid esters, fatty alcohols, fatty amines, reaction products of alkylphenols or alkylarylphenols with ethylene oxide and / or propylene oxide and / or butylene oxide and their sulfate esters, mono- and diesters of phosphoric acid, and reaction products of ethylene oxide and propylene oxide, as well as alkyl sulfonates, alkyl sulfates, aryl sulfates, tetraalkylammonium halides, trialkylarylammonium halides, alkylamine sulfonates, end-capped and non-end-capped alkoxylated linear and branched saturated and unsaturated alcohols (e.g., butoxypolyethylene-propylene glycol), and polyethylene glycols and polypropylene glycols.

[0097] The emulsifiers may be used individually or in mixtures. Preferred examples include reaction products of castor oil with ethylene oxide in a molar ratio of 1:20 to 1:60, reaction products of C6-C20 alcohols with ethylene oxide in a molar ratio of 1:5 to 1:50, reaction products of C6-C20 alcohols with propylene oxide and ethylene oxide in a molar ratio of 1:1:1 to 1:5:10, reaction products of fatty amines with ethylene oxide in a molar ratio of 1:2 to 1:25, reaction products of 1 mol of phenol with 2-3 mol of styrene and 10-50 mol of ethylene oxide, reaction products of C8-C12 alkylphenols with ethylene oxide in a molar ratio of 1:5 to 1:30, alkyl glycosides, C8-C16 alkylbenzenesulfonates, such as calcium salts, monoethanolammonium salts, diethanolammonium salts and triethanolammonium salts.

[0098] Useful humectants are any material typically usable for this purpose in pesticide compositions. Water-soluble liquids are preferred, examples of which include glycerol and 1,2-propylene glycol.

[0099] Useful antifoaming agents are any of the materials typically usable for this purpose in pesticide compositions. Silicone oils, such as SAG 1572, and magnesium stearate are preferred.

[0100] Useful antioxidants are any of the materials typically usable for this purpose in pesticide compositions. Butylhydroxytoluene is preferred.

[0101] Useful dyes are any material that can typically be used for this purpose in pesticide compositions. Examples include titanium dioxide, pigment black, zinc oxide and blue pigments, and Permanent Red FGR.

[0102] Possible stabilizers used may be, for example, acids or bases. Examples of acids include citric acid, formic acid, acetic acid, or boric acid. Examples of bases include sodium salts of carboxylic acids and mono- or poly-alkyl-substituted amines.

[0103] In a preferred embodiment, the present invention provides an insecticidal composition comprising: a. Compound of formula (I) [ka]

[0104] The compounds of formula (I) have the following definitions: W is methyl; X is chlorine or methyl; Y is chlorine, bromine or methyl; A, B and the carbon atom to which they are attached are saturated C6-cycloalkyl substituted by an alkylenedioxy group, which together with the carbon atom to which it is attached form a 5- or 6-membered ketal; G is hydrogen (a) or one of the following groups: [ka]

[0105] During the ceremony, M is oxygen, E is one metal ion equivalent or an ammonium ion, R 1 is a linear or branched C1-C4 alkyl; R 2 is a straight-chain or branched C1-C4 alkyl. b. The at least one active ingredient is preferably the nAChR agonist, flonicamid, and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluorovinyl)amino]-5 -methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0106] c. at least one ammonium salt selected from the group consisting of ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP); d. Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) [ka]

[0107] (wherein R is a C1 to C4 fragment, preferably a C3 to C4 fragment, and more preferably a C4 fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably consisting of 15 to 35 PO units, and more preferably consisting of 20 to 30 PO units; B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units with 0-10 propylene glycol (PO) units (Formula III-c), preferably consisting of 20-40 EO units with 0-8 PO units, more preferably consisting of 30-40 EO units with 0-5 PO units), [ka]

[0108] and alkylpolypropylene glycol-polyethylene glycol compounds of general formula (IIId) RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId) wherein the individual groups and indices have the following definitions: R and R' are independently hydrogen, a linear C1- to C5-alkyl group or a branched C3- or C4-alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; in which one group n or m has the meaning 2 and the other group n or m has the meaning 3), e. At least one surfactant selected from the group consisting of polycarboxylate type, salts of sulfated formaldehyde condensation products with alkyl aromatics, salts of sulfated formaldehyde condensation products with ditolyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, lignosulfonates and salts thereof, sulfated alkylarylsulfonates and salts thereof, di- / tristyrylphenol ethoxylate phosphates and salts thereof, and alcohol ethoxylate phosphates.

[0109] f. At least one filler selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite, and fillers based on synthetic polymers.

[0110] g. at least one solvent selected from a compound or mixture of compounds represented by formula 4, y=1~5 A, B = independently of each other H or linear C1-C4 alkyl; M=H); or g) is selected from a compound or mixture of compounds represented by formula 4, wherein: y=1~5 A and B are H or linear C1-C4 alkyl M=C1-C2-alkyl; However, this does not include 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0111] h. Additional adjuvants.

