Formulation of an insecticide containing a glycol ether-based solvent

Abstract

The present invention relates to an insecticidal active ingredient formulation comprising at least one active ingredient or a combination of active ingredients in solid form having good storage stability at high and low temperatures and high active ingredient penetration, a method for producing the same, and its use for applying the active ingredients present.

Description

[Technical Field]

[0001] The present invention relates to an insecticidal active ingredient formulation containing a solid-form active ingredient or combination of active ingredients having high active ingredient permeability that provides good storage stability at high and low temperatures and high efficacy, a method for producing the same, and the use thereof for the application of the existing active ingredient. The present invention further relates to adjuvant combinations for an insecticidal active ingredient formulation containing a solid-form active ingredient or combination of active ingredients for improving the permeability of the active ingredient or combination of active ingredients. [Background technology]

[0002] To exhibit biological efficacy, systemic pesticide active ingredients, particularly systemic insecticides, require formulations that allow for uptake of the active ingredient by the plant / target organism. The best effect can be achieved when the corresponding active ingredient is diluted in an aqueous solution for use and / or is already dissolved in a concentrated solution, ensuring that high concentrations of the active ingredient are available at any time.

[0003] This is always the case when the active ingredient or combination of active ingredients is formulated as an emulsion (EC) or a soluble solution (SL), but the availability of the dissolved and suspended active ingredients is limited by the solubility equilibrium.

[0004] Furthermore, the physiological activity can be further enhanced by optionally adding a suitable adjuvant / penetrating agent.

[0005] As described above, in formulations such as suspensions (SC) and / or oily suspensions (OD), the active ingredient or combination of active ingredients is in solid, particulate form rather than dissolved form, and therefore these active ingredients in the formulation typically do not have good bioavailability. Here, it is possible to enhance the physiological activity essentially only by adding a suitable adjuvant / penetrating agent, but even so, this results in a decrease in physiological activity compared to the EC or SL formulations described above.

[0006] Pesticide active ingredients are known to differ from one another in terms of their physicochemical properties, such as solubility in water, solvents, and / or oils, melting and boiling points, polarity, and molar mass. These properties affect the formulation properties of the active ingredient. For example, many known pesticide active ingredients have high melting points, allowing them to withstand thermal stress, such as that generated during the manufacture of suspensions (caused by grinding). In contrast, pesticide active ingredients with low melting points have difficulty withstanding such manufacturing conditions, and softening or melting of the pesticide active ingredient is expected at relatively high temperatures, meaning that they can only be manufactured as storage-stable suspensions to a very limited extent. However, when the active ingredient is no longer in crystalline form, the physical and sometimes chemical stability of the formulated product decreases significantly, often rendering it impractical.

[0007] Furthermore, organic substances are known to have different water solubility, and this water solubility can be pH-dependent, for example, through salt formation, depending on their chemical properties.

[0008] A key characteristic of a stable suspension is its physical and chemical storage stability over a long period (12-24 months) and a wide temperature range (0-54°C). This wide temperature range is advantageous because it allows a single formulation with the same active ingredient or combination of active ingredients to be used in different climatic regions.

[0009] The storage stability of suspensions is characterized in particular by the fact that the containers of these suspensions undergo little to no phase separation during storage. Further parameters relating to the stability of suspensions include, for example, the stability of the dispersion in the concentrate, in the presence or absence of aggregates in the concentrate.

[0010] WO2011 / 029552 describes pesticide formulations containing alkyl polypropylene glycol-polyethylene glycol (e.g., Antarox B / 848), in which these surfactants are used as emulsifiers and / or penetrants for the active ingredients of pesticides.

[0011] Furthermore, WO2003 / 000053 describes certain alkyl polypropylene glycol-polyethylene glycols, such as Atlas G5000, as dispersants for organic crop protection products in oil.

[0012] The use of ammonium salts to enhance the action of pesticide active ingredients is known in the literature. For example, WO2011 / 131623 (US2011 / 0281727A1, Fischer et al.) describes insecticide and / or herbicide formulations based on heterocyclic tetramic acid that exhibit improved efficacy in the presence of ammonium salts. Furthermore, WO2007 / 068428 describes the activity-enhancing effect of phenyl-substituted cyclic keto-enols in the presence of ammonium salts. WO2011 / 131623 relates to a single active ingredient selected from the group of substances of formula [I], in combination with an organic or inorganic ammonium or phosphonium salt, and to the use thereof in aqueous spray solutions in or without a suitable penetrating agent. Proceeding from the teachings of WO2011 / 131623, experts cannot draw any conclusions regarding formulations with further combinations of active ingredients, or the physical and chemical stability of these mixture formulations. Suitable penetrating agents are described in broad terms in paragraphs

[0111] to

[0171] and are generally claimed in

[0178] , but only rapeseed oil methyl ester is cited as an example of a vegetable oil derivative, and only Genapol LRO is cited as an example of an anionic alcohol ether sulfate. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] WO2011 / 029552 [Patent Document 2] WO2003 / 000053 [Patent Document 3] WO2011 / 131623 [Patent Document 4] WO2007 / 068428

Summary of the Invention

Problems to be Solved by the Invention

[0014] The formulation having good penetration of the insoluble active ingredient according to the present invention is not described or suggested in WO2011 / 131623.

[0015] Oil-based formulations containing ammonium salts are also known in the literature. For example, WO2008 / 151725 describes an adjuvant composition based on oil in which ammonium salts are in a dispersed form. Furthermore, EP2193712A1 describes an oil-based pesticide formulation in which ammonium salts are in a dispersed form. However, there is no description at all about the suspension of ammonium salts in a water-miscible solvent.

[0016] However, in summary, none of the above-cited documents, either individually or comprehensively, points out that an alkyl polypropylene glycol - polyethylene glycol, such as Antarox B / 848, can be used as an effective dispersant for inorganic ammonium salts in a high loading amount in a polar water-soluble solvent such as glycol ether, especially in combination with a suspended active ingredient.

[0017] The soluble aqueous concentrates of tetramic acid derivatives are known from the prior art, for example WO2009 / 115262. Due to solubility problems, these cannot be combined with specific crop protection products and formulation components. Furthermore, these aqueous SL formulations generally have a high pH value, which also leads to incompatibility with specific base-sensitive crop protection products and formulation components.

[0018] Therefore, the problem addressed is to develop a stable formulation consisting of a suspended active ingredient or a combination of suspended active ingredients, having good bioavailability and penetration ability of the suspended active ingredient or the combination of suspended active ingredients, and having good storage stability at both high and low temperatures. The active ingredient is preferably an insecticide.

Means for Solving the Problem

[0019] This problem has been solved by the following preparations containing an active ingredient or a combination of active ingredients, an ammonium salt, and a glycol ether as a solvent.

[0020] Therefore, the present invention provides a. At least one active ingredient that is solid at room temperature, preferably insoluble or slightly soluble in the selected solvent f), b. At least one ammonium salt, c. At least one dispersant from the group of alkyl propoxylate ethoxylates (e.g., according to Formula III-a or III-d), d. Optionally, one or more surfactants, e. At least one water-insoluble filler, f. At least one solvent from the group of glycol ethers, and g. Optionally, further adjuvants and provides an insecticidal composition.

[0021] In a preferred embodiment, component d) is essential.

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

[0023] In another embodiment, components d) and g) are essential.

[0024] Furthermore, the composition in a preferred embodiment does not contain water or is essentially free of water.

Brief Description of the Drawings

[0025] [Figure 1] Shows the X-ray diffraction pattern of Modification A.

Modes for Carrying Out the Invention

[0026] According to the present invention, it has been found that the corresponding composition has high stability.

[0027] In the present invention, in formula (I), for example, the group that may be substituted may be monosubstituted or polysubstituted unless otherwise specified, and in the case of polysubstituted groups, the substituents may be the same or different.

[0028] Furthermore, within the preferred scope described in the present invention, different preferred levels should be understood to be able to be combined with one another in permutations, but in any case the same level of preference, in particular the most preferred embodiment / preferred level in each case, should be combined with one another, and in fact, they are disclosed in such combinations.

[0029] The composition described in this application, consisting only of essential components (and not optional components), should also be considered to be disclosed in the same manner.

