Insecticide formulations containing glycol ether solvents

Abstract

The present invention relates to insecticidal active ingredient preparations comprising at least one active ingredient or active ingredient combination in solid form, which have good storage stability at high and low temperatures and high active ingredient permeability, to a process for their preparation and to their use for applying the active ingredients present.

Description

[0001] The present invention relates to insecticidal active ingredient formulations comprising an active ingredient or active ingredient combination in solid form, which have good storage stability and high active ingredient permeability at high and low temperatures, resulting in high efficacy, a method for their preparation, and their use for applying the active ingredient present. The present invention also relates to adjuvant combinations for insecticidal active ingredient formulations comprising an active ingredient or active ingredient combination in solid form, in order to improve the permeability of the active ingredient or active ingredient combination.

[0002] In order to demonstrate biological efficacy, systemic active agrochemical ingredients, especially systemic insecticides, require formulations that allow the active ingredient to be absorbed into the plant / target organism. Optimal results are achieved when the active ingredient is used diluted in an aqueous solution and / or preferably already dissolved in a concentrate, so that a high active ingredient concentration is always available.

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

[0004] In addition, the biological activity may optionally be further enhanced by adding suitable adjuvants / penetrants.

[0005] As mentioned above, in formulations such as suspension concentrates (SC) and / or oil-based suspension concentrates (OD), the active ingredient or active ingredient combination is not in dissolved form but in solid, particulate form, and therefore these active ingredients in the formulation are generally not well bioavailable. In this case, the bioactivity can essentially be increased simply by adding suitable adjuvants / penetrants, but this still results in reduced bioactivity compared to the EC or SL formulations described above.

[0006] Known active agricultural chemical ingredients differ from each other in various aspects, including their physicochemical properties (e.g., solubility in water, solvents and / or oils), melting and boiling points, polarity, molar mass, etc. These properties affect the composability of the active ingredient. Many known active agricultural chemical ingredients, for example, have high melting points and can therefore withstand the thermal stresses that occur, for example, (caused by grinding), in the preparation of suspension concentrates. In contrast, because the active ingredient is expected to soften or melt at higher temperatures, active ingredients with low melting points are difficult to withstand these preparation conditions and can only prepare storage-stable suspensions to a very limited extent. However, if the active ingredient is no longer in crystalline form, the physical stability and sometimes chemical stability of the formulated product will typically be significantly reduced and will no longer have any practical use.

[0007] It is further known that organic substances have different water solubilities which, depending on the chemical properties, can be pH-dependent, for example through salt formation.

[0008] A characteristic of stable suspension concentrates is that they are physically and chemically storage stable over long periods of time (12-24 months) and over a wide temperature range (0 to 54° C.). This wide temperature range is required so that advantageously only one single formulation with the same active ingredient or combination of active ingredients can be used in different climatic regions.

[0009] The storage stability of the suspension concentrates is characterized in particular by the fact that the containers of these suspension concentrates have only low phase separation, if any, during storage.Another parameter for the stability of the suspension concentrates is, for example, the stability of the dispersion in the concentrate, which is manifested by the presence or absence of agglomerates in the concentrate.

[0010] WO 2011 / 029552 describes agrochemical formulations containing alkylpolypropylene glycol-polyethylene glycol (eg Antarox B / 848), in which this surfactant class acts as an emulsifier and / or penetrant for the active agrochemical ingredients.

[0011] Furthermore, WO 2003 / 000053 describes specific alkylpolypropylene 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 effects of active agricultural chemical ingredients is known in the literature; for example, WO 2011 / 131623 (US 2011 / 0281727 A1, Fischer et al.) describes insecticidal and / or herbicidal formulations based on heterocyclic tetramic acids that have improved efficacy in the presence of ammonium salts. In addition, WO 2007 / 068428 describes the enhanced activity of phenyl-substituted cyclic ketone-enols in the presence of ammonium salts. WO 2011 / 131623 relates to combinations of single active ingredients selected from substances of formula [I] and organic or inorganic ammonium salts or phosphonium salts, and to their use in aqueous spray solutions with or without suitable penetrants. Based on the teachings of WO 2011 / 131623, professionals cannot draw any conclusions about formulations with other active ingredient combinations or about the physical and chemical stability of these mixture formulations. Suitable penetrants are described in general terms in paragraphs

[0111] to

[0171] and are primarily claimed in

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

[0013] WO 2011 / 131623 does not describe or suggest the good permeability formulation of the present invention of an undissolved active ingredient.

[0014] Oil-based formulations containing ammonium salts are also known in the literature. For example, WO 2008 / 151725 describes an oil-based adjuvant composition in which the ammonium salt is in dispersed form. In addition, EP 2193712A1 describes an oil-based agricultural chemical formulation in which the ammonium salt is in dispersed form. However, no suspensions of ammonium salts in water-miscible solvents are described.

[0015] In summary, however, none of the documents cited above, either individually or collectively, suggest that alkylpolypropylene glycol-polyethylene glycols (e.g. Antarox B / 848) can be used as effective dispersants for high loads of inorganic ammonium salts in polar, water-soluble solvents such as glycol ethers, especially when combined with suspended active ingredients.

[0016] Soluble, water-based concentrates of tetramic acid derivatives are known from the prior art (e.g., WO 2009 / 115262). Due to solubility problems, these cannot be combined with certain crop protection products and formulation ingredients. Furthermore, these water-based SL formulations often have a high pH, ​​which also leads to incompatibility with certain alkali-sensitive crop protection products and formulation ingredients.

[0017] The problem to be solved is therefore to develop a stable formulation consisting of a suspended active ingredient or a suspended combination of active ingredients, which has good bioavailability and permeability of the suspended active ingredient or the suspended combination of active ingredients and has good storage stability at high and low temperatures. The active ingredient is preferably a pesticide.

[0018] This problem is solved by a formulation comprising the active ingredient or a combination of the active ingredient and an ammonium salt and a glycol ether as solvent.

[0019] Therefore, the present invention provides an insecticidal composition comprising:

[0020] a. at least one active ingredient which is solid at room temperature and which is preferably insoluble or slightly soluble in the selected solvent f),

[0021] b. at least one ammonium salt,

[0022] c. at least one dispersant selected from alkyl propoxylated ethoxylates (eg, formula III-a or III-d),

[0023] d. optionally one or more surfactants,

[0024] e. at least one water-insoluble filler,

[0025] f. at least one solvent selected from glycol ethers, and

[0026] g. Optionally, other adjuvants.

[0027] In a preferred embodiment, component d) is essential.

[0028] In another preferred embodiment, component g) is essential.

[0029] In another embodiment, components d) and g) are required.

[0030] Furthermore, the compositions of preferred embodiments are free of water or substantially free of water.

[0031] According to the invention, it has been found that corresponding compositions have a high stability.

[0032] In the present invention, in formulae, for example formula (I), unless otherwise stated, optionally substituted groups may be monosubstituted or polysubstituted, where in the case of polysubstitution the substituents may be identical or different.

[0033] Furthermore, within the preferred ranges described herein, different preference levels are to be understood such that they can be combined with one another in permutations, but in any case the same preference levels, in particular the most preferred embodiments / preferential levels, will in each case be combined with one another and are indeed disclosed in such combinations.

[0034] Compositions described in this application consisting only of the essential components (and not the optional components) are also considered disclosed.

[0035] Unless otherwise stated, room temperature in the context of the present invention refers to a temperature of 20°C to 25°C.

[0036] Components ag are further defined below.

[0037] a. Active ingredient that is solid at room temperature

[0038] The active ingredient which is solid at room temperature is preferably selected from the group consisting of insecticides, herbicides and fungicides. Furthermore, preferably, the selected active ingredient is insoluble or only slightly soluble in the selected solvent f). Furthermore, active insecticidal ingredients which are solid at room temperature and insoluble or only slightly soluble in the selected solvent f) are preferred.

[0039] In the context of the present invention, a sparingly soluble or insoluble active ingredient is an active ingredient which is solid at room temperature and whose solubility in the selected solvent f) at 20° C. is preferably not more than 5 g / L, further preferably not more than 4 g / L, even further preferably not more than 2.5 g / L and particularly preferably not more than 1 g / L.

