Insecticidal mixture formulations containing propylene carbonate

Abstract

The present invention relates to insecticidal active substance preparations, which contain at least one dissolved active substance and at least one solid active substance, and which have good storage stability at high and low temperatures and high active substance permeability; a process for their preparation; and their use for applying the substances contained therein.

Description

[0001] The present invention relates to an insecticidal active ingredient preparation, which comprises at least one dissolved active ingredient and one active ingredient in solid form and has good storage stability and high active ingredient permeability at high and low temperatures; to a method for preparing the same and to its use for applying the active ingredient present. The present invention also relates to an adjuvant composition for an insecticidal active ingredient preparation having at least one dissolved active ingredient and at least one active ingredient in solid form, which is used to improve the permeability of the two active ingredients.

[0002] In order to exhibit biological efficacy, systemic agrochemical active ingredients, in particular systemic insecticides, require formulations that enable the active ingredient to be absorbed into the plant / target organism. The best effect can be achieved by diluting the corresponding active ingredient in an aqueous solution for use and / or preferably already in a dissolved state in a concentrate so that a high concentration of the active ingredient is readily available.

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

[0004] In addition, the biological activity may be further enhanced by optionally 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 generally do not have good bioavailability. Here, the biological activity can be increased substantially only by adding suitable adjuvants / penetrants, but this still results in reduced biological activity compared to the above-mentioned EC or SL formulations.

[0006] Known agrochemical active ingredients differ from each other in the following aspects: including their physicochemical properties, such as solubility in water, solvents and / or oils, melting points and boiling points, polarity, molar mass, etc. These properties affect the composability of the active ingredient. For example, many known agrochemical active ingredients have high melting points and can therefore withstand the thermal stress that occurs, for example, in the preparation of suspension concentrates. In contrast, low-melting active ingredients are difficult to withstand these preparation conditions and can only be prepared into storage-stable suspensions to a very limited extent, because it is expected that the active ingredient will soften or melt at higher temperatures. However, if the active ingredient is no longer in crystalline form, the physical stability of the formulated product will usually be significantly reduced, and it will no longer have any practical utility.

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

[0008] It is also known that it is often appropriate to combine agrochemical active ingredients with one another, for example, to prevent the development of resistance (for example, by combining different mechanisms of action), or when pests react differently to different active ingredients, or in order to expand the spectrum of action of the mixture. In the latter case, for example, the mixing of active ingredients can significantly reduce the effective application rate, which enables specific control of harmful insects without excessive or no damage to beneficial organisms. Another reason for using active ingredient mixtures may be that the duration of action of the active ingredients (half-life in plants or soil) is different, whereby protection can be produced over a long period of time with just one treatment.

[0009] A characteristic of stable suspension concentrates is that they are physically and chemically stable for storage over a relatively long period of time (12-24 months) and over a wide temperature range (0 to 54° C.). This wide temperature range is desirable so that only a single formulation with the same active ingredient or combination of active ingredients can be used advantageously in different climatic zones.

[0010] The storage stability of suspension concentrates is characterized in particular in that the contents of these suspension concentrates have only low phase separation, if any, during storage. Another parameter for the stability of 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.

[0011] The prior art also discloses propylene carbonate as a solvent for agrochemical active ingredients. For example, WO 2006 / 089661 (US 2008 / 0255204 A1, Davies et al.) describes agrochemical formulations containing propylene carbonate, wherein the agrochemical active ingredient is in dissolved form. No conclusions can be drawn from it about the physical stability of the composite suspension concentrate described in the present invention; the formulation of the present invention is based on a composition of propylene carbonate and a dissolved and dispersed active ingredient in the presence of dispersed ammonium salts and specific polymeric surfactants. WO 2006 / 089661 is related to agrochemical formulations with a single dissolved active ingredient throughout. Potential mixtures with other soluble active ingredients are only mentioned in

[0009] by way of example, but are not described in detail. Paragraph

[0015] describes the use of propylene carbonate, in particular as a penetration aid for crop protection compositions, which is also described in

[0041] -

[0050] . However, the effect of imparting permeability is discussed using only one active ingredient (imidacloprid) as an example; moreover, the effect of imparting permeability of propylene carbonate shown in WO 2006 / 089661 should be considered to be relatively small in the formulation compared to a formulation without propylene carbonate. Due to the structural differences in crop protection compositions and the resulting different physicochemical properties, even the expert cannot directly infer that this effect of imparting permeability will also apply to other active ingredients, not to mention compositions of different active ingredients, especially when they are in different stages.