[0030] In the context of this invention, room temperature means a temperature of 20°C to 25°C unless otherwise specified.

[0031] Components a to g are further defined below.

[0032] a. Active ingredients that are solid at room temperature The active ingredient, which is solid at room temperature, is preferably selected from the group consisting of insecticides, herbicides, and fungicides. More preferably, the selected active ingredient is insoluble or slightly soluble in the selected solvent f). Even more preferably, it is an insecticidal active ingredient that is solid at room temperature and insoluble or slightly soluble in the selected solvent f).

[0033] In the context of the present invention, a slightly soluble or insoluble active ingredient is an active ingredient that is solid at room temperature and has a solubility in a selected solvent f) at 20°C of preferably 5 g / L or less, more preferably 4 g / L or less, even more preferably 2.5 g / L or less, and particularly preferably 1 g / L or less.

[0034] More preferably, the active ingredient is selected from the group comprising diamide insecticides (brofuranilide, chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyhalodiamide, flubendiamide, tetrachlorantraniliprole, and tetraniliprole), spinosins (IRAC group 5), those referred to as "mectins" (e.g., abamectin, emamectin benzoate, milbemectin; IRAC group 6), ethiprole, triflumulone, β-cyfluthrin, deltamethrin, and tetronic acid and tetramic acid derivatives (IRAC group 23, e.g., compounds of formulas I and II described below).

[0035] In a preferred embodiment, component a) in the composition according to the present invention is a keto-enol based on tetramic acid, preferably a compound of formula (I), [ka]

[0036] During the ceremony, W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine, or fluorine. X is a C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, or iodine. A, B, and the carbon atoms to which they are bonded are C3-C6-cycloalkyl groups which may be substituted with C1-C4-alkyl- or C1-C4-alkoxy-C1-C2-alkyl groups, and together with the carbon atoms to which they are bonded, they form a 5-membered or 6-membered ketal. G is either hydrogen (a) or one of the following groups: [ka]

[0037] During the ceremony, E is a metal ion or an ammonium ion. M is oxygen or sulfur, R 1These are linear or branched C1-C6 alkyl groups. R 2 These are linear or branched C1-C6 alkyl groups.

[0038] Particularly preferred and usable are tetramic acid derivatives of the above formula (I) in which the group is 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 atoms to which they are bonded are more preferably saturated C6-cycloalkyl groups substituted with alkylenedioxy groups, and together with the bonded carbon atoms, they form a 5-membered or 6-membered ketal. G is more preferably hydrogen (a) or one of the following groups: [ka]

[0039] During the ceremony, M is oxygen, E is a single metal ion equivalent or ammonium ion (specifically sodium or potassium), R 1 More preferably, it is a linear or branched C1-C4 alkyl group. R 2 The more preferably, the C1-C4 alkyl group is a linear or branched C1-C4 alkyl group.

[0040] Specifically useful are the tetraminic acid derivatives of the above formula (I) where G = hydrogen (a).

[0041] Similarly, a particularly useful example is the tetramic acid derivative of the above formula (I) where G=E(d).

[0042] Particularly preferred and useful are tetramic acid derivatives of the above formula (I), in which the group is defined as follows: [ka] [Table 1]

[0043] In a particularly preferred embodiment, component a) is a compound of the following formula. [ka]

[0044] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure. Its crystal structure and further physical data were measured as follows: Sample preparation: Compound I-2(C 19 H 22 ClNO4 (363.84 g / mol) was crystallized from methanol and dried at room temperature to obtain transformation A.

[0045] The I-2 transformation A can be characterized by X-ray powder diffraction based on the corresponding diffraction pattern recorded using Cu-Kα1 radiation (1.5406 Å) at 25°C (Figure 1).

[0046] Transformation 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 Figure 1.

[0047] Transformation A according to the present invention can also be characterized by the X-ray diffraction pattern shown in Figure I.

[0048] Crystallographic studies of single crystals of transformation A have revealed that its crystal structure is monoclinic. Its unit cell has a P21 / c space group.

[0049] Table 2: Crystallographic properties of transformation A [Table 2]

[0050] a, b, c = lengths of the sides of the unit cell α, β, γ = angles of the unit cell Z = number of molecules in the unit cell.

[0051] Table 2 a / b: Crystallographic data of modification A / Reflection [°2θ] [Table 3]

[0052] The polymorph of modification A of I-1 can be determined by IR spectroscopy using the corresponding spectrum recorded at 25 °C using a diamond ATR apparatus with a resolution of 4 cm -1 As shown in Table 2c, the modification A of the present invention exhibits at least 3, preferably at least 5, more preferably at least 7, and most preferably all of the bands.

[0053] Table 2c) IR band [cm -1 [Table 4]

[0054] In another embodiment, component a) comprises a tetramic acid of the following formula (II): [Chemical formula]

[0055] wherein 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 ​These are 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 These are hydrogen, halogen, C1-C6-alkyl, or C1-C6-alkoxy. V 3 is hydrogen or halogen, A, B, and the carbon atoms to which they are bonded are saturated C5-C6-cycloalkyl groups, in which one ring member is replaced by oxygen and which may be monosubstituted with C1-C8-alkyl, C1-C8-alkoxy, or C1-C6-alkyloxy-C1-C6-alkyl groups. G is either hydrogen (a) or one of the following groups: [ka]

[0056] During the ceremony, E is a metal ion or an ammonium ion. L is oxygen or resource, M is oxygen or sulfur, R 1 These are linear or branched C1-C6 alkyl groups. R 2 These are linear or branched C1-C6 alkyl groups.

[0057] Particularly preferred and useful are tetramic acid derivatives of the above formula (I) in which the group is defined as follows: W is more preferably hydrogen or methyl. X is more preferably chlorine or methyl, Y is more preferably hydrogen, V 1 This is more preferably fluorine or chlorine (specifically, fluorine or chlorine at position 4), V 2This is more preferably hydrogen or fluorine (specifically, fluorine at position 3), V 3 This is more preferably hydrogen or fluorine (specifically, fluorine at position 5), A, B, and the carbon atoms to which they are bonded are more preferably saturated C6-cycloalkyl groups in which one ring member is replaced by oxygen. G is more preferably hydrogen (a), or one of the following groups: [ka]

[0058] During the ceremony, E is more preferably a single metal ion equivalent or ammonium ion (specifically sodium or potassium), R 1 The more preferably is a linear or branched C1-C4 alkyl group. R 2 The more preferably, it is a linear or branched C1-C4 alkyl group.

[0059] Specifically useful are the tetraminic acid derivatives of the above formula (I) where G = hydrogen (a).

[0060] Similarly, a particularly useful example is the tetramic acid derivative of the above formula (I) where G=E(d).

[0061] Particularly preferred and useful are tetramic acid derivatives of the above formula (II) in which the group is defined as follows: [Table 5]

[0062] In another particularly preferred embodiment, a) is as follows: [ka]

[0063] b. Ammonium salts The ammonium salt is preferably selected from the group including water-soluble inorganic ammonium salts.

[0064] More preferably, b) is selected from the group consisting of ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP).

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

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

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

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

[0069] and compounds of general formula (IIId): [ka]

[0070] In the formula, each base and exponent has the following definitions: R and R' are independently hydrogen, a linear C1-~C5 alkyl group, or a branched C3- or C4-alkyl group; m is either 2 or 3; n is either 2 or 3; x is between 5 and 150; y is between 5 and 150. Here, n and m of one group mean 2, and n or m of the other group mean 3.

[0071] In the context of the present invention, a linear C1-~C5 alkyl group is understood to mean a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group.

[0072] In the context of this invention, branched C3-~C4 alkyl groups are understood to mean isopropyl groups, isobutyl groups, or tert-butyl groups.

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

[0074] In a more preferred embodiment, the R and R′ groups are independently selected from the group consisting of n-butyl groups and hydrogen.

[0075] Regarding the arrangement of polyethylene and polypropylene units, (a) We can assume that m is value 2 and n is value 3; or (b) We can assume that m is valued at 3 and n is valued at 2.

[0076] Preferably, configuration (b) is such that m=3 and n=2.