[0112] In a further preferred embodiment, the present invention provides an insecticidal composition comprising: a. A compound of formula (I) selected from the following compounds: [ka] [Table 7]

[0113] b. The at least one active ingredient is preferably imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, sulfoxaflor, nitenpyram, and flupyradifurone, flonicamid, and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one,

[0023] The insecticide is selected from the group of insecticides comprising 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0114] c. at least one ammonium salt selected from the group consisting of ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP); d. Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) [ka]

[0115] (wherein R is a C1 to C4 fragment, preferably a C3 to C4 fragment, and more preferably a C4 fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably consisting of 15 to 35 PO units, and more preferably consisting of 20 to 30 PO units; B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units with 0-10 propylene glycol (PO) units (Formula III-c), preferably consisting of 20-40 EO units with 0-8 PO units, more preferably consisting of 30-40 EO units with 0-5 PO units), [ka]

[0116] and alkylpolypropylene glycol-polyethylene glycol compounds of general formula (IIId) RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId) wherein the individual groups and indices have the following definitions: R and R' are independently hydrogen, a linear C1- to C5-alkyl group or a branched C3- or C4-alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; in which one group n or m has the meaning 2 and the other group n or m has the meaning 3), e. at least one surfactant selected from the group consisting of polycarboxylate type, salts of sulfated formaldehyde condensation products with alkyl aromatics, salts of sulfated formaldehyde condensation products with ditolyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, and lignosulfonates and their salts; f. At least one filler selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite, and fillers based on synthetic polymers.

[0117] g. at least one solvent selected from a compound or mixture of compounds represented by formula 4, y=1~3 A, B = H or methyl independently of each other; M = methyl; (Except 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0118] h. Additional adjuvants.

[0119] In an even more preferred embodiment, the present invention provides an insecticidal composition comprising: a. A compound having the formula (I-2) having the following structure: [ka]

[0120] b. Flupyradifurone, c. at least one ammonium salt selected from the group consisting of ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP); d. Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) [ka]

[0121] (wherein R is a C1 to C4 fragment, preferably a C3 to C4 fragment, and more preferably a C4 fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably consisting of 15 to 35 PO units, and more preferably consisting of 20 to 30 PO units; B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units with 0-10 propylene glycol (PO) units (Formula III-c), preferably consisting of 20-40 EO units with 0-8 PO units, more preferably consisting of 30-40 EO units with 0-5 PO units), [ka]

[0122] and alkylpolypropylene glycol-polyethylene glycol compounds of general formula (IIId) RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId) wherein the individual groups and indices have the following definitions: R and R' are independently hydrogen, a linear C1- to C5-alkyl group or a branched C3- or C4-alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; in which one group n or m has the meaning 2 and the other group n or m has the meaning 3), e. at least one surfactant selected from the group comprising polycarboxylate types; f. At least one filler selected from the group consisting of fumed silica and attapulgite.

[0123] g. at least one solvent selected from a compound or mixture of compounds represented by formula 4, y=1~3 A, B = H or methyl independently of each other; M = methyl; except for 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0124] h. Additional adjuvants.

[0125] In a most preferred embodiment, the present invention provides an insecticidal composition comprising: a. A compound having the formula (I-2) having the following structure: [ka]

[0126] b. Flupyradifurone, c. at least one ammonium salt selected from the group consisting of ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP); d. Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) [ka]

[0127] (wherein R is a C1 to C4 fragment, preferably a C3 to C4 fragment, and more preferably a C4 fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably consisting of 15 to 35 PO units, and more preferably consisting of 20 to 30 PO units; B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units with 0-10 propylene glycol (PO) units (Formula III-c), preferably consisting of 20-40 EO units with 0-8 PO units, more preferably consisting of 30-40 EO units with 0-5 PO units), [ka]

[0128] and alkylpolypropylene glycol-polyethylene glycol compounds of general formula (IIId) RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId) wherein the individual groups and indices have the following definitions: R and R' are independently hydrogen, a linear C1- to C5-alkyl group or a branched C3- or C4-alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; in which one group n or m has the meaning 2 and the other group n or m has the meaning 3), e. at least one surfactant selected from the group comprising polycarboxylate types; f. At least one filler selected from the group consisting of fumed silica and attapulgite.

[0129] g. at least one solvent or solvent mixture selected from the group consisting of dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, and dipropylene glycol h. Additional adjuvants.

[0130] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorph.

[0131] Percentages should be considered as weight percents where the weight % of the composition totals 100 unless otherwise stated.

[0132] The percentages of the individual components below are based on the total weight of the composition, with component h) (solvent) accounting for up to 1 liter of the total composition. Therefore, the percentage of component h) is preferably 1% to 80% by weight, more preferably 20 to 60% by weight.

[0133] The proportion of solid active ingredient (component a) in the composition according to the invention is: Preferably 0.5 to 30% by weight, More preferably, 1 to 20% by weight More preferably, it is 1 to 15% by weight.