[0012] WO 2011 / 029552 describes agrochemical formulations containing alkylpolypropylene glycol-polyethylene glycols (eg Antarox B / 848), wherein such surfactants are used as emulsifiers and / or penetrants for the agrochemical active ingredients.

[0013] Furthermore, WO 2003 / 000053 describes specific alkylpolypropylene glycol-polyethylene glycols, for example Atlas G5000, as dispersants for organic crop protection products in oil.

[0014] The use of ammonium salts to enhance the effect of agrochemical active ingredients is known in the literature; for example, WO 2011 / 131623 (US 2011 / 0281727 A1, Fischer et al.) records that insecticidal and / or herbicidal formulations based on tetramic acid based on heterocyclic groups have improved efficacy in the presence of ammonium salts. In addition, WO 2007 / 068428 records the activity enhancement effect of phenyl-substituted cyclic ketone-enols in the presence of ammonium salts. WO 2011 / 131623 relates to a composition of a single active ingredient selected from a substance of formula [I] and an organic or inorganic ammonium salt or phosphonium salt, and its use in an aqueous spray liquid in the presence or absence of a suitable penetrant. From the teachings of WO 2011 / 131623, professionals cannot draw any conclusions about the physical and chemical stability of the formulations of the compositions containing other active ingredients or these mixture formulations. Suitable penetrants are described generally in paragraphs

[0111] to

[0171] and are generally claimed in

[0178] , but only rapeseed oil methyl ester is listed as an example of a vegetable oil derivative and Genapol LRO as an example of an anionic alcohol ether sulfate. Propylene carbonate, due to its chemical properties, does not correspond to the examples listed or to the main substance described as a penetrant. Therefore, it is not possible to establish a direct correlation between the effect of propylene carbonate on compounds selected from the substances of formula [I] or on compounds not covered by the description of formula [I].

[0015] The preparations of the invention with dissolved active ingredient and undissolved active ingredient having good permeability are neither described nor suggested in WO 2011 / 131623.

[0016] Oil-based formulations containing ammonium salts are also known in the literature. For example, WO 2008 / 151725 records an adjuvant composition based on oils, wherein the ammonium salt is in dispersed form. In addition, EP 2193712 A1 records an oil-based agrochemical formulation, wherein the ammonium salt is in dispersed form. However, no suspension of the ammonium salt in a water-soluble solvent is recorded.

[0017] In summary, however, none of the above cited documents, taken individually or in combination, give any suggestion that alkylpolypropylene glycol-polyethylene glycols, such as Antarox B / 848, can be used as effective dispersants for high loads of inorganic ammonium salts in polar water-soluble solvents such as propylene carbonate, especially in combination with suspended and dissolved active ingredients.

[0018] Soluble water-based concentrates of tetramic acid derivatives are known in the prior art, for example WO 2009 / 115262. Due to solubility problems, they cannot be combined with certain crop protection products and formulation ingredients. In addition, these water-based SL formulations usually have a high pH value, which likewise leads to incompatibility with certain alkali-sensitive crop protection products and formulation ingredients.

[0019] Therefore, the problem to be solved is to develop a stable formulation consisting of a combination of a dissolved active ingredient and a suspended active ingredient, having good bioavailability and permeability of both active ingredients and good storage stability at both high and low temperatures. The active ingredient is preferably an insecticide.

[0020] This problem is solved by the formulation described below comprising an active ingredient combination and an ammonium salt and a carbonate as solvent.

[0021] Therefore, the present invention provides an insecticidal composition comprising:

[0022] a. at least one active ingredient which is solid at room temperature and which is preferably insoluble or slightly soluble in the selected solvent g),

[0023] b. at least one active ingredient other than a) which is soluble in an organic solvent,

[0024] c. at least one ammonium salt,

[0025] d. at least one dispersant selected from alkyl propoxylated ethoxylates,

[0026] e. optionally one or more surfactants,

[0027] f. at least one water-insoluble filler,

[0028] g. at least one solvent selected from carbonates, and

[0029] h. Optionally, other adjuvants.

[0030] In a preferred embodiment, component e) is essential.

[0031] Furthermore, in a preferred embodiment, the composition is free of water, or in another alternative embodiment, the composition is substantially free of water.

[0032] It has been found according to the invention that the corresponding compositions have good penetration-promoting properties and high stability for the two agrochemical active ingredients present. This is surprising in view of the different properties of the active ingredients a) and b).

[0033] In the present invention, in the formulae, for example in formula (I), unless otherwise indicated, optionally substituted radicals may be monosubstituted or polysubstituted, wherein in the case of polysubstitution the substituents may be identical or different.