[0077] What is particularly desirable is, m is 3, n is 2, x is between 5 and 80. y is between 5 and 80. R is n-butyl or hydrogen, R′ is hydrogen. It is an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId).

[0078] d. A suitable surfactant d) in the context of the present invention is selected from the group including the following: d1) Polycarboxylate-type surfactants, e.g., hydrophobic modified comb polymers, e.g., polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or maleic anhydride copolymer with olefin (isobutylene or diisobutylene, etc.), acrylic acid and itaconic acid copolymer, methacrylic acid and itaconic acid copolymer, maleic acid or maleic anhydride copolymer with styrene, acrylic acid and methacrylic acid copolymer, acrylic acid and methacrylate copolymer, acrylic acid and vinyl acetate copolymer, styrene and methacrylic acid copolymer, styrene and methacrylic acid modified copolymer, maleic acid or maleic anhydride copolymer with acrylic acid, N-methyl fatty acids (e.g., C8-C 18 ) Sarcosinates, carboxylic acids, for example resin acids or fatty acids (for example, C8-C 18) or surfactants such as salts of such carboxylic acids. The copolymers described above may also be in the form of their salts, for example alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines. 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. d2) Surfactants selected from the group consisting of salts of sulfated formaldehyde condensation products with alkyl aromatics, e.g., MORWET D-425 (Akzo Nobel); OPARYL DT 120, OPARYL DT 201, OPARYL DT 530 (Bozzetto); TERSPERSE 2020 (Huntsman); and salts of sulfated formaldehyde condensation products with dityl ethers (e.g., BAYKANOL SL, Levaco); and salts of sulfated formaldehyde condensation products with cyclohexanone (e.g., LUCRAMUL DAC 210, Levaco), and d3) 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 Tembec; AGRINOL DN from Tembec. Selected from the group consisting of 19 and Agrinol C12, and lignosulfonates and their salts, d4) Surfactants selected from the group consisting of sulfated alkylaryl sulfonates and their salts, for example, alkylaryl sulfonates and their salts such as 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 d5) Surfactants of the group consisting of di- / tristyrylphenol ethoxylate phosphates and their salts, including 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, such as EMPIPHOS 03 D (Akzo Nobel); MULTITROPE 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).

[0079] More preferably, a suitable surfactant is selected from the group comprising surfactants d1), d2), d3), and d4).

[0080] More preferably, a suitable surfactant is selected from the group comprising surfactants d1), d2), and d3).

[0081] More preferably, the preferred surfactant is selected from the group comprising surfactants d1) and d2).

[0082] More preferably, suitable surfactants are selected from the group including surfactant d1).

[0083] Of particular preference are surfactants of the sodium salt of maleic acid-olefin copolymer (e.g., Geropon T / 36 / Solvay; Duramax D-305 / Dow); and the sodium salt of methacrylic acid-styrene copolymer (Tersperse 2700 / Huntsman; Atlox Metasperse 500S / Croda); in particular, group d1 including the sodium salt of maleic acid-olefin copolymer (e.g., Geropon T / 36).

[0084] Suitable surfactants, such as Tersperse 2700, are also listed in WO2008036865A2.

[0085] The above surfactants can be used individually or in combination, and preferred are combinations of a surfactant selected from the group of sodium salts of maleic acid and olefin copolymers with a salt of a sulfated formaldehyde condensation product with an alkyl aromatic, as well as lignosulfonates and salts thereof.

[0086] e. Water-insoluble filler A suitable filler is preferably selected from the group including the following: e2) Synthetic silicates and fumed silica, such as Sipernat®, Aerosil®, or Durosil® series (Degussa), CAB-O-SIL® series (Cabot), or Van Gel series (RTVanderbilt), and e3) Fillers based on synthetic polymers, such as the Thixin® or Thixatrol® series (Elementis) thickeners.

[0087] Even more preferable are the fillers of group e2.

[0088] Particularly preferred are fumed silica as a filler, such as Aerosil products, Aerosil R products, and Cab-O-Sil products, either alone or in mixtures, and attapulgite.

[0089] f. solvent The solvent f) is preferably selected from compounds represented by formula 4: [ka]

[0090] During the ceremony, y = 1 to 9, A, B=H, or a linear alkyl group, M = H, or alkyl.

[0091] More preferably, f) is selected from the compounds represented by formula 4: y = 1 to 3, A, B=H, or a linear alkyl group, M = H, or alkyl.

[0092] More preferably, f) is selected from the compounds represented by formula 4: y = 1 to 3, A, B = H, or methyl, M = H, or methyl.

[0093] Most preferably, f) is selected from the compounds represented by formula 4: y = 1 to 2, If A=H, then B=methyl, and if A=methyl, then B=H. M = H, or methyl.

[0094] Examples of solvent f) include Dow's Dowanol glycol ether products, or various grades of polyethylene glycol ether (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, various grades of polypropylene glycol ethers (e.g., 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, tripropylene glycol monobenzyl ether).

[0095] calcium. Further adjuvants The compositions of the present invention further include adjuvants g), for example, optionally substances from the group consisting of emulsifiers, humectants, anti-foaming agents, preservatives, colorants, stabilizers, and antioxidants.

[0096] Useful emulsifiers include all conventional nonionogenic, anionic, cationic, and amphoteric substances with surface-active properties typically used in agrochemical products. These substances include 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, as well as their sulfate esters, phosphate monoesters and phosphate diesters, and reaction products of ethylene oxide and propylene oxide, and further include alkyl sulfonates, alkyl sulfates, aryl sulfates, tetraalkylammonium halides, trialkylarylammonium halides, alkylamine sulfonates, terminal-capped and non-terminal-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g., butoxypolyethylene-propylene glycol), as well as polyethylene glycol and polypropylene glycol.

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

[0098] Useful humectants are all substances that can be typically used for this purpose in pesticide compositions. Water-soluble liquids are preferred, and examples include glycerol, 1,2-propylene glycol, and dipropylene glycol.

[0099] Useful anti-foaming agents are all substances that can be typically used for this purpose in pesticide compositions. Silicone oils, such as SAG1572, and magnesium stearate are preferred.

[0100] Useful antioxidants are all substances that can be typically used for this purpose in pesticide compositions. Butylhydroxytoluene is preferred.

[0101] Useful pigments are all substances that can be typically used for this purpose in pesticide compositions. Examples include titanium dioxide, black pigments, zinc oxide, and blue pigments, as well as 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 polyalkyl-substituted amines.

[0103] In a preferred embodiment, the present invention provides an insecticidal composition comprising the following:

[0104] a. Compounds of formula (I) [ka]

[0105] Here, the compound of formula (I) has the following definition: W is methyl, X is chlorine or methyl, Y is chlorine, bromine, or methyl. A, B, and the carbon atoms to which they are bonded are saturated C6-cycloalkyl groups substituted with alkylenedioxy groups, forming a 5-membered or 6-membered ketal. G is either hydrogen (a) or one of the following groups: [ka]

[0106] During the ceremony, M is oxygen, E is a single metal ion equivalent or ammonium ion. R 1 These are linear or branched C1-C4 alkyl groups. R 2 These are linear or branched C1-C4 alkyl groups.

[0107] b. At least one ammonium salt selected from the group comprising ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP).

[0108] c. Alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): [ka]

[0109] [In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment. A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably 15 to 35 PO units, and more preferably 20 to 30 PO units. B is a random copolymer polyethylene glycol-polypropylene glycol fragment consisting of 10 to 50 ethylene oxide (EO) units (formula III-c) and 0 to 10 propylene glycol (PO) units, preferably consisting of 20 to 40 EO units and 0 to 8 PO units, and more preferably consisting of 30 to 40 EO units and 0 to 5 PO units. [ka] ], and alkyl polypropylene glycol-polyethylene glycol compounds of general formula (IIId): [ka] [In the formula, Each base and exponent has the following definitions:

[0110] R and R' are independently hydrogen, a linear C1-C5 alkyl group, or a branched C3- or C4-alkyl group. m is 2 or 3, n is either 2 or 3. x is between 5 and 150. y is between 5 and 150. Here, n or m in one base has the meaning of 2, and n or m in the other base has the meaning of 3. At least one dispersant selected from the group including the above.