[0040] Still further preferably, the active ingredient is selected from the group consisting of 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, beta-cyfluthrin, deltamethrin, tetronic acid, cypermethrin, thiamethoxam, cyproconazole, thiamethoxam, cyproconazole, chloranilamide ... acid) and tetramic acid derivatives (IRAC Group 23, including compounds of Formula I and II specified below).

[0041] In a preferred embodiment, component a) of the composition of the present invention is a ketoenol based on tetramic acid, preferably a compound of formula (I)

[0042]

[0043] in

[0044] W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine,

[0045] X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine,

[0046] A, B and the carbon atom to which they are bonded are C3-C6-cycloalkyl, said C3-C6-cycloalkyl being substituted by an alkylenedioxy group which is optionally substituted by a C1-C4-alkyl group or a C1-C4-alkoxy-C1-C2-alkyl group, said alkylenedioxy group together with the carbon atom to which it is bonded forming a 5-membered or 6-membered ketal, G is hydrogen (a) or one of the following groups

[0047] E(d)

[0048] in

[0049] E is a metal ion or an ammonium ion,

[0050] M is oxygen or sulfur,

[0051] R 1 is a linear or branched C1-C6-alkyl group,

[0052] R 2 It is a straight-chain or branched C1-C6-alkyl group.

[0053] Particularly preferably, tetramic acid derivatives of the above-mentioned formula (I) can be used, in which the radicals are defined as follows:

[0054] W is more preferably methyl,

[0055] X is more preferably chlorine or methyl (more preferably methyl),

[0056] Y is more preferably chlorine, bromine or methyl,

[0057] A, B and the carbon atom to which they are bonded are more preferably a saturated C6-cycloalkyl group substituted with an alkylenedioxy group, wherein the alkylenedioxy group together with the carbon atom to which it is bonded forms a 5-membered or 6-membered ketal.

[0058] G is more preferably hydrogen (a) or one of the following groups

[0059] E(d),

[0060] in

[0061] M is oxygen,

[0062] E is a metal ion equivalent or ammonium ion (especially sodium or potassium),

[0063] R 1 More preferably, it is a linear or branched C1-C4-alkyl group,

[0064] R 2 More preferred are linear or branched C1-C4-alkyl groups.

[0065] In particular, use can be made of the above-mentioned tetramic acid derivatives of the formula (I) in which G = hydrogen (a).

[0066] In particular, use may also be made of tetramic acid derivatives of the abovementioned formula (I) in which G═E(d).

[0067] Particularly preferably, tetramic acid derivatives of the above-mentioned formula (I) can be used, in which the radicals are defined as follows:

[0068]

[0069]

[0070]

[0071] In a particularly preferred embodiment, component a) is a compound of the formula:

[0072]

[0073] Compound I-2 is preferably used in its most thermodynamically stable polymorphic form. The crystal structure and other physical data are determined as follows:

[0074] Sample preparation:

[0075] Compound I-2 (C 19 H 22 ClNO4 / MW=363.84 g / mol), and dried at room temperature to obtain modification A.

[0076] Modification A of I-2 can be determined by X-ray powder diffraction at 25 °C and Cu-Kα1 radiation. The corresponding diffraction patterns were recorded below (Figure 1).

[0077] As shown in FIG1 , variant A of the present invention exhibits at least 3, preferably at least 5, further preferably at least 7, even further preferably at least 10 and most preferably all reflections:

[0078] Variant A of the present invention can also be characterized by the X-ray diffraction pattern shown in FIG1 .

[0079] Crystallographic studies of single crystals of modification A have shown that the crystal structure is monoclinic and the unit cell has a P21 / c space group.

[0080] Table 2: Crystallographic properties of variant A

[0081]

[0082]

[0083] a, b, c = lengths of the unit cell sides α, β, γ = angles of the unit cell

[0084] Z = number of molecules in the unit cell

[0085] Table 2a / b: Crystallographic data / reflections [°2θ] of modification A

[0086]

[0087]

[0088] The polymorphic form of modification A of I-1 can be determined by IR spectroscopy using the corresponding spectra at 25° C. using a diamond ATR instrument with a wavelength of 4 cm -1As shown in Table 2c, variant A of the present invention exhibits at least 3, preferably at least 5, further preferably at least 7 and more preferably all bands.

[0089] Table 2c) IR bands [cm -1 ]

[0090]

[0091] In an alternative embodiment, component a) comprises tetramic acid of formula (II)

[0092]

[0093] in

[0094] W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine,

[0095] X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine,

[0096] 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,

[0097] V 2 is hydrogen, halogen, C1-C6-alkyl or C1-C6-alkoxy,

[0098] V 3 is hydrogen or halogen,

[0099] A, B and the carbon atom to which they are bonded are saturated C5-C6-cycloalkyl, one ring member of which is replaced by oxygen, and the saturated C5-C6-cycloalkyl is optionally monosubstituted by C1-C8-alkyl, C1-C8-alkoxy or C1-C6-alkoxy-C1-C6-alkyl,

[0100] G is hydrogen (a) or one of the following groups

[0101] E(d)

[0102] in

[0103] E is a metal ion or an ammonium ion,

[0104] L is oxygen or sulfur, and

[0105] M is oxygen or sulfur,

[0106] R 1is a linear or branched C1-C6-alkyl group,

[0107] R 2 It is a straight-chain or branched C1-C6-alkyl group.

[0108] Particularly preferably, tetramic acid derivatives of the above-mentioned formula (I) can be used, in which the radicals are defined as follows:

[0109] W is more preferably hydrogen or methyl,

[0110] X is more preferably chlorine or methyl,

[0111] Y is more preferably hydrogen,

[0112] V 1 More preferably, it is fluorine or chlorine (especially fluorine or chlorine at the 4-position),

[0113] V 2 More preferably, it is hydrogen or fluorine (especially fluorine at the 3-position),

[0114] V 3 More preferably, it is hydrogen or fluorine (especially fluorine at the 5-position),

[0115] A, B and the carbon atom to which they are bonded are more preferably saturated C6-cycloalkyl, one of the ring members of which is replaced by oxygen,

[0116] G is more preferably hydrogen (a) or one of the following groups

[0117] E(d), where

[0118] More preferably, E is a metal ion equivalent or an ammonium ion (especially sodium or potassium),

[0119] R 1 More preferably, it is a linear or branched C1-C4-alkyl group,

[0120] R 2 More preferred are linear or branched C1-C4-alkyl groups.

[0121] In particular, use can be made of the above-mentioned tetramic acid derivatives of the formula (I) in which G = hydrogen (a).

[0122] In particular, use may also be made of tetramic acid derivatives of the abovementioned formula (I) in which G═E(d).

[0123] Particularly preferably, tetramic acid derivatives of the above-mentioned formula (II) can be used, in which the radicals are defined as follows:

[0124]

[0125] In a particularly preferred alternative embodiment, a) is

[0126]

[0127] b. ammonium salts

[0128] The ammonium salt is preferably selected from water-soluble inorganic ammonium salts.

[0129] Further preferably, b) is selected from ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0130] More preferably, b) is DAHP and AMS.

[0131] c. dispersants

[0132] Component c) is preferably selected from alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a)

[0133] ROABH

[0134] (III-a)

[0135] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0136] A is a polypropylene glycol segment 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,

[0137] B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment, which is composed of 10-50 ethylene oxide (EO) units (Formula III-c) and 0-10 propylene oxide (PO) units, preferably composed of 20-40 EO units and 0-8 PO units, and more preferably composed of 30-40 EO units and 0-5 PO units.

[0138]

[0139] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are:

[0140]

[0141]

[0142] and compounds of formula (IIId)

[0143] RO-(C m H 2m O) x -(C n H2n O) y -R'(IIId)

[0144] The various groups and subscripts have the following definitions:

[0145] R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl;

[0146] m is 2 or 3;

[0147] n is 2 or 3;

[0148] x is 5 to 150; and

[0149] y is 5 to 150,

[0150] Here, the meaning of one of n or m is 2, and the meaning of the other of n or m is 3.

[0151] In the context of the present invention, straight-chain C1- to C5-alkyl is understood to mean methyl, ethyl, n-propyl, n-butyl or n-pentyl.

[0152] In the context of the present invention, branched C3- to C4-alkyl is understood to mean isopropyl, isobutyl or tert-butyl.

[0153] In a preferred embodiment, the R and R' groups are independently selected from methyl, n-butyl and hydrogen.