[0034] Furthermore, within the preferred scope of the present invention, different preference levels are to be understood in such a way that they can be combined with one another in permutations, but in any case the same preference levels and in particular the most preferred embodiments / preferential levels can be combined with one another in each case and are indeed disclosed in such combinations.

[0035] Compositions described in this application consisting only of the essential components (and no optional components) should also be considered disclosed.

[0036] In the context of the present invention, room temperature refers to a temperature of 20°C to 25°C, unless otherwise stated.

[0037] Component ah is further defined below.

[0038] a. Active ingredient that is solid at room temperature

[0039] The active ingredient which is solid at room temperature is preferably selected from the group consisting of pesticides, herbicides and fungicides. Further preferably, the selected active ingredient is insoluble or only slightly soluble in the selected solvent g). Further preferred are active insecticidal ingredients which are solid at room temperature and insoluble or only slightly soluble in the selected solvent g).

[0040] In the context of the present invention, sparingly soluble or insoluble active ingredients are active ingredients which are solid at room temperature and have a solubility in the selected solvent g) at 20° C. of 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.

[0041] Even further preferably, the active ingredient is selected from the diamide insecticides (broflanilide, chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyhalodiamide, flubendiamide, tetrachlorantraniliprole and tetraniliprole), spinosads (IRAC group 5), which are known as "mectins" (e.g. abamectin, emamectin benzoate, milbemectin; IRAC group 6), ethiprole, triflumuron, deltamethrin and tetronic acid and tetramic acid derivatives (IRAC Group 23, including compounds of formula I and II described below).

[0042] In a preferred embodiment, component a) of the composition according to the invention is a keto-enol based on tetramic acid, preferably a compound of formula (I)

[0043]

[0044] in

[0045] W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine,

[0046] X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine,

[0047] A, B together with the carbon atom to which they are bound are C3-C6-cycloalkyl substituted by alkylenedioxy, which is optionally substituted by C1-C4-alkyl or C1-C4-alkoxy-C1-C2-alkyl and forms together with the carbon atom to which they are bound a 5- or 6-membered ketal,

[0048] G is hydrogen (a) or one of the following groups

[0049]

[0050] in

[0051] E is a metal ion or an ammonium ion,

[0052] M is oxygen or sulfur,

[0053] R1 is a straight-chain or branched C1-C6-alkyl group,

[0054] R 2 It is a straight-chain or branched C1-C6-alkyl group.

[0055] Particularly preferably, tetramic acid derivatives of the abovementioned formula (I) can be used, in which the radicals are defined as follows:

[0056] W is more preferably methyl,

[0057] X is more preferably chlorine or methyl (more preferably methyl),

[0058] Y is more preferably chlorine, bromine or methyl,

[0059] A, B together with the carbon atom to which they are bound are more preferably a saturated C6-cycloalkyl group substituted by an alkylenedioxy group, said alkylenedioxy group together with the carbon atom to which it is bound forming a 5-membered or 6-membered ketal,

[0060] G is more preferably hydrogen (a) or one of the following groups

[0061]

[0062] in

[0063] M is oxygen,

[0064] E is a monovalent metal ion or an ammonium ion (especially sodium or potassium),

[0065] R 1 More preferably, it is a straight-chain or branched C1-C4-alkyl group,

[0066] R 2 More preferred is a straight-chain or branched C1-C4-alkyl group.

[0067] Particularly useful are tetramic acid derivatives of the abovementioned formula (I) in which G = hydrogen (a).

[0068] Likewise particularly useful are tetramic acid derivatives of the abovementioned formula (I) in which G═E(d).

[0069] Particularly preferably used are tetramic acid derivatives of the abovementioned formula (I) in which the radicals are defined as follows:

[0070]

[0071]

[0072] In a particularly preferred embodiment, component a) is a compound of the formula

[0073]

[0074] Compound I-2 is preferably used in its most thermodynamically stable polymorphic structure. The crystal structure and other physical data are determined as follows:

[0075] Sample preparation:

[0076] Compound I-2 (C 19 H 22 ClNO4 / MW = 363.84 g / mol) was crystallized from methanol and dried at room temperature to give modification A.

[0077] Modification A of I-2 can be characterized by x-ray powder diffraction based on the corresponding diffraction pattern at 25° C. and using Cu-Kα1 radiation (1.5406 ) to record ( Figure 1 ).