[0111] d. At least one surfactant selected from the group comprising polycarboxylate type, salts of sulfated formaldehyde condensation products with alkyl aromatics, salts of sulfated formaldehyde condensation products with dityl ethers, salts of sulfated formaldehyde condensation products with cyclohexanone, lignosulfonates and their salts, and sulfated alkylaryl sulfonates and their salts.

[0112] e. At least one filler selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates, and fillers based on fumed silica, attapulgite, and synthetic polymers.

[0113] f. At least one solvent selected from the compounds represented by formula 4: [ka]

[0114] During the ceremony, y = 1 to 9, A, B=H, or a linear alkyl group, M = H, or alkyl.

[0115] g. Further adjuvants.

[0116] In a further preferred embodiment, the present invention provides an insecticidal composition comprising the following:

[0117] a. Compound of formula (I) selected from the following compounds: [ka] [Table 7]

[0118] b. At least one ammonium salt selected from the group comprising ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP).

[0119] c. Alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): [ka]

[0120] [In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment. A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably 15 to 35 PO units, and more preferably 20 to 30 PO units. B is a random copolymer polyethylene glycol-polypropylene glycol fragment consisting of 10 to 50 ethylene oxide (EO) units (formula III-c) and 0 to 10 propylene glycol (PO) units, preferably consisting of 20 to 40 EO units and 0 to 8 PO units, more preferably consisting of 30 to 40 EO units and 0 to 5 PO units: [ka] ], and alkyl polypropylene glycol-polyethylene glycol compounds of general formula (IIId): [ka] [In the formula, Each base and exponent has the following definitions:

[0121] R and R' are independently hydrogen, a linear C1-C5 alkyl group, or a branched C3- or C4-alkyl group. m is 2 or 3, n is either 2 or 3. x is between 5 and 150. y is between 5 and 150. Here, n or m in one base has the meaning of 2, and n or m in the other base has the meaning of 3. At least one dispersant selected from the group including the above.

[0122] d. At least one surfactant selected from the group comprising polycarboxylate type, salts of sulfated formaldehyde condensation products with alkyl aromatics, salts of sulfated formaldehyde condensation products with dityl ethers, salts of sulfated formaldehyde condensation products with cyclohexanone, and lignosulfonates and salts thereof.

[0123] e. At least one filler selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates, and fillers based on fumed silica, attapulgite, and synthetic polymers.

[0124] f. At least one solvent selected from the compounds represented by formula 4: [ka]

[0125] During the ceremony, y = 1 to 3, A, B=H, or a linear alkyl group, M = H, or alkyl.

[0126] g. Further adjuvants.

[0127] In a more preferred embodiment, the present invention provides an insecticide composition comprising the following:

[0128] a. Compounds having the following structure and formula (I-2): [ka]

[0129] b. At least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP).

[0130] c. Alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): [ka]

[0131] [In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment. A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably 15 to 35 PO units, and more preferably 20 to 30 PO units. B is a random copolymer polyethylene glycol-polypropylene glycol fragment consisting of 10 to 50 ethylene oxide (EO) units (formula III-c) and 0 to 10 propylene glycol (PO) units, preferably consisting of 20 to 40 EO units and 0 to 8 PO units, more preferably consisting of 30 to 40 EO units and 0 to 5 PO units: [ka] ], and alkyl polypropylene glycol-polyethylene glycol compounds of general formula (IIId): [ka] [In the formula, Each base and exponent has the following definitions:

[0132] R and R' are independently hydrogen, a linear C1-~C5-alkyl group, or a branched C3- or C4-alkyl group. m is 2 or 3, n is either 2 or 3. x is between 5 and 150. y is between 5 and 150. Here, n or m in one base means 2, and n or m in the other base means 3. At least one dispersant selected from the group including the above.

[0133] d. At least one surfactant selected from the group including polycarboxylate types.

[0134] e. At least one filler selected from the group comprising fumed silica and attapulgite.

[0135] f. At least one solvent selected from the compounds represented by formula 4: [ka]

[0136] During the ceremony, y = 1 to 3, A, B = H, or methyl, M = H, or methyl.

[0137] g. Further adjuvants.

[0138] In its most preferred embodiment, the present invention provides an insecticide composition comprising the following:

[0139] a. Compounds having the following structure and formula (I-2): [ka]

[0140] b. At least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP).

[0141] c. Alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): [ka]

[0142] [In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment. A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably 15 to 35 PO units, and more preferably 20 to 30 PO units. B is a random copolymer polyethylene glycol-polypropylene glycol fragment consisting of 10 to 50 ethylene oxide (EO) units (formula III-c) and 0 to 10 propylene glycol (PO) units, preferably consisting of 20 to 40 EO units and 0 to 8 PO units, more preferably consisting of 30 to 40 EO units and 0 to 5 PO units: [ka] ], and alkyl polypropylene glycol-polyethylene glycol compounds of general formula (IIId): [ka] [In the formula, Each base and exponent has the following definitions: R and R' are independently hydrogen, a linear C1-C5 alkyl group, or a branched C3- or C4-alkyl group. m is 2 or 3, n is either 2 or 3. x is between 5 and 150. y is between 5 and 150. Here, n or m in one base has the meaning of 2, and n or m in the other base has the meaning of 3. At least one dispersant selected from the group including the above.

[0143] d. At least one surfactant selected from the group including polycarboxylate types.

[0144] e. At least one filler selected from the group comprising fumed silica and attapulgite.

[0145] f. At least one solvent selected from the compounds represented by formula 4: [ka]

[0146] During the ceremony, y = 1 to 2, If A=H, then B=methyl, and if A=methyl, then B=H. M = H, or methyl.

[0147] g. Further adjuvants.

[0148] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure.

[0149] Percentages should be considered weight percentages unless otherwise specified, and the weight percentages of the composition should total 100.

[0150] The proportions of each component below are based on the total weight of the composition, with component f) (solvent) making up to a maximum of 1 liter of the total composition. Therefore, the proportion of component f) is preferably 1% to 80% by weight, and more preferably 20% to 60% by weight.

[0151] The proportion of the solid active ingredient (component a) in the composition according to the present invention is: Preferably 0.5 to 30% by weight, More preferably 1 to 20% by weight, Comfortable 1-15% by weight, Most preferably 1.5 to 15% by weight That is the case.

[0152] The proportion of the soluble active ingredient (component b) in the composition according to the present invention is: Preferably 1 to 40% by weight, More preferably 5 to 35% by weight, Comfortable 15-30% by weight That is the case.

[0153] The proportion of the dispersant (component c) in the composition according to the present invention is, Preferably 0.5 to 40% by weight, More preferably 5 to 35% by weight, Comfort 10-30% by weight That is the case.

[0154] The proportion of surfactant (component d) in the composition according to the present invention is, Preferably 0-10% by weight, More preferably 0.3 to 8% by weight, Comfortable 0.5-5% by weight That is the case.

[0155] The proportion of the filler (component e) in the composition according to the present invention is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, even more preferably 1 to 5% by weight is.

[0156] The proportion of the adjuvant (component g) in the composition according to the present invention is preferably 0 to 20% by weight, more preferably 1 to 20% by weight, even more preferably 2.5 to 17.5% by weight, even more preferably 5 to 15% by weight is.

[0157] A preferred embodiment of the present invention is the components: a) 0.5 to 30% by weight b) 1 to 40% by weight c) 0.5 to 40% by weight d) 0 to 10% by weight e) 0.1 to 10% by weight g) 0 to 20% by weight f) up to 1 liter is a composition containing.

[0158] A further preferred embodiment of the present invention is the components: a) 1 to 20% by weight b) 5 to 35% by weight c) 5 to 35% by weight d) 0.3 to 8% by weight e) 0.5 to 10% by weight g) 1 to 20% by weight f) up to 1 liter is a composition containing.

[0159] An even more preferred embodiment of the present invention is the components: a) 1 to 20% by weight b) 5 to 35% by weight c) 5 to 35% by weight d) 0.3 to 8% by weight e) 0.5 to 10% by weight g) 2.5 to 17.5% by weight f) up to 1 liter The composition contains the following.