[0154] In an even more preferred embodiment, the R and R' groups are independently selected from n-butyl and hydrogen.

[0155] Regarding the setup of ethylene oxide and propylene oxide units,

[0156] (a) Alternatively, m can be 2 and n can be 3;

[0157] (b) Alternatively, m can be 3 and n can be 2.

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

[0159] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of the formula (IIId) in which

[0160] m is 3,

[0161] n is 2,

[0162] x is 5 to 80,

[0163] y is 5 to 80,

[0164] R is n-butyl or hydrogen, and

[0165] R' is hydrogen.

[0166] d. In the context of the present invention, suitable surfactants d) are selected from:

[0167] d1) Polycarboxylate surfactants, for example those hydrophobically modified comb polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (for example isobutylene or diisobutylene), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride and styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylic acid esters, copolymers of acrylic acid and vinyl acetate, copolymers of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, copolymers of maleic acid or maleic anhydride and acrylic acid, N-methyl fatty acids (for example C8-C 18 )-sarcosinate, carboxylic acid such as resin acid or fatty acid (e.g. C8-C 18 ) or a salt of such a carboxylic acid. The above 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. Examples of the above include Geopon T / 36, Geopon TA / 72, Tersperse 2700, Atlox Metasperse 550S, Geopon Ultrasperse, Narlex D-72, Versa TL3 and Agrilan 789Dry, and

[0168] d2) surfactants selected from the group consisting of salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, 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 xylyl ether (such as BAYKANOL SL available from Levaco) and sulfated formaldehyde condensation products with cyclohexanone (such as LUCRAMUL DAC 210 available from Levaco), and

[0169] d3) a surfactant selected from lignin sulfonates and salts thereof, preferably selected from the group consisting of 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 available 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 available from Ingevity; T; AGRINOL DN 19 and Agrinol C12 from Tembec, and

[0170] d4) surfactants selected from sulfated alkylarylsulfonates and salts thereof, for example alkylarylsulfonates and salts thereof, such as AEROSOL OS (from Solvay); AGNIQUE ANS 3DNP-U, AGNIQUE ANS 4DNP, AGNIQUE NSC2NP-U, NEKAL BX DRY (from BASF); MORWET B, MORWET DB, MORWET EFW, MORWET IP (from AkzoNobel); OPARYL MT 704, OPARYL MT 800, OPARYL MT 804 (from Bozzetto); RHODACAL BX78, SUPRAGIL WP (from Solvay); SURFOM HRB (from Oxiteno), and

[0171] d5) surfactants selected from di- / tristyrylphenol ethoxylate phosphates and salts thereof: DISPERSOGEN LFH, DISPERSOGEN TP 160 (available from Clariant); LUCRAMUL PPS 16, LUCRAMUL PPS K 16 (available from Levaco); PHOSPHOLAN PHB 14 (available from Akzo Nobel); SOPROPHOR 3D 33, SOPROPHOR TS20-F, SOPROPHOR FL, SOPROPHOR FLK (available from Solvay); STEPFAC TSP-PE, STEPFAC TSP PE-K (available from Stepan); SURFOM 1323SC, SURFOM 1325SC (available from Oxiteno); TERSPERSE 2222 (available from Huntsman); and surfactants selected from alcohol ethoxylate phosphates, for example EMPIPHOS 03D (available from AkzoNobel); MULTITROPE 1214, Crodafos series, Atphos 3226 (available from Croda); PHOSPHOLAN PE 169 (available from Akzo Nobel); RHODAFAC RS-410, RHODAFAC RS-710, RHODAFAC TD 20F (available from Solvay); SERVOXYL VPDZ 20 / 100 (available from Elementis); STEPFAC 8180 (available from Stepan); CRAFOL AP261 (available from BASF); GERONOL CF / AR (available from Clariant).

[0172] Further preferably, suitable surfactants are selected from the group consisting of surfactants d1), d2), d3) and d4).

[0173] Further preferably, suitable surfactants are selected from the group consisting of surfactants d1), d2) and d3).

[0174] Even further preferably, suitable surfactants are selected from the group consisting of surfactants d1) and d2).

[0175] More preferably, suitable surfactants are selected from surfactants d1).

[0176] Very particular preference is given to surfactants selected from d1), 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).

[0177] Suitable surfactants such as Tersperse 2700 are also described in WO 2008036865 A2.

[0178] The above surfactants can be used alone or in combination, preferably a combination of surfactants selected from sodium salts of copolymers of maleic acid and olefins, salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, and lignin sulfonates and their salts.

[0179] e. Water-insoluble fillers

[0180] Suitable fillers are preferably selected from:

[0181] e2) Synthetic silicates and fumed silica, e.g. from or series (Degussa), series (Cabot) or Van Gel series (RT Vanderbilt) silicates, and

[0182] e3) Fillers based on synthetic polymers, e.g. from or Thickener from the Elementis series.

[0183] The filler of e2 is more preferred.

[0184] Particular preference is given to fumed silica as filler e), for example the Aerosil products, Aerosil R products and Cab-O-Sil products, and also attapulgite, both alone and in mixtures.

[0185] f. solvent

[0186] The solvent f) is preferably selected from the compounds represented by formula 4,

[0187]

[0188] in

[0189] y=1-9

[0190] A, B=H, or straight chain alkyl

[0191] M=H, or alkyl

[0192] More preferably, f) is selected from the compound represented by formula 4, wherein

[0193] y=1-3

[0194] A, B=H, or straight chain alkyl

[0195] M=H, or alkyl

[0196] Even further preferably, f) is selected from the compounds represented by formula 4, wherein

[0197] y=1-3

[0198] A, B=H, or methyl

[0199] M=H, or methyl

[0200] Most preferably, f) is selected from the compounds represented by formula 4, wherein

[0201] y=1-2

[0202] If A=H, then B=methyl, if A=methyl, then B=H

[0203] M=H, or methyl

[0204] Examples of solvents f) are Dow's Dowanol glycol ether products, 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).

[0205] Or 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, tripropylene glycol monobenzyl ether).

[0206] g. Other additives

[0207] The compositions according to the invention comprise further adjuvants g), for example substances optionally selected from emulsifiers, moisturizers, foam suppressants, preservatives, dyes, stabilizers and antioxidants.

[0208] Useful emulsifiers include all conventional nonionic, anionic, cationic and zwitterionic substances with surface-active properties commonly 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 and their sulfates, monoesters and diesters of phosphoric acid, as well as ethylene oxide and propylene oxide, and additionally, alkylsulfonates, alkylsulfates, arylsulfates, tetraalkylammonium halides, trialkylarylammonium halides, alkylaminesulfonates, end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxypolyethylene glycol-propylene glycol), and reaction products of polyethylene glycol and polypropylene glycol.

[0209] The emulsifiers can be used alone or in the form of a mixture. Preferred examples include the reaction product of castor oil and ethylene oxide in a molar ratio of 1:20 to 1:60, C6-C 20 The reaction products of alcohols and ethylene oxide, C6-C 20 Reaction products of alcohols with propylene oxide and ethylene oxide, 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 to 3 mol of styrene and 10 to 50 mol of ethylene oxide, C8-C 12 -Alkylphenol reaction products with ethylene oxide, alkyl glycosides, C8-C 16 - Alkylbenzenesulfonates, for example calcium, monoethanolammonium, diethanolammonium and triethanolammonium salts.

[0210] Useful humectants are all substances which can usually be used for this purpose in agrochemical compositions. Preference is given to water-soluble liquids, examples including glycerol, 1,2-propylene glycol and dipropylene glycol.

[0211] Useful foam suppressors are all substances which can usually be used for this purpose in agrochemical compositions. Silicone oils, for example SAG 1572, and magnesium stearate are preferred.

[0212] Useful antioxidants are all substances which can usually be used for this purpose in agrochemical compositions. Butylated hydroxytoluene is preferred.

[0213] Useful dyes are all substances which can usually be used for this purpose in agrochemical compositions. Examples include titanium dioxide, pigment black, zinc oxide and blue pigments as well as permanent red FGR.

[0214] The stabilizer that can be used can be, for example, an acid or a base. 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.