[0134] The proportion of dissolved active ingredient (component b) in the composition according to the invention is Preferably 1 to 20% by weight, More preferably, 1 to 16% by weight, More preferably, it is 1 to 12% by weight.

[0135] The proportion of ammonium salt (component c) in the composition according to the invention is Preferably 1 to 40% by weight, More preferably, 5 to 35% by weight, More preferably, it is 15 to 30% by weight.

[0136] The proportion of dispersant (component d) in the composition according to the invention is: Preferably 0.5 to 40% by weight, More preferably, 2.5 to 35% by weight, More preferably, it is 5 to 30% by weight.

[0137] The proportion of surfactant (component e) in the composition according to the invention is: Preferably 0 to 10% by weight, More preferably, 0.3 to 8% by weight More preferably, it is 0.5 to 2.5% by weight.

[0138] The proportion of filler (component f) in the composition is Preferably 0.1 to 10% by weight, More preferably, 0.5 to 10% by weight More preferably, it is 2 to 10% by weight.

[0139] The proportion of additional adjuvant (component h) in the composition according to the invention is Preferably 1 to 20% by weight, More preferably, 2.5 to 17.5% by weight, More preferably, it is 5 to 15% by weight.

[0140] A preferred embodiment of the present invention is a composition comprising the following components: a)1~30% by weight b)1~20% by weight c)1~40% by weight d)1~40% by weight e) 0~10% by weight f)0.1~15% by weight h)1~20% by weight g) Up to 1 litre.

[0141] A further preferred embodiment of the present invention is a composition comprising the following components: a)2~20% by weight b)1~60% by weight c)5~35% by weight d)5~35% by weight e)0.3~8wt% f)0.5~12.5wt% h)2.5~17.5wt% g) Up to 1 litre.

[0142] An even more preferred embodiment of the present invention is a composition comprising the following components: a)2~15% by weight b)1~12% by weight c)15~30% by weight d) 10~30% by weight e)0.5~2.5wt% f)1~10% by weight h)5~15% by weight g) Up to 1 litre.

[0143] The present invention further relates to an adjuvant combination for an insecticidal active ingredient formulation having at least one dissolved active ingredient and one active ingredient in solid form to improve the penetration of both active ingredients, the adjuvant combination comprising: c. at least one ammonium salt; d. at least one dispersant from the class of alkyl propoxylated ethoxylates.

[0144] In a preferred embodiment, the adjuvant combination further comprises: g. A solvent selected from a compound or mixture of compounds represented by formula 4 [ka]

[0145] (wherein y=1 to 9) A, B = independently of each other H or linear C1-C4 alkyl; M=H or C1-C2-alkyl; (Except 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0146] The ammonium salt from the adjuvant combination is preferably selected from the group comprising water-soluble inorganic ammonium salts.

[0147] More preferably, c) is selected from the group comprising ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate (AMS), ammonium hydrogen carbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0148] More preferably, b) is DAHP and AMS.

[0149] Component d) (dispersing agent) of the adjuvant combination is preferably selected from the group comprising alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a) [ka]

[0150] In the formula, R is a C1 to C4 fragment, preferably a C3 to C4 fragment, and more preferably a C4 fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably consisting of 15 to 35 PO units, and more preferably consisting of 20 to 30 PO units; B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO-) units (Formula III-c) with 0-10 propylene glycol (PO) units, preferably consisting of 20-40 EO units with 0-8 PO units, more preferably consisting of 30-40 EO units with 0-5 PO units. [ka]

[0151] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are as follows: [Table 8]

[0152] and compounds of general formula (IIId) RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId) wherein the individual groups and indices have the following definitions: R and R' are independently hydrogen, a linear C1- to C5-alkyl group or a branched C3- or C4-alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; wherein one group n or m has the meaning of 2 and the other group n or m has the meaning of 3).

[0153] In the context of the present invention, a straight-chain C1- to C5-alkyl group is understood to mean a methyl, ethyl, n-propyl, n-butyl or n-pentyl group.

[0154] In the context of the present invention, a branched C3- or C4-alkyl group is understood to mean an isopropyl, isobutyl or tert-butyl group.

[0155] In a preferred embodiment, the R and R' groups are independently selected from the group consisting of methyl, n-butyl, and hydrogen.

[0156] In an even more preferred embodiment, the R and R' groups are independently selected from the group consisting of n-butyl and hydrogen.

[0157] Regarding the arrangement of polyethylene units and polypropylene units, (a) m may take the value 2 and n may take the value 3, (b) Alternatively, m may take the value 3 and n may take the value 2.

[0158] Configuration (b) where m=3 and n=2 is preferred.

[0159] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of formula (IIId), in which m is 3, n is 2, x is 5 to 80; y is 5 to 80; R is n-butyl or hydrogen, and R' is hydrogen.