[0160] A more preferred embodiment of the present invention is a composition containing the components: a) 1 to 15% by weight b) 15 to 30% by weight c) 10 to 30% by weight d) 0.5 to 5% by weight e) 1 to 5% by weight g) 5 to 15% by weight f) up to 1 liter The composition contains the following.

[0161] The most preferred embodiment of the present invention is a composition containing the components: a) 1.5 to 5% by weight b) 15 to 30% by weight c) 10 to 30% by weight d) 0.5 to 5% by weight e) 1 to 5% by weight g) 5 to 15% by weight f) up to 1 liter The composition contains the following.

[0162] The present invention further relates to an adjuvant combination for an insecticidal active ingredient formulation having at least one active ingredient in solid form for improving the penetration of both active ingredients, b. at least one ammonium salt, and c. at least one dispersant selected from the group of alkylpropoxylated ethoxylates The combination contains the following.

[0163] In a preferred embodiment, the adjuvant combination further contains f. a solvent selected from the compounds represented by Formula 4,

Chemical formula

[0164] During the ceremony, y = 1 to 9, A, B=H, or a linear alkyl group, M = H, or alkyl.

[0165] The ammonium salt from the adjuvant combination is preferably selected from the group including water-soluble inorganic ammonium salts.

[0166] More preferably, b) is selected from the group comprising ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate, and diammonium hydrogen phosphate (DAHP).

[0167] More preferably, b) is DAHP and AMS.

[0168] Component c) (dispersant) of the adjuvant combination is preferably selected from the group comprising alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a), [ka]

[0169] In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment. A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), preferably 15 to 35 PO units, and more preferably 20 to 30 PO units. B is a random copolymer polyethylene glycol-polypropylene glycol fragment consisting of 0 to 10 propylene glycol (PO-) units and 10 to 50 ethylene oxide (EO-) units (Formula III-c), preferably consisting of 0 to 8 PO units and 20 to 40 EO units, and more preferably consisting of 0 to 5 PO units and 30 to 40 EO units. [ka]

[0170] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are listed below: [Table 8]

[0171] and Compounds of general formula (IIId): [ka] And, During the ceremony, Each base and exponent has the following definitions: R and R' are independently hydrogen, a linear C1-~C5 alkyl group, or a branched C3- or C4-alkyl group; m is either 2 or 3; n is either 2 or 3; x is between 5 and 150; y is between 5 and 150. Here, n or m in one group means 2, and n or m in the other group means 3.

[0172] In the context of the present invention, a linear C1-~C5 alkyl group is understood to mean a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group.

[0173] In the context of the present invention, branched C3- or C4-alkyl groups are understood to mean isopropyl groups, isobutyl groups, or tert-butyl groups.

[0174] In a preferred embodiment, the R and R′ groups are independently selected from the group consisting of a methyl group, an n-butyl group, and hydrogen.

[0175] In a more preferred embodiment, the R and R′ groups are independently selected from the group consisting of n-butyl groups and hydrogen.

[0176] Regarding the arrangement of polyethylene and polypropylene units, (a) Can we assume that m is value 2 and n is value 3? (b) We can assume that m is value 3 and n is value 2.

[0177] A preferred configuration is (b) where m=3 and n=2.

[0178] What is particularly desirable is, m is 3, n is 2, x is between 5 and 80. y is between 5 and 80. R is n-butyl or hydrogen, R′ is hydrogen. It is an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId).

[0179] The solvent f) used with the adjuvant combination is more preferably selected from the compounds represented by formula 4, [ka]

[0180] During the ceremony, y = 1 to 3, A, B=H, or a linear alkyl group, M = H, or alkyl, More preferably, f) is selected from the compounds represented by formula 4, y = 1 to 3, A, B = H, or methyl, M = H, or methyl.

[0181] Most preferably, f) is selected from the compounds represented by formula 4, y = 1 to 2, If A=H, then B=methyl, and if A=methyl, then B=H. M = H, or methyl.

[0182] A preferred embodiment of the present invention is an adjuvant combination in which the ratio of b):c) (on a mass basis in each case) is 3:1 to 1:3, preferably 2:1 to 1:2 and more preferably 1.3:1 to 1:1.3.

[0183] The ratio of adjuvant combinations based on the total weight of the formulation is preferably b)1~40% by weight c)1~40% by weight And, More preferably b)5~35% by weight c)5~35% by weight And, More preferably b) 15~30% by weight c)10~30% by weight That is the case.

[0184] The application rate of the formulation according to the present invention can be varied within a relatively wide range. This depends on the respective active ingredients and their content in the composition. The application volume of the formulation according to the present invention in aqueous spray solutions can also be varied within a relatively wide range; that is, the applicable spray volume can be varied from 10 to 500 liters / ha.

[0185] By using the composition according to the present invention, the insecticidal active ingredient mixture can be sprayed in a manner particularly advantageous to plants and / or their habitats.

[0186] All plants and plant parts can be processed using the compositions according to the present invention. In this context, plants are understood to include all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants that can be obtained by conventional breeding and optimization methods, or by biotechnology and genetic engineering methods or combinations thereof, including transgenic plants and plant cultivars that are protected or unprotected by the rights of plant breeders. Plant parts should be understood to mean all parts and organs of plants above and below ground, 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 products and vegetative and reproductive materials, such as cuttings, tubers, rhizomes, twigs and seeds.

[0187] Preferably, the formulation according to the present invention is used by spray application against animal pathogens of the following families: Species from the family Pemphigidae: For example, species of the genera Eriosoma and Pemphigus are preferred in crops such as citrus fruits, pome fruits, drupes, leafy vegetables, root vegetables and tuberous vegetables, and ornamental plants.

[0188] Grape lice (Phylloxeridae): Species of the genus Phylloxera found in grapes, nuts, and citrus fruits are preferred.

[0189] Species from the Psyllidae family: for example, crops such as pome fruits, drupes, citrus fruits, vegetables, potatoes, and tropical crops, particularly species of the genera Psylla, Paratrioza, Tenalaphala, Diaphorina, and Trioza.

[0190] Species from the Coccidae family: for example, species of the genera Ceroplastes, Drosicha, Pulvinaria, Protopulminaria, Saissetia, and Coccus are preferred in perennial crops such as citrus fruits, pome fruits, drupes, olives, grapes, coffee, tea, tropical crops, ornamental plants, and vegetables.

[0191] From the family Diaspididae: for example, species of Quadraspidiotus, Aonidiella, Lepidosaphes, Aspidiotus, Aspis, Diaspis, Parlatoria, Pseudaulacaspis, Unaspis, and Pinnaspis found on crops such as citrus fruits, pomelo, drupes, almonds, pistachios, nuts, olives, tea, ornamental plants, grapes, and tropical crops. Species of the genus Selenaspidus (spp.) are preferred.

[0192] Species from the family Ortheziidae (scale insects): Orthezia spp. species found in citrus fruits, pome fruits, and drupes are preferred.

[0193] Species from the Pseudococcidae family (mealybugs): For example, Pericerga, Pseudococcus spp., Planococcus spp., and Dysmicoccus spp. are preferred in crops such as citrus fruits, drupes and pomelo, tea, grapes, vegetables, ornamental plants, and tropical crops.

[0194] From the family Aleyrodidae: for example, tobacco whitefly (Bemisia tabaci), silverleaf whitefly (Bemisia argentifolii), greenhouse whitefly (Trialeurodes vaporariorum), citrus cotton whitefly (Aleurothrixus floccosus), species of the genera Aleurodes (Aleurodes spp.), species of the genera Dialeurodes (Dialeurodes spp.), and bayberry whitefly (Parabemisia myricae) are preferred for crops such as vegetables, melons, potatoes, tobacco, soft fruits, citrus fruits, ornamental plants, cotton, soybeans, and tropical crops.