[0215] In a preferred embodiment, the present invention provides an insecticidal composition comprising:

[0216] a. Compounds of formula (I)

[0217]

[0218] The compounds of formula (I) have the following definitions:

[0219] W is a methyl group,

[0220] X is chlorine or methyl,

[0221] Y is chlorine, bromine or methyl,

[0222] A, B and the carbon atom to which they are bonded are saturated C6-cycloalkyl substituted by an alkylenedioxy group, and the alkylenedioxy group together with the carbon atom to which it is bonded forms a 5-membered or 6-membered ketal,

[0223] G is hydrogen (a) or one of the following groups

[0224] E(d),

[0225] in

[0226] M is oxygen,

[0227] E is a metal ion equivalent or ammonium ion,

[0228] R 1 is a straight-chain or branched C1-C4-alkyl group,

[0229] R 2 It is a straight-chain or branched C1-C4-alkyl group.

[0230] b. at least one ammonium salt selected from the group consisting of ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP),

[0231] c. At least one dispersant selected from the group consisting of alkyl polypropylene glycol-polyethylene glycol compounds of formula (III-a)

[0232] ROABH

[0233] (III-a)

[0234] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0235] A is a polypropylene glycol segment 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,

[0236] B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 10-50 ethylene oxide (EO) units (Formula III-c) and 0-10 propylene oxide (PO) units, preferably consisting of 20-40 EO units and 0-8 PO units, more preferably consisting of 30-40 EO units and 0-5 PO units,

[0237]

[0238] and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId)

[0239] RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId)

[0240] The various groups and subscripts have the following definitions:

[0241] R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl;

[0242] m is 2 or 3;

[0243] n is 2 or 3;

[0244] x is 5 to 150; and

[0245] y is 5 to 150,

[0246] Where one of n or m means 2, and the other of n or m means 3,

[0247] d. at least one surfactant selected from the group consisting of polycarboxylates, salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, salts of sulfated formaldehyde condensation products with xylyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, lignin sulfonates and salts thereof, sulfated alkylaryl sulfonates and salts thereof;

[0248] e. at least one filler selected from modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite and synthetic polymer-based fillers;

[0249] f. at least one solvent selected from the compound represented by formula 4, wherein

[0250]

[0251] y=1-9

[0252] A, B=H, or straight chain alkyl

[0253] M=H, or alkyl

[0254] g. Other additives.

[0255] In a further preferred embodiment, the present invention provides an insecticidal composition comprising:

[0256] a. a compound of formula (I) selected from the group consisting of:

[0257]

[0258]

[0259] b. at least one ammonium salt selected from the group consisting of ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP),

[0260] c. At least one dispersant selected from the group consisting of alkyl polypropylene glycol-polyethylene glycol compounds of formula (III-a)

[0261] ROABH

[0262] (III-a)

[0263] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0264] A is a polypropylene glycol segment 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,

[0265] B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 10-50 ethylene oxide (EO) units (Formula III-c) and 0-10 propylene oxide (PO) units, preferably consisting of 20-40 EO units and 0-8 PO units, more preferably consisting of 30-40 EO units and 0-5 PO units,

[0266]

[0267] and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId)

[0268] RO-(C m H2m O) x -(C n H 2n O) y -R' (IIId)

[0269] The various groups and subscripts have the following definitions:

[0270] R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl;

[0271] m is 2 or 3;

[0272] n is 2 or 3;

[0273] x is 5 to 150; and

[0274] y is 5 to 150,

[0275] Where one of n or m means 2, and the other of n or m means 3,

[0276] d. at least one surfactant selected from the group consisting of polycarboxylates, salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, salts of sulfated formaldehyde condensation products with xylyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, and lignin sulfonates and their salts,

[0277] e. at least one filler selected from modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite and synthetic polymer-based fillers;

[0278] f. at least one solvent selected from the compound represented by formula 4, wherein

[0279]

[0280] Formula 4

[0281] y=1-3

[0282] A, B=H, or straight chain alkyl

[0283] M=H, or alkyl

[0284] g. Other additives.

[0285] In a further preferred embodiment, the present invention provides an insecticidal composition comprising:

[0286] a. a compound of formula (I-2) having the following structure:

[0287]

[0288] b. at least one ammonium salt selected from ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP),

[0289] c. At least one dispersant selected from the group consisting of alkyl polypropylene glycol-polyethylene glycol compounds of formula (III-a)

[0290] ROABH

[0291] (III-a)

[0292] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0293] A is a polypropylene glycol segment 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,

[0294] B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 10-50 ethylene oxide (EO) units (Formula III-c) and 0-10 propylene oxide (PO) units, preferably consisting of 20-40 EO units and 0-8 PO units, more preferably consisting of 30-40 EO units and 0-5 PO units,

[0295]

[0296] and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId)

[0297] RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId)

[0298] The various groups and subscripts have the following definitions:

[0299] R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl;

[0300] m is 2 or 3;

[0301] n is 2 or 3;

[0302] x is 5 to 150; and

[0303] y is 5 to 150,

[0304] Where one of n or m means 2, and the other of n or m means 3,

[0305] d. at least one surfactant selected from the polycarboxylate type,

[0306] e. at least one filler selected from fumed silica and attapulgite;

[0307] f. at least one solvent selected from the compound represented by formula 4, wherein

[0308]

[0309] y=1-3

[0310] A, B=H, or methyl

[0311] M=H, or methyl

[0312] g. Other additives.

[0313] In a most preferred embodiment, the present invention provides an insecticidal composition comprising:

[0314] a. a compound of formula (I-2) having the following structure:

[0315]

[0316] b. at least one ammonium salt selected from ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP),

[0317] c. At least one dispersant selected from the group consisting of alkyl polypropylene glycol-polyethylene glycol compounds of formula (III-a)

[0318] ROABH

[0319] (III-a)

[0320] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0321] A is a polypropylene glycol segment 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,

[0322] B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 10-50 ethylene oxide (EO) units (Formula III-c) and 0-10 propylene oxide (PO) units, preferably consisting of 20-40 EO units and 0-8 PO units, more preferably consisting of 30-40 EO units and 0-5 PO units,

[0323]

[0324] and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId)

[0325] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0326] The various groups and subscripts have the following definitions:

[0327] R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl;

[0328] m is 2 or 3;

[0329] n is 2 or 3;

[0330] x is 5 to 150; and

[0331] y is 5 to 150,

[0332] Where one of n or m means 2, and the other of n or m means 3,

[0333] d. at least one surfactant selected from the polycarboxylate type,

[0334] e. at least one filler selected from fumed silica and attapulgite;

[0335] f. at least one solvent selected from the compound represented by formula 4, wherein

[0336]

[0337] y=1-2

[0338] If A=H, then B=methyl, if A=methyl, then B=H

[0339] M=H, or methyl

[0340] g. Other additives.

[0341] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure.

[0342] Unless otherwise indicated, percentages are to be considered as percentages by weight, wherein the weight percents of the composition total 100.

[0343] The proportions of the following components are each based on the total weight of the composition, wherein the proportion of the entire composition to 1 liter is made up by component f) (solvent). Therefore, the proportion of component f) is preferably 1% to 80% by weight, more preferably 20-60% by weight.

[0344] The proportion of the solid active ingredient (component a) in the composition of the present invention is

[0345] Preferably 0.5-30% by weight,

[0346] More preferably, 1-20% by weight, and

[0347] More preferably 1-15% by weight,

[0348] Most preferably, it is 1.5-5% by weight.

[0349] The ratio of ammonium salt (component b) in the composition of the present invention is

[0350] Preferably 1-40% by weight,

[0351] More preferably, 5-35% by weight, and

[0352] More preferably, it is 15-30% by weight.

[0353] The proportion of the dispersant (component c) in the composition of the present invention is

[0354] Preferably 0.5-40% by weight,

[0355] More preferably, 5-35% by weight, and

[0356] More preferably, it is 10-30% by weight.

[0357] The ratio of surfactant (component d) in the composition of the present invention is

[0358] Preferably 0-10% by weight

[0359] More preferably, 0.3-8% by weight, and

[0360] More preferably, it is 0.5-5% by weight.

[0361] The proportion of filler (component e) in the composition is

[0362] Preferably 0.1-10% by weight

[0363] More preferably, 0.5-10% by weight, and

[0364] More preferably, it is 1-5% by weight.