[0160] The solvent g) used with the adjuvant combination is further preferably selected from a compound or mixture of compounds represented by formula 4, wherein: y=1~5 A, B = independently of each other H or linear C1-C4 alkyl; M=H; or g) is selected from a compound or mixture of compounds represented by formula 4, wherein: y=1~5 A and B are H or linear C1-C4 alkyl M=C1-C2-alkyl; However, this does not include 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0161] Even more preferably, g) is selected from compounds represented by formula 4, wherein: y=1~3 A, B = H or methyl independently of each other; M = methyl; except for 1,2-propylene glycol, which is expressly excluded from the definition under g).

[0162] Most preferably, g) is selected from the group comprising dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol.

[0163] In a preferred embodiment, the solvent g) according to the present invention can occur in a mixture. The mixture of any one of g) can be present in a ratio ranging from 1:50 to 50:1, preferably in a ratio ranging from 1:25 to 25:1, more preferably in a ratio ranging from 1:10 to 10:1, for example, 1:10, 1:8, 1:6, 1:5, 1:2, 1:1, 2:1, 5:1, 6:1, 8:1 or 10:1. Yet another preferred embodiment comprises a mixture of any one of g) in a ratio ranging from 1:8 to 1:1, or in a ratio ranging from 1:1 to 8:1.

[0164] A preferred embodiment of the present invention is an adjuvant combination having a ratio of c) to d) (in each case by mass) of 3:1 to 1:3, preferably 2:1 to 1:2, more preferably 1.3:1 to 1:1.3.

[0165] The proportions of the adjuvant combination based on the weight of the total formulation are preferably as follows: c)1~40% by weight d) 1~40% by weight, More preferably c)5~35% by weight d) 5 to 35% by weight, and Even more preferably c)15~30% by weight d) 10-30% by weight.

[0166] The application rate of the formulation according to the present invention can be varied within a relatively wide range.It depends on each active ingredient and its content in the composition.The application volume of the formulation according to the present invention in the aqueous spray solution can also be varied within a relatively wide range, which means that the applicable spray volume can be varied from 10 to 500 l / ha.

[0167] The compositions according to the invention can be used to distribute insecticidal active ingredient mixtures on plants and / or their habitats in a particularly advantageous manner.

[0168] The composition according to the present invention can be used to treat any plant and plant part.In this context, plants are understood to include any plant and plant population, for example, desirable and undesirable wild plants or crop plants (including naturally occurring crop plants).Crop plants can be plants that can be obtained by conventional breeding and optimization methods, or by biotechnology and genetic engineering methods, or a combination of these methods, including transgenic plants, including plant cultivars that can or cannot be protected by plant breeder's rights.Plant parts are understood to mean all parts and organs of above-ground and underground plants, such as shoots, leaves, flowers, and roots, and examples include leaves, needles, stalks, stems, flowers, fruiting bodies, fruits, and seeds, as well as tubers, roots, and rhizomes.Plant parts also include harvested materials, and vegetative and reproductive propagation materials, such as cuttings, tubers, rhizomes, shoots, and seeds.

[0169] Preferably, the formulations according to the invention are used by spray application against animal pests of the following pest families: For example, in crops such as citrus fruits, pome fruits, stone fruits, leafy vegetables, root and tuberous vegetables and ornamental plants, from the family of woolly aphids (Pemphigidae), Eriosoma spp., Pemphigus spp. are preferred.

[0170] For grapes, nuts and citrus fruits, insects from the grapevine lice (Phylloxeridae) family to phylloxera spp. are preferred.

[0171] For example, in crops such as pome fruits, stone fruits, citrus fruits, vegetables, potatoes, and tropical crops, psyllids from the family Psylla (Psyllidae) are preferred, including Psylla spp., Paratrioza spp., Tenalaphara spp., Diaphorina spp., and Trioza spp.

[0172] For example, in perennial crops such as citrus fruits, pome fruits, stone fruits, olives, grapes, coffee, tea, tropical crops, ornamental plants, and vegetables, insects from the family of scale insects (Coccidae) such as Ceroplastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., and Coccus spp. are preferred.

[0173] For example, in crops such as citrus fruits, pome fruits, stone fruits, almonds, pistachios, nuts, olives, tea, ornamental plants, grapes and tropical crops, from the family of scale insects (Diaspididae) Quadraspidiotus spp., Aonidiella spp., Lepidosaphes spp., Aspidiotus spp., Aspis spp., Diaspis spp., Parlatoria spp., Pseudaulacaspis spp., Unaspis spp., Pinnaspis spp. spp.), and up to Selenaspidus spp. are preferred.

[0174] For citrus fruits, pome fruits and stone fruits, insects from the family of scale insects (Ortheziidae) up to Orthezia spp. are preferred.

[0175] For example, in crops such as citrus fruits, stone and pome fruits, tea, grapes, vegetables, ornamental plants and tropical crops, from the family of mealybugs (Pseudococcidae) Pericerga, Pseudococcus spp., Planococcus spp., Dysmicoccus spp. are preferred.