[0195] Furthermore, from the family Aphididae: Myzus species (Myzus spp.) used in tobacco, drupes, soft fruits, fruit vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamental plants, and spices. Pea aphid (Acyrthosiphon onobrychis) on vegetables, Tobacco, citrus fruits, pome fruits, drupes, melons, strawberries, soft fruits, fruit vegetables, leafy vegetables, tubers, stems and root vegetables, ornamental plants, potatoes, pumpkins, spices, and species of the genus Aphis. Rhodobium porosum (rose green aphid) on strawberries. Lettuce aphid (Nasonovia ribisnigri) on leafy vegetables, Ornamental plants, potatoes, leafy vegetables and fruit vegetables, and Macrosiphum species in strawberries. Phorodon humuli in Hop Radish aphid (Brevicoryne brassicae) on leafy vegetables, Toxoptera species (Toxoptera spp.) in citrus fruits, drupes, almonds, nuts, and spices. Aulacorthum species (Aulacorthum spp.) in citrus fruits, potatoes, fruit vegetables, and leafy vegetables. Anuraphis cardui as a vegetable, Brachycaudus helycrisii on a sunflower. Pea aphid (Acyrthosiphon onobrychis) on vegetables It is preferable.

[0196] Similarly, from the family Thrips (Thripidae): for example, species of the genera Anaphothrips, Baliothrips, Caliothrips, Frankliniella, Heliothrips, Hercinosa, Rhipiphorothrips, Scirtothrips, and Kakothrips in crops such as fruits, cotton, grapes, tea, nuts, tropical crops, ornamental plants, conifers, tobacco, spices, vegetables, soft fruits, melons, citrus fruits, and potatoes. Species of the genera Selenothrips (spp.), Selenothrips (spp.), and Thrips (spp.) are preferred.

[0197] Furthermore, species from the leafminer fly (Agromyzidae) and root maggot fly (Anthomyiidae) families are preferred: for example, species from the genera Agromyza, Amauromyza, Atherigona, Chlorops, Liriomyza, Oscinella, and Pegomyia found in crops such as vegetables, melons, potatoes, nuts, and ornamental plants.

[0198] Leafhoppers (Cicadellidae) and planthoppers (Delphacidae): For example, species from the genera Circulifer, Dalbus, Empoasca, Erythroneura, Homalodisca, Iodioscopus, Laodelphax, Nephotettix, and Nilaparvata in crops such as citrus fruits, fruits, grapes, potatoes, vegetables, ornamental plants, conifers, melons, soft fruits, tea, nuts, rice, and tropical crops. Species of the genera Oncometopia (spp.), Oncometopia (spp.), and Sogatella (spp.) are preferred.

[0199] Leaf minor mosses (from the family Gracilaria): Species of the genera Caloptilia, Gracilaria, Lithocolletis, Leucoptera, Phtorimaea, and Phyllocnistis are preferred for crops such as pome fruits, drupes, grapes, nuts, citrus fruits, conifers, potatoes, and coffee.

[0200] From the family Cecidomyiidae: For crops such as citrus fruits, pome fruits, drupes, vegetables, potatoes, spices, soft fruits, conifers, and hops, species of the genera Contarinia, Dasineura, Diplosis, Prodiplosis, Thecodiplosis, Sitodiplosis, and Haplodiplosis are preferred.

[0201] Similarly, from the family Tephritidae: Species of the genera Anastrepha, Ceratitis, Dacus, and Rhagoletis are preferred for crops such as vegetables, soft fruits, melons, pomelo and drupes, ornamental plants, potatoes, grapes, tropical crops, citrus fruits, and olives.

[0202] Furthermore, from the families of spider mites (Tetranychidae) and gall mites (Eriophydae): Species of the genera Tetranychus, Panonychus, and Aculops are preferred for crops such as vegetables, potatoes, ornamental plants, citrus fruits, grapes, and conifers.

[0203] Treatment of plants and parts of plants according to the present invention with the compositions according to the present invention is carried out by conventional treatment methods, such as drenching, immersion, spraying, evaporation, atomization, spraying, and coating, and in the case of seeding materials, especially seeds, by applying one or more coatings, either directly or by allowing the compositions to act on the surroundings, environment, or storage space.

[0204] Preferably, the plants to be treated are selected from the group consisting of cotton, soybeans, tobacco, vegetables, spices, ornamental plants, conifers, citrus plants, fruits, tropical crops, nuts, and grapes.

[0205] Preferably, the composition according to the present invention acts against pathogenic organisms from the families of mealybugs, grape lice, psyllids, scale insects, round scale insects, leaf scale insects, mealybugs, whiteflies, aphids, thrips, leafhoppers, planthoppers, leafminer flies, gall midges, fruit flies, leafminer mosses, spider mites, and gall mites.

[0206] Furthermore, it was found that the composition according to the present invention can be manufactured by a method having the following steps.

[0207] 1) Mix components (a) to (g), then homogenize and grind the mixture into beads. Apparatus for homogenization and grinding into beads is known to those skilled in the art.

[0208] This method also forms part of the subject matter of the present invention.

[0209] Finally, it was found that the compositions according to the present invention have excellent suitability for application of existing pesticide active ingredients to plants and / or their habitats.

[0210] Materials used in the examples:

Table 9

[0211] TIFF2023500580000050.tif74160

[0212] Tests and methods used in the examples The evaluation of the characteristics of the formulation is carried out in the same manner as DIN 10964 "Sensory analysis - Simple descriptive test". In this regard, the samples to be examined are inspected visually and, if necessary, by shaking and tilting for shape, state of matter and color as well as further characteristics (especially, for example, lumps, solidification, precipitate formation, subsequent thickening, marbling of precipitates, etc.).

[0213] rotational viscosity is measured according to CIPAC MT 192. A stable and convenient formulation is expected to exhibit a medium range of viscosity in order to facilitate the opening and cleaning of the bottle.

[0214] Rheology was measured using a Bohlin Gemini viscometer. The measurements of G′ (elastic modulus), G″ (viscosity coefficient) and phase angle are carried out at room temperature at different frequencies (0.01~5 Hz) using a frequency sweep routine either by strain or stress control. The reported values are those obtained at 0.5 Hz / 20°C. It is recognized by those skilled in the art that a small phase angle and a large value of G′ (>G″) indicate a high possibility of a stable formulation, and a large phase angle and a small value of G′ (<G″) indicate a high possibility of a formulation with low stability.

[0215] particle sizeThis is measured using laser diffraction in accordance with CIPAC MT 187 Malvern Mastersizer (medium: propylene glycol), or using an optical microscope (40x magnification). A stable and convenient formulation is expected to contain small particles to ensure both good storage stability in the concentrate and good suspension stability in the aqueous diluent.

[0216] agglomeration This is measured using an optical microscope (40x magnification). A stable and convenient formulation is expected to be free of aggregates to ensure both good storage stability in the concentrated solution and good suspension stability in the aqueous dilution.

[0217] Suspension stability The evaluation is performed according to a simplified method compliant with CIPAC MT 180, using a 2% aqueous dilution in CIPAC C or CIPAC D water, and measured after standing for 1 hour. A stable and convenient formulation is expected to have little to no precipitate forming at the bottom of the test container to ensure uniform application of the spray solution.

[0218] Storage stability The tests are conducted for a specified number of weeks (w) at different temperatures such as 0°C, 20°C, 30°C, 40°C, 54°C, or a thaw-freeze cycle (=TW; repeating a constant temperature change from -15°C to +30°C within one week).

[0219] Sample Redispersibility This is qualitatively determined by shaking the sample and then evaluating the bottom surface of the sample container.

[0220] Immediately after storage phase separation This is reported as the sediment content, calculated from the quotient obtained by dividing H1 [interface layer level between the sedimentary phase and the supernatant] by H0 [total packing height of the sample], or, as in this case, reported as the supernatant content.

[0221] Sediment content = (H1 / H0) × 100 [%], or Supernatant content = 100-Sediment content [%] Stable and convenient formulations are expected to not undergo phase separation, or only minimal phase separation, even when stored at high temperatures for extended periods, and to be easily re-homogenized. Significant phase separation after short storage times indicates limited storage stability and a strong tendency to form deposits during storage that, if absent, are difficult to disperse.