[0078] like Figure 1 As shown, variant A of the present invention shows at least 3, preferably at least 5, further preferably at least 7, even further preferably at least 10 and most preferably all reflections:

[0079] Variant A of the present invention is also characterized in that Figure 1 The x-ray diffraction pattern shown.

[0080] Crystallographic studies of single crystals of modification A show that the crystal structure is monoclinic and the unit cell has a P21 / c space group.

[0081] Table 2: Crystallographic properties of modification A

[0082]

[0083]

[0084] a, b, c = length of unit cell side

[0085] α, β, γ = angles of the unit cell

[0086] Z = number of molecules in the unit cell

[0087] Table 2a / b: Crystallographic data / reflections [°2θ] of modification A

[0088]

[0089]

[0090] 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 at 4 cm -1 Record at a resolution of Figure 2 ).like Figure 2 As shown and as described 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.

[0091] Table 2c) IR bands [cm -1 ]

[0092]

[0093]

[0094] In an alternative embodiment, component a) comprises tetramic acid of formula (II)

[0095]

[0096] in

[0097] W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine,

[0098] X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine,

[0099] 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,

[0100] V 2 is hydrogen, halogen, C1-C6-alkyl or C1-C6-alkoxy,

[0101] V 3 is hydrogen or a halogen,

[0102] A, B together with the carbon atoms to which they are bound are saturated C5-C6-cycloalkyl, one ring member of which is substituted by oxygen, and the C5-C6-cycloalkyl is optionally monosubstituted by C1-C8-alkyl, C1-C8-alkoxy or C1-C6-alkoxy-C1-C6-alkyl,

[0103] G is hydrogen (a) or one of the following groups

[0104]

[0105] in

[0106] E is a metal ion or an ammonium ion,

[0107] L is oxygen or sulfur, and

[0108] M is oxygen or sulfur,

[0109] R 1 is a straight-chain or branched C1-C6-alkyl group,

[0110] R 2 is a straight-chain or branched C1-C6-alkyl group,

[0111] Particularly preferably used are tetramic acid derivatives of the abovementioned formula (I) in which the radicals are defined as follows:

[0112] W is more preferably hydrogen or methyl,

[0113] X is more preferably chlorine or methyl,

[0114] Y is more preferably hydrogen,

[0115] V 1 More preferably, it is fluorine or chlorine (especially fluorine or chlorine at the 4-position),

[0116] V 2 More preferably, it is hydrogen or fluorine (especially fluorine at the 3-position),

[0117] V 3 More preferably, it is hydrogen or fluorine (especially fluorine at the 5-position),

[0118] A, B together with the carbon atoms to which they are bound are more preferably saturated C6-cycloalkyl, one of the ring members being substituted by oxygen,

[0119] G is more preferably hydrogen (a) or one of the following groups

[0120]

[0121] in

[0122] More preferably, E is a monovalent metal ion or an ammonium ion (especially sodium or potassium),

[0123] R 1 More preferably, it is a straight-chain or branched C1-C4-alkyl group,

[0124] R 2 More preferred is a straight-chain or branched C1-C4-alkyl group.

[0125] Particularly useful are tetramic acid derivatives of the abovementioned formula (I) in which G = hydrogen (a).

[0126] Likewise particularly useful are tetramic acid derivatives of the abovementioned formula (I) in which G═E(d).

[0127] Particularly preferably used are tetramic acid derivatives of the abovementioned formula (II) in which the radicals are defined as follows:

[0128]

[0129] In a particularly preferred alternative embodiment, a) is

[0130]

[0131] b. Soluble active ingredients

[0132] The soluble active ingredient is preferably selected from pesticides, herbicides and fungicides. Further preferably, the selected active ingredient has good or sufficient solubility in the selected solvent g), preferably at least 10 g / l at 20° C., further preferably at least 20 g / l, even further preferably at least 30 g / l, more preferably at least 40 g / l.

[0133] The soluble active ingredient is preferably selected from insecticides. Even further preferably, the active ingredient is selected from nAChR agonists (IRAC Group 4, such as imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, sulfoxaflor, nitenpyram and flupyradifurone), flonicamid and WO Other insecticides described in 2007 / 115644, for example 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one

[0013] The pesticides described in WO 2009 / 118025 include 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, or other pesticides as described in WO 2009 / 118025, for example 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0134] More preferably, the active ingredient b) is selected from imidacloprid, clothianidin, flupyradone and acetamiprid.

[0135] Most preferably, the active ingredient b) is flupyralidone.

[0136] c. Ammonium salt

[0137] The ammonium salt is preferably selected from water-soluble inorganic ammonium salts.