[0176] Furthermore, in crops such as vegetables, melons, potatoes, tobacco, soft fruits, citrus fruits, ornamental plants, cotton, soybeans and tropical crops, whiteflies from the family of whiteflies (Aleyrodidae) are preferred, including Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes spp., Dialeurodes spp., and Parabemisia myricae.

[0177] Furthermore, from the family of aphids (Aphidae), Myzus spp. in tobacco, stone fruits, soft fruits, fruit vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamental plants, and spices; In vegetables, the pea aphid (Acyrthosiphon onobrychis), Aphis spp. in tobacco, citrus fruits, pome fruits, stone fruits, melons, strawberries, soft fruits, fruit vegetables, leafy vegetables, tubers, stem and root vegetables, ornamental plants, potatoes, pumpkins, and spices; On strawberries, the rose aphid (Rhodobium porosum) In leafy vegetables, lettuce aphid (Nasonovia ribisnigri), Macrosiphum spp. in ornamental plants, potatoes, leafy and fruit vegetables, and strawberries; In hops, Phorodon humuli, In leafy vegetables, the radish aphid (Brevicoryne brassicae) Toxoptera spp. in citrus fruits, stone fruits, almonds, nuts, and spices; Aulacorthum spp. in citrus fruits, potatoes, fruiting and leafy vegetables, In vegetables, Anuraphis cardui, In sunflowers, Brachycaudus helycrisii, On vegetables, the pea aphid is preferred.

[0178] Likewise, in crops such as, for example, fruit, cotton, grapes, tea, nuts, tropical crops, ornamentals, conifers, tobacco, spices, vegetables, soft fruits, melons, citrus fruits and potatoes, from the family of thrips (Thripidae) Anaphothrips spp., Baliothrips spp., Caliothrips spp., Frankliniella spp., Heliothrips spp., Hercinothrips spp., Rhipiphorothrips spp., Scirtothrips spp., Kakothrips spp., Selenothrips spp.) and Thrips spp. are preferred.

[0179] Furthermore, in crops such as vegetables, melons, potatoes, nuts, ornamentals, etc., preference is given to insects from the families of the leaf miner flies (Agromyzidae) and root maggot flies (Anthomyiidae), including Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., and Pegomyia spp.

[0180] For example, in crops such as citrus fruits, berries, grapes, potatoes, vegetables, ornamentals, conifers, melons, soft fruits, tea, nuts, rice and tropical crops, from the families of leafhoppers (Cicadellidae) and planthoppers (Delphacidae), such as Circulifer spp., Dalbus spp., Empoasca spp., Erythroneura spp., Homalodisca spp., Iodioscopus spp., Laodelphax spp., Nephotettix spp., Nilaparvata spp., Oncometopia spp. spp.), and up to Sogatella spp. are preferred.

[0181] From the family of leaf-miner moths (Gracillariidae), For example, in crops such as pome fruits, stone fruits, grapes, nuts, citrus fruits, conifers, potatoes, and coffee, Caloptilia spp., Gracilaria spp., Lithocolletis spp., Leucoptera spp., Phtorimaea spp., and Phyllocnistis spp. are preferred.

[0182] From the family of gall gnats (Cecidomyiidae), In crops such as citrus fruits, pome fruits, stone fruits, vegetables, potatoes, spices, soft fruits, conifers, and hops, Contarinia spp., Dasineura spp., Diplosis spp., Prodiplosis spp., Thecodiplosis spp., Sitodiplosis spp., and Haplodiplosis spp. are preferred.

[0183] Similarly, from the family of fruit flies (Tephritidae), In crops such as vegetables, soft fruits, melons, pome and stone fruits, ornamentals, potatoes, grapes, tropical crops, citrus fruits, olives, Anastrepha spp., Ceratitis spp., Dacus spp., and even Rhagoletis spp. are preferred.

[0184] Furthermore, from the families of spider mites (Tetranychidae) and eriophyid mites (Eriophydae): In crops such as vegetables, potatoes, ornamental plants, citrus fruits, grapes, and conifers, two-spotted spider mites (Tetranychus spp.), round spider mites (Panonychus spp.), and aculops spp. are preferred.

[0185] The inventive treatment of plants and plant parts with the compositions according to the invention is carried out directly or by applying the composition to their surroundings, environment or storage space by customary treatment methods, for example by irrigation, immersion, spraying, evaporation, atomization, scattering, painting, and in the case of propagation material, in particular seeds, by applying one or more coatings.

[0186] Preferably, the plants to be treated are selected from the group consisting of cotton, soybeans, tobacco, vegetables, spices, ornamentals, conifers, citrus plants, fruits, tropical crops, nuts and grapes.

[0187] Preferably, the compositions according to the invention act against pests from the families of woolly aphids, grape lice, psyllids, scale, square scale, leaf scale, mealybugs, whiteflies, aphids, thrips, leafhoppers, planthoppers, leaf miner flies, gall flies, fruit flies, leaf miner moths, spider mites and eriophyid mites.