[0222] Example I Combine all formulations from the experiments described in Tables Ia-c in a 25 mL PE screw-cap bottle and add 10 g of glass beads (size 1-1.25 mm). Close the bottle and clamp it to a stirrer (Retsch MM301) and process at 30 Hz for 40 minutes; during this process, the sample will be heated. After the time has elapsed, cool the sample to room temperature and evaluate the consistency of the formulation. Then, use a microscope (Zeiss transmission light microscope, 40x magnification) to measure the particle size by laser dispersion and evaluate the properties of the dispersion. Very small particle size indicates good pulverability, while the presence of aggregates indicates poor dispersion properties.

[0223] Table 1 (Numbers are weight %) [Table 10]

[0224] Evaluation of the experiment : Formulations based on I-2, ammonium salts, and Dowanol DPM containing different amounts of surfactant (Experiments 1-1, 1-2) exhibited the basic pulverability of the respective ammonium salts and I-2 under specified experimental conditions. However, in the absence of sufficient surfactant (>1%) in the formulation, significant aggregation of salt crystals in the concentrate was observed under a microscope, indicating very poor dispersibility of individual particles, even if none were present in the liquid phase. Only certain surfactants could adequately disperse the ammonium salts and I-2 (e.g., 1-2, 1-7), and alkylpropoxylates ethoxylates alone could not do so, as evidenced by the high viscosity and presence of aggregates in samples pulverized only with Antarox B / 848 (1-9).

[0225] The most effective and surprising combination is a small amount of two different surfactants (Experiments 1-10 to 1-14). This combination (Geropon T-36 and Morwet D-425) is particularly surprising because 1.00% of each surfactant is far more effective in grinding and stabilizing DAHP or AMS than 5.00% of each surfactant alone.

[0226] Example II For the purpose of testing suitable thickeners and carriers in the presence of suitable dispersion aids, all formulation components listed in Tables 2, 3, and 4 are combined and ground by one of the methods described below.

[0227] 1) The formulation components are homogenized using a colloidal mill, and then ground using a bead mill (Dispermat SL50, 80% 2mm beads, 4000 rpm, 40 minutes of cyclic grinding). After the time has elapsed, the sample is cooled to room temperature and the rheological properties of the formulation are evaluated.

[0228] 2) Mix the formulation components in a bottle, seal it, and clamp it to a stirrer (Retsch MM301) for 40 minutes at 30 Hz. During this time, the sample is heated. After the time has elapsed, the sample is cooled to room temperature and the rheological properties of the formulation are evaluated.

[0229] The rheological properties of the formulation were evaluated using a Gemini Rheometer (Bohlin Instruments). G′ (modulus of elasticity), G″ (viscosity coefficient), and phase angle were measured at different frequencies (0.01–5 Hz) at room temperature using a frequency sweep routine controlled by either strain or stress. Viscosity was evaluated at room temperature according to the method described in CIPAC MT192; "Viscosity of Liquids by rotational viscometry".

[0230] Table 2 (Values ​​are in weight %) [Table 11]

[0231] Evaluation of the experiment in Table 2 : The formulation using Aerosil R812 S (Example No. 2-2) is the only one with a low phase angle, which indicates that these formulations have much higher elastic properties and are therefore expected to be more stable with respect to sedimentation stability. Furthermore, the sedimentation stability of Example 2-2 is achieved without producing the high viscosity observed in the other examples, which have much higher dynamic viscosity than Example 2-2 at a low shear rate of 1 / 24.

[0232] Table 3 (Values ​​are in weight %) [Table 12]

[0233] TIFF2023500580000054.tif53170

[0234] Evaluation of the experiment in Table 3 Formulations using dipropylene glycol monomethyl ether (Examples 3-1, 3-2, and 3-3) all exhibit excellent rheological properties, namely high modulus of elasticity (low phase angle <30°) and shear viscosity reduction. Furthermore, formulations containing propylene glycol (Example 3-1) or dipropylene glycol (Example 3-2) exhibit relatively low viscosity at low shear rates (<700 mPas @ 24 / s). Other carriers, such as 1-methoxy-2-propanol (Example 3-4) or diethylene glycol monomethyl ether (Example 3-5), also yield formulations with low phase angles, and in the case of Example 3-4, relatively low viscosity at low shear rates. PEG 400 is extremely viscous, making it impossible to obtain a processable formulation (Example 3-6), but this can be improved by the addition of propylene glycol (Example 3-11), which makes the formulation more elastic (phase angle 23° @ 0.5 Hz) and, in terms of viscosity, more manageable (114 mPas @ 24 Hz). Neither tripropylene glycol monomethyl ether (Example 3-7) nor dipropylene glycol monopropyl ether (Example 3-9) imparted enough elasticity to the formulation to suggest that a stable product would be more likely to precipitate. This can be seen at very high phase angles (>45°) of the formulation, which primarily exhibit viscous behavior. Nevertheless, both formulations can become elastically dominant (phase angle <45°) with the addition of propylene glycol. Examples 3.8 and 3.10, phase angles @0.5Hz: 39° and 34°, respectively.

[0235] Table 4 (Values ​​are in weight %) [Table 13]

[0236] Evaluation of the experiment in Table 4: The formulations according to the present invention can be manufactured using different amounts of the active ingredient without losing their satisfactory rheological properties. In fact, formulations 4-1, 4-2, and 4-3 all retain their elastic-rheological properties (phase angle <30°) while exhibiting shear viscosity reduction behavior. Furthermore, as can be seen from the properties of formulation 4-4, which exhibits a high phase angle (>45°) due to the high concentrations of the dispersants Geropon T-36 and Morwet D-425, the use of large amounts of surfactant is not necessary to control the rheological behavior of the formulation. As can be seen in formulation 4-5, surfactant concentrations in the 0.5% range are suitable for the formulation's high elasticity (phase angle 16°) and shear viscosity reduction behavior.

[0237] Example III To investigate the long-term stability of the most suitable formulation, a suitable thickener is combined with a suitable dispersing agent listed in Table 5 and pulverized by one of the methods described below.

[0238] 1) The formulation components are homogenized using a colloidal mill, and then ground using a bead mill (Dispermat SL50, 80% 2mm beads, 4000 rpm, circulating grinding for 40 minutes). After the time has elapsed, the sample is cooled to room temperature and the rheological properties of the formulation are evaluated.

[0239] 2) Mix the formulation components in a bottle, seal it, and clamp it to a stirrer (Retsch MM301) for 40 minutes at 30 Hz. During this time, the sample is heated. After the time has elapsed, the sample is cooled to room temperature and the rheological properties of the formulation are evaluated.

[0240] Subsequently, storage tests are conducted at high temperatures to perform qualitative and quantitative evaluations of appearance, phase separation, rheological properties, dispersion stability after storage (e.g., viscosity), and active ingredient concentration.

[0241] The visual evaluation shall be carried out in the same manner as DIN 10964, "Sensory analysis - Simple descriptive test." For this purpose, the test sample shall be examined visually and, if necessary, by shaking and tilting, for its shape, state and color, as well as further properties (in particular, e.g., lumps, solidification, precipitate formation, subsequent thickening, and precipitate marbling).

[0242] Phase separation immediately after storage is reported as sediment content, calculated from the quotient obtained by dividing H1 [interface layer level between sediment phase and supernatant] by H0 [total packing height of the sample], or as in this case, as reported as supernatant percentage.

[0243] Sediment content = (H1 / H0) × 100 [%], or Supernatant content = 100-Sediment content [%]

[0244] The rheological properties of the formulation were evaluated using a Gemini Rheometer (Bohlin Instruments). G′ (modulus of elasticity), G″ (viscosity coefficient), and phase angle were measured at different frequencies (0.01–5 Hz) at room temperature using a frequency sweep routine controlled by either strain or stress. Viscosity was evaluated at room temperature according to the method described in CIPAC MT192; "Viscosity of Liquids by rotational viscometry".

[0245] The dispersion stability of a 2% aqueous dilution is determined by analyzing the amount of precipitated residue after a certain period of time, according to the CIPAC MT 180 method, "Dispersion stability of suso-emulsions." [Table 14]

[0246] TIFF2023500580000057.tif254156

[0247] TIFF2023500580000058.tif254162

[0248] TIFF2023500580000059.tif40162

[0249] Evaluation of the experiment in Table 5: By using fillers such as Aerosil R812S and different combinations of propylene glycol / dipropylene glycol monomethyl ether, it is possible to produce stable formulations with different viscosities (Formulations 5-1, 5-2). In fact, both formulations are stable during storage and exhibit very good sedimentation stability. After storing the formulations at room temperature or 54°C for 4 weeks, the observed phase separation in both Examples 5-1 and 5-2 is very small.