[0365] The ratio of other adjuvants (component g) in the composition of the present invention is

[0366] Preferably 0-20% by weight,

[0367] More preferably, 1-20% by weight,

[0368] More preferably, 2.5-17.5 wt %, and

[0369] More preferably, it is 5-15% by weight.

[0370] A preferred embodiment of the present invention is a composition comprising the following components:

[0371] a) 0.5-30 wt%

[0372] b) 1-40% by weight

[0373] c) 0.5-40% by weight

[0374] d) 0-10% by weight

[0375] e) 0.1-10% by weight

[0376] g) 0-20% by weight

[0377] f) Make up to 1 litre.

[0378] A further preferred embodiment of the present invention is a composition comprising: a) 1-20% by weight

[0379] b) 5-35 wt%

[0380] c) 5-35% by weight

[0381] d) 0.3-8% by weight

[0382] e) 0.5-10% by weight

[0383] g) 1-20% by weight

[0384] f) Make up to 1 litre.

[0385] A further preferred embodiment of the present invention is a composition comprising: a) 1-20% by weight

[0386] b) 5-35 wt%

[0387] c) 5-35% by weight

[0388] d) 0.3-8% by weight

[0389] e) 0.5-10% by weight

[0390] g) 2.5-17.5 wt%

[0391] f) Make up to 1 litre.

[0392] A more preferred embodiment of the present invention is a composition comprising the following components:

[0393] a) 1-15 wt%

[0394] b) 15-30% by weight

[0395] c) 10-30% by weight

[0396] d) 0.5-5% by weight

[0397] e) 1-5% by weight

[0398] g) 5-15% by weight

[0399] f) Make up to 1 litre.

[0400] A most preferred embodiment of the present invention is a composition comprising the following components:

[0401] a) 1.5-5% by weight

[0402] b) 15-30% by weight

[0403] c) 10-30% by weight

[0404] d) 0.5-5% by weight

[0405] e) 1-5% by weight

[0406] g) 5-15% by weight

[0407] f) Make up to 1 litre.

[0408] The present invention also relates to an adjuvant combination for use in an insecticidal active ingredient formulation having at least one active ingredient in solid form to improve the permeability of the two active ingredients, the adjuvant combination comprising:

[0409] b. at least one ammonium salt, and

[0410] c. At least one dispersant selected from the group consisting of alkyl propoxylate ethoxylates.

[0411] In a preferred embodiment, the auxiliary agent combination further comprises

[0412] f. a solvent selected from a compound represented by formula 4, wherein

[0413]

[0414] y=1-9

[0415] A, B=H, or straight chain alkyl

[0416] M=H, or alkyl

[0417] The ammonium salt of the auxiliary agent combination is preferably selected from water-soluble inorganic ammonium salts.

[0418] Further preferably, b) is selected from ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0419] More preferably, b) is DAHP and AMS.

[0420] Component c) of the auxiliary combination (dispersant) is preferably selected from the group consisting of alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a)

[0421] ROABH

[0422] (III-a)

[0423] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0424] A is a polypropylene glycol segment 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,

[0425] B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment, which is composed of 10-50 ethylene oxide (EO-) units (Formula III-c) and 0-10 propylene glycol (PO-) units, preferably composed of 20-40 EO units and 0-8 PO units, and more preferably composed of 30-40 EO units and 0-5 PO units.

[0426]

[0427] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are:

[0428]

[0429] and compounds of formula (IIId)

[0430] RO-(C m H 2m O) x -(C n H 2n O) y -R'(IIId)

[0431] The various groups and subscripts have the following definitions:

[0432] R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl;

[0433] m is 2 or 3;

[0434] n is 2 or 3;

[0435] x is 5 to 150; and

[0436] y is 5 to 150,

[0437] Here, the meaning of one of n or m is 2, and the meaning of the other of n or m is 3.

[0438] In the context of the present invention, straight-chain C1- to C5-alkyl is understood to mean methyl, ethyl, n-propyl, n-butyl or n-pentyl.

[0439] In the context of the present invention, branched C3- or C4-alkyl is understood to mean isopropyl, isobutyl or tert-butyl.

[0440] In a preferred embodiment, the R and R' groups are independently selected from methyl, n-butyl and hydrogen.

[0441] In an even more preferred embodiment, the R and R' groups are independently selected from n-butyl and hydrogen.

[0442] Regarding the setup of ethylene oxide and propylene oxide units,

[0443] (a) Alternatively, m can take the value 2 and n can take the value 3;

[0444] (b) Alternatively, m can be 3 and n can be 2.

[0445] Configuration (b) is preferred, wherein m=3 and n=2.

[0446] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of the formula (IIId) in which

[0447] m is 3,

[0448] n is 2,

[0449] x is 5 to 80,

[0450] y is 5 to 80,

[0451] R is n-butyl or hydrogen, and

[0452] R' is hydrogen.

[0453] The solvent f) used in combination with the auxiliary agent is further preferably selected from the compound represented by formula 4, wherein

[0454]

[0455] y=1-3

[0456] A, B=H, or straight chain alkyl

[0457] M=H, or alkyl

[0458] More preferably, f) is selected from the compound represented by formula 4, wherein

[0459] y=1-3

[0460] A, B=H, or methyl

[0461] M=H, or methyl

[0462] Most preferably, f) is selected from the compounds represented by formula 4, wherein

[0463] y=1-2

[0464] If A=H, then B=methyl, if A=methyl, then B=H

[0465] M=H, or methyl.

[0466] A preferred embodiment of the present invention is an auxiliary combination whose ratio of b) to c) (in each case based on mass) is from 3:1 to 1:3, preferably from 2:1 to 1:2, more preferably from 1.3:1 to 1:1.3.

[0467] Based on the weight of the entire preparation, the proportion of the auxiliary agent combination is preferably

[0468] b) 1-40% by weight

[0469] c) 1-40% by weight

[0470] Further optimization

[0471] b) 5-35 wt%

[0472] c) 5-35% by weight, and

[0473] Even more preferred

[0474] b) 15-30% by weight

[0475] c) 10-30% by weight.

[0476] The application rate of the formulations according to the invention can be varied within a relatively wide range. The application rate is determined by the respective active ingredient and its content in the composition. The application rate of the formulations according to the invention in the aqueous spray solution can also be varied within a relatively wide range, meaning that the applicable spray volume can vary from 10 to 500 l / ha.

[0477] With the aid of the compositions according to the invention, insecticidal active ingredient mixtures can be applied in a particularly advantageous manner to plants and / or their habitat.

[0478] The composition of the present invention can be used for processing all plants and plant parts.In this article, plant should be understood to include all plants and plant populations, such as needed and unwanted 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 the combination of these methods, including transgenic plants and including plant cultivars that may or may not be protected by plant breeders' rights.Plant parts should be understood to mean all positions and organs on the ground and underground of plant, such as bud, leaf, flower and root, and examples are leaf, needle, stem, dry, flower, fruiting body, fruit and seed, and tuber, root and rhizome.Plant parts also include harvested material and asexual and sexual propagation materials, such as cuttings, tuber, rhizome, bud and seed.

[0479] Preferably, the formulations of the present invention are used after spray application to combat animal pests from the following pest families:

[0480] Preference is given to woolly aphid family (Pemphigidae): Eriosoma spp., Pemphigus spp. in crops such as citrus fruits, pome fruits, stone fruits, leafy vegetables, root and tuber vegetables and ornamental plants.

[0481] Preference is given to grape lice family (Phylloxeridae): Phylloxera spp. in grapes, nuts, citrus fruits.

[0482] Preference is given to the family of jumping plant lice (Psyllidae): Psylla spp., Paratrioza spp., Tenalaphara spp., Diaphorina spp., Trioza spp. in crops, tropical crops, such as pome fruits, stone fruits, citrus fruits, vegetables, potatoes.

[0483] Preference is given to the soft scale family (Coccidae): Ceroplastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., Coccus spp. in perennial crops such as citrus fruits, pome fruits, stone fruits, olives, grapes, coffee, tea, tropical crops, ornamentals, vegetables.

[0484] Preferred are armored scale insects (Diaspididae): Quadraspidiotus spp., Aonidiella spp., Lepidosaphes spp., Aspidiotus spp., Aspis spp., Diaspis spp., Parlatoria spp., Pseudaulacaspis spp., Unaspis spp., Pinnaspis spp., Selenaspidus spp., and other insects in crops. spp.), such as citrus fruits, pome fruits, stone fruits, almonds, pistachios, nuts, olives, tea, ornamentals, grapes, tropical crops.