[0188] It has been found that the composition according to the invention can be produced by a process having the following steps: 1) Mixing components (a) to (h) followed by homogenization and bead milling. Relevant equipment for homogenization and bead milling is known to those skilled in the art.

[0189] This process also forms part of the subject matter of the present invention.

[0190] Finally, it has been found that the composition according to the present invention has a very good compatibility with the application of existing active pesticide ingredients to plants and / or their habitats.This process also forms part of the subject matter of the present invention.The following examples will explain the subject matter of the present invention without limiting it. [Table 9]

[0191] The following tests and methods are applicable: The rotational viscosity is measured according to CIPAC MT 192. A stable and convenient formulation is predicted to exhibit a viscosity in a medium range to enable easy emptying and cleaning of the bottle.

[0192] The rheology was measured using a Bohlin Gemini Rheometer. The measured values of G’ (elastic modulus), G’’ (viscous modulus) and phase angle were measured at different frequencies (0.01 - 5 Hz) at room temperature using a frequency sweep routine with either strain control or stress control, and the values were reported at 0.5 Hz. It is generally recognized by those skilled in the art that for a stable formulation, a small phase angle and large value of G’ (> G’’) indicate a high probability, while for a formulation with low stability, a large phase angle and small value of G’ (< G’’) indicate a high probability.

[0193] The particle size is determined by laser diffraction using a CIPAC MT 187 Malvern Mastersizer, medium: propylene glycol), or by using an optical microscope (40x magnification). A stable and convenient formulation is predicted to contain small particles to ensure good storage stability in the concentrate and good suspension stability in the aqueous diluent.

[0194] The suspension stability is evaluated according to a simplified method by CIPAC MT 180, measured in a 2% aqueous dilution in CIPAC D water, and determined after a standing time of 1 hour. A stable and convenient formulation is predicted to show no or very little precipitate formation at the bottom of the test container to ensure uniform application of the spray solution.

[0195] Storage tests are carried out at different temperatures, e.g., 0 °C, 20 °C, 30 °C, 40 °C, 54 °C, or a thaw-freeze cycle (or temperature cycle; continuous temperature change from -15 °C to +30 °C and reversal within one week) over a given number of weeks (w).

[0196] The redispersibility of the sample is determined qualitatively by shaking the sample and then evaluating the base of the sample container.

[0197] The formulation properties are evaluated in the same way as in DIN 10964 "Sensory analysis - Simple descriptive test". For this purpose, the sample to be examined is examined visually and, if necessary, by shaking and tilting, for shape, state of matter and color, as well as for additional characteristics (in particular, for example, lumps, caking, sediment formation, subsequent thickening, marbling of the sediment, etc.).

[0198] The phase separation immediately after storage is reported as the sediment fraction, calculated from the quotient H1 [the level of the interfacial layer between the sediment phase and the supernatant] divided by H0 [the total filling height of the sample], or as in this case as the supernatant fraction: Precipitate fraction = (H1 / H0)*100[%] or Supernatant fraction = 100 - sediment content [%] A stable and convenient formulation is expected to exhibit little or no phase separation upon prolonged storage at elevated temperatures and be easily rehomogenized. Significant phase separation after short storage times indicates limited storage stability and a significant tendency for precipitates to form, even if difficult to disperse, during storage.

[0199] Example I All experimental formulation ingredients listed in Table I are combined in a suitable container and homogenized by stirring. This is followed by bead milling (e.g., Dispermat SL50, 80% 2 mm beads, 4000 rpm, circular milling) until a particle size of 10-15 μm is reached (determined by microscopy). The resulting formulations are analyzed, for example, by suspension stability and rotational viscosity. This is followed by storage testing at elevated temperatures, followed by a quantitative assessment of phase separation after storage. [Table 10]

[0200] Discussion: As shown in Table I, the formulations prepared according to Examples I-1 to I-3 exhibit suitable particle sizes and excellent suspension stability, along with low to moderate viscosities and very little phase separation, after two weeks of storage under different conditions. The formulation prepared according to Example I-4 is not in accordance with the present invention, as it exhibits high viscosity in combination with coarse particles. In this case, high viscosity had already accumulated after a few minutes of grinding, which stopped the grinding process, so preparation of a sample with a smaller particle size was not continued.