[0250] Both Examples 5-1 and 5-2 exhibit considerably high elastic rheological behavior during storage at room temperature. This is evident from the fact that the initially high phase angle becomes considerably smaller (<35°) after 4 weeks at room temperature. Increased elastic rheological behavior translates to increased sedimentation stability. Particularly beneficial is that Example 5-1 exhibits higher elastic behavior (and therefore more stable) than Example 5-2 without a proportional increase in viscosity.

[0251] A further factor in ensuring formulation stability is the dispersion stability of the formulation in aqueous diluents. Both Examples 5-1 and 5-2 are dispersible in water, and after storage at room temperature or possibly 54°C, phase separation of the diluted formulations is relatively small (≤0.1 mL).

[0252] The use of fillers other than the silica-based Aerosil R812S results in formulations with significant drawbacks. This is exemplified in Comparative Examples 5-3, 5-4, and 5-5, which use the organic clay-based fillers Bentone 34, Bentone 38, and Bentone LT, respectively. The use of these organic clay fillers results in formulations with very high viscosity, as seen in 5-3 and 5-4, which increases during storage. Due to this viscosity increase, Comparative Examples 5-3 and 5-4 eventually become solid at some point during storage, only becoming fluid after vigorous shaking.

[0253] Furthermore, the dispersion stability behavior of Comparative Examples 5-3, 5-4, and 5-5 is significantly worse than that of Examples 5-1 and 5-2 according to the present invention. In fact, one hour after dispersion in water, the Comparative Examples produced a large amount of precipitate, while the Examples according to the present invention produced almost no precipitate of insoluble matter. For example, the insoluble residue generated by the Comparative Examples can clog application equipment or adversely affect the bioavailability of the active ingredient, so this is an advantage of the Examples according to the present invention.

[0254] In conclusion, silica fillers (examples according to the present invention) and organic clay fillers (comparative examples) have different technical characteristics, and the examples according to the present invention have significant advantages in viscosity, handling, and the usability of the formulation when dispersed in water. Furthermore, by using fumed silica, a stable formulation (with very limited phase separation during storage) can be obtained without producing the very high viscosity measured for some of the comparative examples. Therefore, the use of silica fillers in the examples according to the present invention in Table 5 is an improvement over the comparative examples based on organic clay fillers in Table 5.

Claims

1. a) at least one active ingredient that is solid at room temperature; b) at least one ammonium salt; c) at least one dispersant from the class of alkyl propoxylate ethoxylates; d) optionally one or more surfactants; e) at least one water-insoluble filler; f) at least one solvent selected from compounds represented by formula 4: 【Chemistry 1】 [In the formula, y=1 to 9; A and B are H or linear alkyl; M=H or alkyl; and g) Additional adjuvants A composition comprising: wherein the active ingredient a) is insoluble or only slightly soluble in the selected solvent f), and wherein e) is selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite, and fillers based on synthetic polymers, composition.

2. 2. The composition according to claim 1, characterized in that component d) is essential.

3. 3. The composition according to claim 1 or 2, characterized in that a) is selected from the group of insecticidal active ingredients having a solubility in the selected solvent f) of 5 g / L or less, more preferably 4 g / L or less, even more preferably 2.5 g / L or less, particularly preferably 1 g / L or less.

4. 4. Compositions according to one or more of claims 1 to 3, characterized in that a) is selected from the group of diamide insecticides, spinosyns (IRAC group 5), mectins (IRAC group 6), ethiprole, triflumuron, β-cyfluthrin, deltamethrin and tetronic or tetramic acid derivatives (IRAC group 23), including compounds of formula I and II below:

5. 5. The composition according to claim 1, wherein a) is selected from the group of tetronic or tetramic acid derivatives (IRAC group 23), which includes compounds of formulae I and II:

6. 6. The composition according to claim 1, wherein a) is a tetramic acid derivative of formula (I): 【Chemistry 2】 [In the formula, W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine; X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which they are attached are C1-C4-alkyl- or C １ -C ４ -alkoxy-C １ -C ２ -C3-C6-cycloalkyl substituted by an optionally alkyl-substituted alkylenedioxy group (forming together with the carbon atom to which it is attached a 5- or 6-membered ketal), G is hydrogen (a) or one of the following groups: 【Transformation 3】 During the ceremony, E is a metal ion or an ammonium ion; M is oxygen or sulfur; R1 is a linear or branched C1-C6-alkyl; R2 is a linear or branched C1-C6 alkyl.

7. 7. The composition according to claim 1, wherein component a) is a compound of formula (I-2). 【Chemistry 4】

8. 8. Composition according to one or more of claims 1 to 7, characterized in that b) is selected from the group comprising ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate (AMS), ammonium hydrogen carbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

9. c) is an alkyl polypropylene glycol-polyethylene glycol compound of the general formula (III-a): 【Transformation 5】 [In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, 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, more preferably consisting of 20 to 30 PO units; B is a random 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: 【Transformation 6】 ］、 and alkyl polypropylene glycol-polyethylene glycol compounds of general formula (IIId): 【Transformation 7】 [In the formula, R and R′ are independently hydrogen, linear 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; y is 5 to 150; Here, n or m in one group is 2, and n or m in the other group is 3.] 9. Composition according to one or more of claims 1 to 8, characterized in that it is selected from the group comprising:

10. 10. Composition according to one or more of claims 1 to 9, characterized in that d) is a surfactant selected from the group comprising polycarboxylate type, salts of sulfated formaldehyde condensation products with alkylaromatics, salts of sulfated formaldehyde condensation products with ditolyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, and lignosulfonates and their salts.

11. 11. Composition according to one or more of claims 1 to 10, characterized in that f) is selected from the solvents represented by formula 4: 【Transformation 8】 [In the formula, y=1 to 3; A and B are H or linear alkyl; M=H or alkyl.

12. The component is a) 0.5-30% by weight b) 1-40% by weight c) 0.5-40% by weight d) 0-10% by weight e) 0.1-10% by weight g) 0-20% by weight f) up to 1 liter, 12. The composition according to claim 1, wherein the composition is present in a range of from 1 to 11.

13. The component is a) 1-20% by weight b) 5-35% by weight c) 5-35% by weight d) 0.3-8% by weight e) 0.5-10% by weight g) 1-20% by weight f) up to 1 liter, 13. The composition according to claim 1, wherein the composition is present in a range of from 1 to 12.

14. a) A compound having the formula (I-2) having the following structure: 【Chemistry 9】 b) at least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP); c) Alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): 【Chemistry 10】 [In the formula, R is a C1-C4 fragment, preferably a C3-C4 fragment, 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, more preferably consisting of 20 to 30 PO units; B is a random copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10 to 50 ethylene oxide (EO) units (formula III-c) and 0 to 10 propylene glycol (PO) units, preferably consisting of 20 to 40 EO units and 0 to 8 PO units, more preferably consisting of 30 to 40 EO units and 0 to 5 PO units. 【Chemistry 11】 ], and alkyl polypropylene glycol-polyethylene glycol compounds of general formula (IIId): 【Chemistry 12】 [In the formula, The individual groups and indices have the following definitions: R and R′ are independently hydrogen, linear 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; y is 5 to 150; Here, n or m in one group is 2, and n or m in the other group is 3.] at least one dispersant selected from the group comprising d) at least one surfactant selected from the group comprising the polycarboxylate type; e) at least one filler selected from the group comprising fumed silica and attapulgite; f) at least one solvent selected from compounds represented by formula 4: 【Chemistry 13】 [In the formula, y=1 to 2, If A=H then B=methyl, and if A=methyl then B=H; M=H or methyl. g) Additional adjuvants The composition of any one of claims 1 to 13, comprising:

15. Use of a composition according to one or more of claims 1 to 14 for controlling insects.

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