[0485] Preferred are the ensign scale family (Ortheziidae): Orthezia spp. in citrus fruits, pome fruits, stone fruits.

[0486] Preference is given to the mealy bug family (Pseudococcidae): Pericerga spp., Pseudococcus spp., Planococcus spp., Dysmicoccus spp. in crops such as citrus fruits, stone and pome fruits, tea, grapes, vegetables, ornamentals and tropical crops.

[0487] Preference is given to the family of whiteflies (Aleyrodidae): Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes species, Dialeurodes spp., Parabemisia myricae in crops such as vegetables, melons, potatoes, tobacco, soft fruits, citrus fruits, ornamentals, cotton, soybeans and tropical crops.

[0488] Furthermore, preference is given to the aphid family (Aphidae):

[0489] Myzus spp. in tobacco, stone fruits, soft fruits, fruiting vegetables, leafy vegetables, tuber and root vegetables, melons, potatoes, ornamentals, and spice crops.

[0490] Acyrthosiphon onobrychis in vegetables,

[0491] Aphis spp. in tobacco, citrus fruits, pome fruits, stone fruits, melons, strawberries, soft fruits, fruiting vegetables, leafy vegetables, tubers, stem and root vegetables, ornamentals, potatoes, pumpkins, spice crops,

[0492] Rose aphid (Rhodobium porosum) in strawberries,

[0493] Blackcurrant aphid (Nasonovia ribisnigri) in leafy vegetables,

[0494] Macrosiphum spp. in ornamental plants, potatoes, leafy and fruiting vegetables, and strawberries.

[0495] Phorodon humuli in hops,

[0496] Cabbage aphid (Brevicoryne brassicae) in leafy vegetables,

[0497] Toxoptera spp. in citrus fruits, stone fruits, almonds, nuts, and spice crops,

[0498] Aulacorthum spp. in citrus fruits, potatoes, fruiting vegetables and leafy vegetables,

[0499] Anuraphis cardui in vegetables,

[0500] Brachycaudus helycrisii in sunflowers,

[0501] Acyrthosiphon onobrychis in vegetables.

[0502] Likewise, preference is given to 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. in crops. spp.), such as fruit, cotton, grapes, tea, nuts, tropical crops, ornamentals, conifers, tobacco, spice crops, vegetables, soft fruit, melons, citrus fruits, and potatoes.

[0503] Furthermore, preference is given to the families of leaf-miner flies (Agromyzidae) and root-maggot flies (Anthomyiidae): Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., Pegomyia spp. in crops, for example vegetables, melons, potatoes, nuts, ornamentals.

[0504] Preference is given to the family of leafhoppers (Cicadellidae) and planthoppers (Delphacidae): Circulifer spp., Dalbus spp., Empoasca spp., Erythroneura spp., Homalodisca spp., Iodioscopus spp., Laodelphax spp., Nephotettix spp., Nilaparvata spp., Oncometopia spp., Sogatella spp. in crops such as citrus fruits, fruit, grapes, potatoes, vegetables, ornamentals, conifers, melons, soft fruit, tea, nuts, rice and tropical crops.

[0505] Preferred are the leaf-miner moth family (Gracillariidae):

[0506] Caloptilia spp., Gracillaria spp., Lithocolletis spp., Leucoptera spp., Phtorimaea spp., Phyllocnistis spp. in crops such as pome fruits, stone fruits, grapes, nuts, citrus fruits, conifers, potatoes, coffee.

[0507] Gall midge family (Cecidomyiidae) is preferred:

[0508] Contarinia spp., Dasineura spp., Diplosis spp., Prodiplosis spp., Thecodiplosis spp., Sitodiplosis spp., Haplodiplosis spp. in crops such as citrus fruits, pome fruits, stone fruits, vegetables, potatoes, spice crops, soft fruits, conifers, hops.

[0509] Likewise, the fruit fly family (Tephritidae) is preferred:

[0510] Anastrepha spp., Ceratitis spp., Dacus spp., Rhagoletis spp. in crops such as vegetables, soft fruit, melons, pome and stone fruit, ornamentals, potatoes, grapes, tropical crops, citrus fruit, olives.

[0511] Furthermore, mites of the spider mite family (Tetranychidae) and the gall mite family (both Eriophydae) are preferred:

[0512] Tetranychus spp., Panonychus spp., Aculops spp. in crops such as vegetables, potatoes, ornamentals, citrus fruits, grapes, conifers.

[0513] The treatment of plants and plant parts with the composition according to the invention is carried out directly or by allowing the composition to act on their surroundings, environment or storage space by customary treatment methods, such as drenching, impregnation, spraying, evaporation, fogging, scattering, painting and, in the case of propagation material, in particular seeds, also by applying one or more coatings.

[0514] Preferably, the plants to be treated are selected from the group consisting of cotton, soybeans, tobacco, vegetables, spice crops, ornamentals, conifers, citrus plants, fruits, tropical crops, nuts and grapes.

[0515] Preferably, the composition of the present invention is used to combat pests of the family Aphididae, Phylloxera, Psyllids, Soft Scale, Shield Scale, Flag Scale, Mealybugs, Whiteflies, Aphids, Thrips, Leafhoppers, Planthoppers, Leafminers, Gall Midges, Fruit Flies, Leafminers, Spider Mites, and the family Mycoides.

[0516] It has also been found that the composition of the present invention can be prepared by a process having the following steps:

[0517] 1) Mixing of components (a) to (g), followed by homogenization and bead milling. The relevant equipment for homogenization and bead milling is known to those skilled in the art.

[0518] This method also forms part of the subject matter of the present invention.

[0519] Finally, it has been found that the compositions of the present invention are very suitable for applying the active agrochemical ingredients present to plants and / or their habitats. This method also forms part of the subject matter of the present invention. The following examples illustrate the subject matter of the present invention without limiting the subject matter of the present invention.

[0520] Materials used in the examples:

[0521]

[0522]

[0523] Tests and Methods Used in the Examples

[0524] The evaluation of the formulation characteristics was carried out similarly to DIN 10964 "Sensory analysis - Simple descriptive test". For this purpose, the samples to be examined were inspected visually, and if necessary, by shaking and tilting, their shape, state of matter, color and other characteristics (especially for example lumps, caking, sediment formation, subsequent thickening, marbling of sediments, etc.) were examined.

[0525] Rotational viscosity Measured according to CIPAC MT 192. Stable and convenient formulations are expected to exhibit a medium range of viscosities in order to empty and clean the bottles conveniently.

[0526] Rheology Measured using a Bohlin Gemini rheometer. The measurements of G' (elastic modulus), G" (viscous modulus) and phase angle were carried out at room temperature using a sweep frequency program with strain or stress control at different frequencies (between 0.01 - 5 Hz). The reported data were obtained at 0.5 Hz / 20 °C. It is generally accepted by those skilled in the art that small phase angle and large G' (> G") data indicate a high possibility of a stable formulation, while large phase angle and small G' (< G") data indicate a high possibility of a less stable formulation.

[0527] granularity Determined by laser diffraction according to CIPAC MT 187 Malvern Mastersizer (medium: propylene glycol) or by using an optical microscope (40-fold magnification). Stable and convenient formulations are expected to contain small particles to ensure good storage stability in the concentrate and good suspension stability in the aqueous diluent.

[0528] Agglomeration Determined by using an optical microscope (40-fold magnification). Stable and convenient formulations are expected to be free of agglomerates to ensure good storage stability in the concentrate and good suspension stability in the aqueous diluent.

[0529] Suspension stability Evaluated according to the simplified method of CIPAC MT 180, measured in a 2% aqueous dilution of CIPAC C water or CIPAC D water, after standing for 1 hour. Stable and convenient formulations are expected to form little or no sediment at the bottom of the test container, ensuring uniform application of the spray solution.

[0530] Storage stability The tests were performed at different temperatures, e.g. 0°C, 20°C, 30°C, 40°C, 54°C or thaw-freeze cycles (=TW; constant temperature change from -15°C to +30°C with recovery within one week) over a given number of weeks (w).

[0531] Sample Redispersibility Determined qualitatively by shaking the sample and subsequently evaluating the bottom of the sample container.