[0201] Example II All experimental formulation ingredients listed in Table II are combined in a suitable container and homogenized by stirring. This is followed by bead milling (e.g., Dispermat SL50, 80% 2 mm beads, 4000 rpm, circular milling) until a particle size of 10-15 μm is reached (determined by microscope). The resulting formulations are analyzed, for example, by suspension stability, rotational viscosity, and rheology (determination of phase angles G' and G''). This is followed by storage testing at elevated temperatures, followed by a quantitative assessment of phase separation after storage. [Table 11] [Table 12]

[0202] All formulations according to the present invention exhibit viscosities of less than or about 1000 mPa*s at 7.5 1 / s, which can be considered practically useful (Table 1, Examples II-1; II-3 to II-5; II-8; II-9). All examples exhibit small phase angles of 30° or thereabouts, which is attributable to good storage stability. However, all examples according to the present invention exhibit an elastic modulus G' of about 100 Pa or less, and a corresponding viscous modulus G'' significantly below G'. With regard to phase separation, all formulations according to the present invention exhibit no or only low levels of supernatant after 4, 8, or 16 weeks of storage at either 20°C / room temperature, 40°C, or temperature cycling. Thus, a maximum phase separation of 0-10% was observed after 8 or 16 weeks of storage at 40°C, respectively. Formulations containing high amounts of propylene glycol are not according to the invention, as they exhibit relatively high viscosities and / or relatively high levels of supernatant, up to 14% (Table I, Examples II-2; II-6; II-7).

[0203] Example III To test different levels of carrier fluid (g), adjuvant (h), and water-insoluble filler (f), all formulation components from the experiments described in Table III were combined in a suitable container and homogenized by stirring. This was followed by bead milling (e.g., Dispermat SL50, 80% 2 mm beads, 4000 rpm, circular milling) until a particle size of 10-15 μm was reached (determined by microscope). The resulting formulations were analyzed for suspension stability, rotational viscosity, and rheology. Storage testing at elevated temperatures was then performed, followed by a quantitative evaluation of suspension stability after storage. [Table 13]

[0204] Discussion: The formulations prepared according to Examples III-1 and III-2 exhibit moderate viscosity and good suspension stability even after storage. Furthermore, Example III-1 exhibits a small phase angle, an elastic modulus G' of about 100 Pa or less, and a corresponding viscosity modulus G'' significantly lower than G'. Therefore, III-1 and III-2 are examples according to the present invention. The formulation prepared according to Example III-3 exhibits a slightly higher viscosity and a similar G' compared to III-1, which may be due to the increased amount of propylene glycol in the formulation. The formulations prepared according to Examples III-4 and III-5 exhibit increased viscosity and elastic modulus G', which may also be due to the increased amount of propylene glycol in the formulation.

[0205] Example IV To test various combinations of at least one active ingredient that is solid at room temperature a) and at least one active ingredient b), without changing the formulation, suitable active ingredients were selected as shown in Table IV, mixed together under stirring, and homogenized. Subsequently, bead milling was performed (Dispermat SL50, 80% 2 mm beads, 4000 rpm, 40 minutes of circulation milling), and the resulting formulations were analyzed, for example, by suspension stability, rotational viscosity, and particle size evaluation. Subsequently, storage tests were performed at high temperatures, and the samples were further evaluated, including determining phase separation after storage. [Table 14]

[0206] Discussion: Examples IV-1 to IV-7 show rotational viscosities of 850-1500 mPa*s at 7.5 1 / s combined with particle size d90 of 3-6 μm (Malvern results), indicating excellent suspension stability after 1 hour. After 2 weeks of storage, almost no phase separation was detected, and only slight changes in particle size were observed (the exception being Example IV-4, which showed some crystal growth after storage at 54°C), thereby demonstrating stable formulations according to the present invention. Furthermore, the suspension stability after storage is continuously good, and in some cases even excellent.

[0207] [Example V] Epidermal penetration by flupyradifurone and compound I-2 Testing Procedure: This test measures the penetration of an active ingredient through enzymatically isolated cuticle of apple tree leaves.

[0208] Leaves were used that were cut from developed apple trees and isolated by the method described by Schonherr and Riederer (Schonherr, J., Riederer, M. (1986)). Only the upper leaf epidermis, free of stomata and hairs, was used.

[0209] For membrane transport studies, the cuticle membrane thus obtained is placed in a stainless steel diffusion cell (=transport chamber). For this purpose, the epidermis is centered on the silicone-greased edge of the diffusion cell using tweezers and sealed with a similarly greased ring. This orientation is chosen so that the morphological outer side of the epidermis faces the outside, i.e., toward the air, while the original inner side faces the inside of the diffusion cell. The diffusion cell is filled with water or a mixture of water and solvent, buffered to a physiologically relevant pH of 5.5. The medium inside the diffusion cell is considered to mimic the apoplast, i.e., the natural absorption medium within the leaf. This method is well suited for systemic and mechanistic studies aimed at understanding the effects of formulations, adjuvants, and solvents on the penetration of crop protection compositions.

[0210] To determine penetration, 5 μl of the spray solution containing the active ingredients flupyradifurone and I-1 in the specific formulations (see Table V) below are applied to the outer surface of the cuticle. The active ingredient concentrations correspond to the actual customary field application rates. To prepare the spray solution, the given amounts of the corresponding ingredients are poured into tap water and homogenized by mixing.