[0532] Directly after storage Phase separation It is reported as the sediment fraction and is calculated by dividing the quotient H1 [the level of the interface layer between the sediment phase and the supernatant] by H0 [the total filling height of the sample], or as in the present case, as the supernatant fraction:

[0533] Sediment fraction = (H1 / H0) × 100 [%] or supernatant fraction = 100 - sediment content [%]

[0534] It is expected that a stable and convenient formulation will exhibit little or no phase separation upon prolonged storage at elevated temperatures and will be readily rehomogenizable. Significant phase separation after short storage periods indicates limited storage stability and a pronounced tendency to form sediments that are extremely difficult, if any, to disperse during storage.

[0535] Example 1

[0536] All formulation ingredients of the experiments described in Table 1a-c were combined in 25ml PE screw cap bottles and 10g of glass beads (size 1-1.25mm) were added. The bottles were closed, clamped in a stirrer device (Retsch MM301), and processed at 30Hz for 40 minutes; in the process, the samples were heated. After a period of time, the samples were cooled to room temperature and the consistency of the formulations was assessed. Subsequently, the particle size was determined by laser scattering and the properties of the dispersions were assessed using a microscope (Zeiss transmitted light microscope, 40 times magnification). Very small particle sizes indicated good grindability, while the presence of agglomerates indicated poor dispersion properties.

[0537]

[0538] Experimental evaluation:

[0539] Formulations based on I-2, ammonium salts, and Dowanol DPM with varying amounts of surfactant (Experiments 1-1, 1-2) showed substantial grindability of the respective ammonium salts and I-2 under the specified experimental conditions, but unless sufficient surfactant (>1%) was present in the formulation, significant agglomeration of salt crystals in the concentrate was observed under the microscope, implying that the dispersion of the individual particles in the liquid phase was very poor, if any. Only certain surfactants were able to adequately disperse the ammonium salts and I-2 (e.g., 1-2, 1-7), while alkyl propoxylated ethoxylates alone were unable to do so, as evidenced by the high viscosity and presence of agglomerates in the sample (1-9) ground with only Antarox B / 848.

[0540] The most effective and surprising combination of two different surfactants in small amounts (Experiments 1-10 to 1-14) was particularly surprising because 1.00% of each surfactant was more effective at grinding and stabilizing DAHP or AMS than 5.00% of each surfactant alone.

[0541] Example II

[0542] To test suitable thickeners and carriers in the presence of suitable dispersing aids, all formulation ingredients specified in Table 2, Table 3, and Table 4 were combined and milled by one of the following methods:

[0543] 1) The formulation components were homogenized using a colloid mill and subsequently ground in a bead mill (Dispermat SL50, 80% 2 mm beads, 4000 rpm, 40 min of recirculation grinding). After a period of time, the sample was cooled to room temperature and the rheological properties of the formulation were evaluated.

[0544] 2) The formulation components were mixed in a bottle, which was then sealed, clamped to a stirrer (Retsch MM301), and stirred at 30 Hz for 40 minutes; during this process, the sample heated up. After this period, the sample was cooled to room temperature, and the rheological properties of the formulation were evaluated.

[0545] The rheological properties of the formulations were evaluated using a Gemini rheometer (Bohlin Instruments). G' (elastic modulus), G' (viscous modulus), and phase angle were measured at room temperature using a frequency sweep program with strain or stress control at different frequencies (between 0.01 and 5 Hz). Viscosity was assessed according to CIPAC MT192, "Viscosity of Liquids by Rotational Viscometry," at room temperature.

[0546]

[0547] Experimental evaluation in Table 2:

[0548] The formulation using Aerosil R812 S (Example No. 2-2) is the only formulation with a low phase angle, indicating that these formulations have much higher elastic characteristics and are therefore expected to be more stable in terms of sedimentation stability. In addition, the sedimentation stability of Example 2-2 does not have the high viscosity observed in other examples, which have much higher dynamic viscosities than Example 2-2 at a low shear rate of 1 / 24.

[0549]

[0550]

[0551] Experimental evaluation in Table 3:

[0552] The formulations using dipropylene glycol monomethyl ether (Examples 3-1, 3-2, and 3-3) all exhibited very good rheological properties, namely high elasticity (low phase angle <30°) and shear thinning properties. Formulations containing propylene glycol (Example 3-1) or dipropylene glycol (Example 3-2) also had relatively low viscosities (<700 mPas@24 / s) at low shear rates. Other carriers such as 1-methoxy-2-propanol (Example 3-4) or diethylene glycol monomethyl ether (Example 3-5) also provided formulations with low phase angles, and in the case of Example 3-4, relatively low viscosities at low shear rates. Due to its very high viscosity, PEG 400 did not produce a processable formulation (Example 3-6), but this could be improved by adding some propylene glycol (Example 3-11), making the formulation more elastic (phase angle 23°@0.5Hz) and easier to handle in terms of viscosity (114 mPas@24Hz). Neither tripropylene glycol monomethyl ether (Example 3-7) nor dipropylene glycol monopropyl ether (Example 3-9) produces enough elasticity in the formulation to expect a product that is stable with respect to sedimentation. This can be seen in the very high phase angles (>45°) of the formulations, which indicate a predominantly viscous behavior. By adding propylene glycol, both formulations can still be converted to being predominantly elastic (phase angle <45°): Examples 3.8 and 3.10 have phase angles @ 0.5 Hz of 39° and 34°, respectively.

[0553]

[0554] Experimental evaluation in Table 4:

[0555] Preparation of the present invention can be prepared with different amounts of active ingredients without losing their satisfactory rheological properties. In fact, formulation examples 4-1, 4-2, and 4-3 all maintain elastic rheological properties (phase angle < 30 °) while showing shear-thinning behavior. In addition, it is not necessary to use a large amount of surfactants to control the rheological behavior of the preparation, as can be seen from the properties of formulation example 4-4, which demonstrates a high phase angle (> 45 °), which is attributed to the high concentrations of dispersants Geropon T-36 and Morwet D-425. As can be seen in formulation example 4-5, the surfactant concentration of 0.5% is compatible with the high elasticity (phase angle 16 °) and shear-thinning behavior of the preparation.

[0556] Example III

[0557] To test the long-term stability of the most suitable formulation, a suitable thickener was combined in the presence of a suitable dispersing aid as specified in Table 5 and milled by one of the following methods:

[0558] 1) The formulation components were homogenized using a colloid mill and subsequently ground in a bead mill (Dispermat SL50, 80% 2 mm beads, 4000 rpm, 40 min of recirculation grinding). After a period of time, the sample was cooled to room temperature and the rheological properties of the formulation were evaluated.

[0559] 2) The formulation components were mixed in a bottle, which was then sealed, clamped to a stirrer (Retsch MM301), and stirred at 30 Hz for 40 minutes; during this process, the sample heated up. After this period, the sample was cooled to room temperature and the rheological properties of the formulation were evaluated.

[0560] Subsequently, storage tests were performed at elevated temperatures, followed by qualitative / quantitative evaluation of appearance, phase separation, rheological properties and dispersion stability after storage (e.g., viscosity), and active ingredient concentration.

[0561] The appearance is assessed analogously to DIN 10964 "Sensory analysis - Simple descriptive test". For this purpose, the sample to be tested is visually inspected, if necessary by shaking and tilting, to check its shape, the state of the substance, the color, and other properties (e.g., in particular, the presence of lumps, agglomerates, sediment formation, subsequent thickening, marbling of the sediment, etc.).

[0562] Phase separation directly after storage is reported as sediment content and is calculated by the quotient H1 [level of the interface layer between the sediment phase and the supernatant] divided by H0 [total filling height of the sample], or in this context by the supernatant content:

[0563] Sediment content = (H1 / H0) × 100 [%] or supernatant content = 100 - sediment content [%]

[0564] The rheological properties of the formulations were evaluated using a Gemini rheometer (Bohlin Instruments). G' (elastic modulus), G' (viscous modulus), and phase angle were measured at room temperature using a frequency sweep program with strain or stress control at different frequencies (between 0.01 and 5 Hz). Viscosity was assessed according to CIPAC MT192, "Viscosity of Liquids by Rotational Viscometry," at room temperature.

[0565] The dispersion stability in a 2% aqueous dilution is determined in accordance with the CIPAC MT 180 method “Dispersionstability of suspo-emulsions” by analyzing the residual amount deposited after a certain time.