[0211] After application of the spray solution, the water is allowed to evaporate. The chambers are then inverted and placed in a thermostatic chamber, where air of a specified humidity and temperature is sprayed onto the outer surface of the epidermis. Thus, the desired penetration is achieved at a relative humidity of 56% and a temperature of 25°C. Samples are taken at regular intervals using an autosampler, and the content of the penetrated active ingredient is measured by HPLC. The reported values ​​are the average of 5 to 10 individual measurements. [Table 15]

[0212] Evaluation of the experiment: The two active substances tested, flupyradifurone and I-2, were used by themselves and without additives. When used without any additives, they exhibit little, if any, epidermal penetration (Table V, entry 1) The presence of diammonium hydrogen phosphate (DAHP), especially Antarox B / 848 Application of the active ingredients under the skin independently resulted in improved epidermal penetration of both tested active ingredients. (Table V, entries 2-3) Antarox B / 848 and DAHP are combined. As soon as it is used, a maximum osmotic potential is found, which is the individual potential for both active ingredients in the formulation. The additive effect of the different solvents (Table V, entry 4) was observed. Entries 5-8) were present with the combination of Antarox B / 848 and DAHP. A very similar effect can be observed when flupyradifurone is present. whereas I-2 penetration is slightly reduced but still at very high levels. and certainly better than Antarox B / 848 or DAHP alone. In one aspect, the present invention provides the following. [Item 1] a) at least one active ingredient that is solid at room temperature; b) at least one active ingredient other than a) that is soluble in an organic solvent; c) at least one ammonium salt; d) at least one dispersant from the class of alkyl propoxylate ethoxylates; e) optionally one or more surfactants; f) at least one water-insoluble filler; g) at least one solvent selected from compounds represented by formula 4

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Claims

1. a) tetraniliprole, cyantraniliprole, ethiprole, thiacloprid, spirotetramat and compounds of formula (I-2), 【Chemistry 2】 at least one active ingredient selected from the group consisting of: b) at least one active ingredient selected from the group consisting of flupyradifurone and acetamiprid; c) at least one ammonium salt selected from the group consisting of ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP); d) Alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a) 【Transformation 5】 wherein R is a C1-C4 alkyl fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units with 0-10 propylene oxide (PO) units (Formula III-c), 【Transformation 6】 and alkylpolypropylene glycol-polyethylene glycol compounds of general formula (IIId): R-O-(C ｍ H ２ｍ O) ｘ -(C ｎ H ２ｎ O) ｙ -R'(--Id) (In the formula, R and R′ are independently hydrogen, straight chain C １ - C ５ -Alkyl group or branched C ３ - or C ４ - is an alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; in which one group n or m has the meaning 2 and the other group n or m has the meaning 3, e) a surfactant combination comprising a first surfactant selected from the group of sodium salts of copolymers of maleic acid and olefins, and a second surfactant selected from salts of sulfated formaldehyde condensation products with alkylaromatics; f) at least one water-insoluble filler selected from the group of fumed silicas; g) at least one solvent selected from the group consisting of dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, and dipropylene glycol and h) additional adjuvants; A composition comprising: A composition in which the active ingredient a) is insoluble or sparingly soluble in the selected solvent g).

2. 10. The composition of claim 1, wherein the components are present as follows: a) 1-30% by weight b) 1-20% by weight c) 1-40% by weight d) 1-40% by weight e) 10% by weight or less f) 0.1-15% by weight h) 1-20% by weight g) Up to 1 litre.

3. 10. The composition of claim 1, wherein the components are present as follows: a) 2-15% by weight b) 1-12% by weight c) 15-30% by weight d) 10-30% by weight e) 0.5-2.5% by weight f) 1-10% by weight h) 2.5-17.5% by weight g) Up to 1 litre.

4. a) A compound having the formula (I-2) having the following structure: 【Transformation 8】 b) flupyradifurone, c) at least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP); d) Alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a) 【Chemistry 9】 wherein R is a C1-C4 alkyl fragment; A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units with 0-10 propylene oxide (PO) units (Formula III-c), 【Chemistry 10】 and alkylpolypropylene glycol-polyethylene glycol compounds of general formula (IIId): R-O-(C ｍ H ２ｍ O) ｘ -(C ｎ H ２ｎ O) ｙ -R'(--Id) wherein the individual groups and indices have the following definitions: R and R′ are independently hydrogen, straight chain C １ - C ５ -Alkyl group or branched C ３ - or C ４ - is an alkyl group, m is 2 or 3; n is 2 or 3; x is 5 to 150, and y is 5 to 150; in which one group n or m has the meaning 2 and the other group n or m has the meaning 3, e) a surfactant combination comprising a first surfactant selected from the group of sodium salts of copolymers of maleic acid and olefins, and a second surfactant selected from salts of sulfated formaldehyde condensation products with alkylaromatics; f) at least one filler selected from the group consisting of fumed silica; g) at least one solvent selected from the group consisting of dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, and dipropylene glycol; and h) additional adjuvants; The composition of any one of claims 1 to 3, comprising:

5. 5. Use of a composition according to any one of claims 1 to 4 for controlling insects.

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