[0566]

[0567]

[0568]

[0569]

[0570] Experimental evaluation in Table 5:

[0571] Using different combinations of fillers such as Aerosil R812S and propylene glycol / dipropylene glycol monomethyl ether, stable formulations with varying viscosities can be prepared (Formulations 5-1 and 5-2). Both formulations were stable during storage and exhibited very good sedimentation stability. After four weeks of storage at either room temperature or 54°C, very little phase separation was observed for both Examples 5-1 and 5-2.

[0572] Both Examples 5-1 and 5-2 developed more elastic rheological behavior during storage at room temperature. It can be seen that the initially high phase angle becomes significantly smaller (<35°) after 4 weeks at room temperature. This increase in elastic rheological behavior translates into increased sedimentation stability. Particularly advantageously, Example 5-1 exhibits greater elasticity (and therefore greater stability) than Example 5-2 without a proportional increase in viscosity.

[0573] Another factor used to determine formulation stability is the dispersion stability of the formulation in aqueous diluents. Examples 5-1 and 5-2 were both dispersible in water, and after storage at room temperature or 54°C, in some cases, the phase separation of the diluted formulations was relatively small (<=0.1 mL).

[0574] The use of fillers other than silica-based Aerosil R812S results in formulations with significant drawbacks. Take Comparative Examples 5-3, 5-4, and 5-5, which use organoclay-based fillers Bentone 34, Bentone 38, and Bentone LT, respectively, as examples. In the case of 5-3 and 5-4, the use of these organoclay fillers results in formulations with very high viscosities, which increase during storage. This increase in viscosity ultimately causes Comparative Examples 5-3 and 5-4 to become solid at some point during storage and only become flowable after vigorous shaking.

[0575] Furthermore, the dispersion stability behavior of Comparative Examples 5-3, 5-4, and 5-5 was significantly worse than that of Inventive Examples 5-1 and 5-2. Indeed, after one hour of dispersion in water, the Comparative Examples produced a significant amount of sediment, while the Inventive Examples showed virtually no sedimentation of insoluble material. This is an advantage over the Inventive Examples, as insoluble residues produced by the Comparative Examples could, for example, clog administration equipment or negatively impact the bioavailability of the active ingredient.

[0576] In summary, silica fillers (inventive examples) and organoclay fillers (comparative examples) have different technical properties, and the inventive examples have significant advantages in terms of viscosity and handling, as well as the usability of the formulation when dispersed in water. In addition, the use of fumed silica results in stable formulations (very limited phase separation during storage) without the very high viscosity measured in some comparative examples. Therefore, the use of silica fillers in the inventive examples in Table 5 is an improvement over the comparative examples based on organoclay fillers in Table 5.

Claims

1. A composition comprising: a) 1-20% by weight of a compound of formula (I-2) b) 5 to 35% by weight of at least one ammonium salt selected from ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate, ammonium hydrogen carbonate and diammonium hydrogen phosphate, c) 5-35% by weight of at least one dispersant selected from the group consisting of alkyl propoxylate ethoxylates, selected from Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) R—O—A—B—H (III-a) Wherein R is a C1-C4 fragment, A is a polypropylene glycol segment consisting of 10 to 40 propylene oxide (PO) units of formula III-b, B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 10-50 ethylene oxide (EO) units of formula III-c together with 0-10 propylene oxide (PO) units, and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R' (IIId) in R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, Where one of n or m means 2, and the other of n or m means 3, d) 0.3 to 8% by weight of a combination of sodium salts of copolymers of maleic acid and olefins and salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, e) 0.5 to 10% by weight of at least one partially hydrophobic fumed amorphous silica, f) at least one solvent selected from dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and diethylene glycol monomethyl ether, as well as, g) 1-20% by weight of other additives; in, f) is added to make up the volume of the composition to 1 liter.

2. The composition according to claim 1, characterized in that b) is selected from ammonium sulfate and diammonium hydrogen phosphate.

3. The composition according to claim 1, characterized in that d) is a combination of maleic anhydride 2,4,4-trimethylpentene polymer sodium salt and condensed naphthalene formaldehyde sulfonate sodium salt.

4. The composition according to claim 1, characterized in that The components are present as follows: a) 1.5-5% by weight b) 15-30% by weight, c) 10-30% by weight, d) 0.5-5% by weight e) 1 to 5% by weight, and g) 5-15% by weight.

5. The composition according to claim 1, characterized in that c) a dispersant selected from alkyl propoxylated ethoxylates selected from Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) R—O—A—B—H (III-a) Wherein R is a C3-C4 fragment, A is a polypropylene glycol segment consisting of 15 to 35 propylene oxide (PO) units of formula III-b, B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 20-40 ethylene oxide (EO) units of formula III-c and 0-8 propylene oxide (PO) units, and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R' (IIId) in R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, Here, the meaning of one of n or m is 2, and the meaning of the other of n or m is 3.

6. The composition according to claim 1, characterized in that c) a dispersant selected from alkyl propoxylated ethoxylates selected from Alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a) R—O—A—B—H (III-a) Where R is the C4 fragment, A is a polypropylene glycol segment consisting of 20-30 propylene oxide (PO) units of formula III-b, B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 30-40 ethylene oxide units (EO) of formula III-c together with 0-5 propylene oxide (PO) units, and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R' (IIId) in R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, Here, the meaning of one of n or m is 2, and the meaning of the other of n or m is 3.

7. A composition comprising: a) 1-20% by weight of a compound of formula (I-2) b) 5 to 35% by weight of at least one ammonium salt selected from ammonium sulfate and diammonium hydrogen phosphate, c) 5-35% by weight of at least one dispersant selected from the group consisting of alkyl polypropylene glycol-polyethylene glycol compounds of formula (III-a) R—O—A—B—H (III-a) Wherein R is a C1-C4 fragment, A is a polypropylene glycol segment consisting of 10 to 40 propylene oxide (PO) units of formula III-b, B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 10-50 ethylene oxide (EO) units of formula III-c together with 0-10 propylene oxide (PO) units, and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R'(IIId) The various groups and subscripts have the following definitions: R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, Where one of n or m means 2, and the other of n or m means 3, d) 0.3 to 8% by weight of a combination of sodium salts of copolymers of maleic acid and olefins and salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, e) 0.5 to 10% by weight of at least one partially hydrophobic fumed amorphous silica, f) at least one solvent selected from dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and diethylene glycol monomethyl ether, g) 1-20% by weight of other additives; in, f) is added to make up the volume of the composition to 1 liter.

8. The composition according to claim 7, characterized in that d) is a combination of maleic anhydride 2,4,4-trimethylpentene polymer sodium salt and condensed naphthalene formaldehyde sulfonate sodium salt.

9. The composition according to claim 7, characterized in that The components are present as follows: a) 1.5-5% by weight b) 15-30% by weight, c) 10-30% by weight, d) 0.5-5% by weight e) 1 to 5% by weight, and g) 5-15% by weight.

10. The composition according to claim 1, characterized in that c) Alkyl polypropylene glycol-polyethylene glycol compounds selected from the group consisting of general formula (III-a) R—O—A—B—H (III-a) Wherein R is a C3-C4 fragment, A is a polypropylene glycol segment consisting of 15 to 35 propylene oxide (PO) units of formula III-b, B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 20-40 ethylene oxide (EO) units of formula III-c and 0-8 propylene oxide (PO) units, and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R' (IIId) The various groups and subscripts have the following definitions: R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, Here, the meaning of one of n or m is 2, and the meaning of the other of n or m is 3.

11. The composition according to claim 1, characterized in that c) Alkyl polypropylene glycol-polyethylene glycol compounds selected from the group consisting of general formula (III-a) R—O—A—B—H (III-a) Where R is the C4 fragment, A is a polypropylene glycol segment consisting of 20-30 propylene oxide (PO) units of formula III-b, B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment consisting of 30-40 ethylene oxide (EO) units of formula III-c together with 0-5 propylene oxide (PO) units, and an alkyl polypropylene glycol-polyethylene glycol compound of general formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R'(IIId) The various groups and subscripts have the following definitions: R and R' are independently hydrogen, linear C1- to C5-alkyl, or branched C3- or C4-alkyl; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, Here, the meaning of one of n or m is 2, and the meaning of the other of n or m is 3.

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

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