[0138] Further preferably, c) is selected from ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0139] More preferably, c) is DAHP and AMS.

[0140] d. Dispersant

[0141] Component d) is preferably selected from alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a)

[0142] ROABH

[0143] (III-a)

[0144] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0145] 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,

[0146] 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 PO units and 0-5 PO units.

[0147]

[0148] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are:

[0149]

[0150] and a compound of formula (IIId)

[0151] RO-(C m H 2m O) x -(C n H 2n O) y-R' (IIId)

[0152] The groups and subscripts have the following definitions:

[0153] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0154] m is 2 or 3;

[0155] n is 2 or 3;

[0156] x is 5 to 150; and

[0157] y is 5 to 150,

[0158] One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

[0159] 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.

[0160] In the context of the present invention, branched C3 to C4-alkyl is understood to mean isopropyl, isobutyl or tert-butyl.

[0161] In a preferred embodiment, the R and R' groups are independently selected from methyl, n-butyl and hydrogen.

[0162] In an even more preferred embodiment, the R and R' groups are independently selected from n-butyl and hydrogen.

[0163] Regarding the arrangement of polyethylene and polypropylene units,

[0164] (a) The value of m can be set to 2, and the value of n to 3;

[0165] (b) Or the value of m can be set to 3 and the value of n can be set to 2.

[0166] Configuration (b) in which m=3 and n=2 is preferred.

[0167] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of the formula (IIId) in which

[0168] m is 3,

[0169] n is 2,

[0170] x is 5 to 80,

[0171] y is 5 to 80,

[0172] R is n-butyl or hydrogen, and

[0173] R' is hydrogen.

[0174] e. In the context of the present invention, suitable surfactants e) are selected from:

[0175] e1) Surfactants of the polycarboxylic acid ester type, for example hydrophobically modified comb polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (e.g. isobutylene or diisobutylene), copolymers of acrylic acid with itaconic acid, copolymers of methacrylic acid with itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid with methacrylic acid, copolymers of acrylic acid with methacrylate, copolymers of acrylic acid with vinyl acetate, copolymers of styrene with methacrylic acid, modified copolymers of styrene with methacrylic acid, copolymers of maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acids (e.g. C8-C 18 )-sarcosinate, 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 Geropon T / 36, Geropon TA / 72, Tersperse 2700, Atlox Metasperse 550S, Geropon Ultrasperse, Narlex D-72, Versa TL3 and Agrilan 789 Dry, and

[0176] e2) a surfactant selected from the group consisting of salts of sulfated formaldehyde condensation products with alkyl aromatic compounds (e.g. 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 (e.g. BAYKANOL SL, available from Levaco), and salts of sulfated formaldehyde condensation products with cyclohexanone (e.g. LUCRAMULDAC 210, available from Levaco), and

[0177] e3) a surfactant selected from the group consisting of lignin sulfonates and salts thereof, preferably selected from the group consisting of lignin sulfonates and salts thereof 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 T; AGRINOL DN 19 and Agrinol C12 purchased from Tembec, and

[0178] e4) surfactants selected from sulfated alkyl aryl sulfonates and salts thereof, for example alkyl aryl sulfonates and salts thereof, for example AEROSOL OS (available from Solvay); AGNIQUE ANS 3DNP-U, AGNIQUE ANS 4DNP, AGNIQUE NSC2NP-U, NEKAL BX DRY (available from BASF); MORWET B, MORWET DB, MORWET EFW, MORWET IP (available from AkzoNobel); OPARYL MT 704, OPARYL MT 800, OPARYL MT 804 (available from Bozzetto); RHODACAL BX78, SUPRAGIL WP (available from Solvay); SURFOM HRB (available from Oxiteno), and

[0179] e5) surfactants selected from di / tristyrylphenol ethoxylated 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 TS 20-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 ethoxylated phosphates, such as EMPIPHOS 03D (purchased from AkzoNobel); MULTITROPE 1214, Crodafos series, Atphos 3226 (purchased from Croda); PHOSPHOLAN PE 169 (purchased from Akzo Nobel); RHODAFAC RS-410, RHODAFAC RS-710, RHODAFAC TD 20F (purchased from Solvay); SERVOXYL VPDZ 20 / 100 (purchased from Elementis); STEPFAC 8180 (purchased from Stepan); CRAFOL AP261 (purchased from BASF); GERONOL CF / AR (purchased from Clariant).

[0180] Further preferably, suitable surfactants are selected from surfactants e1), e2), e3) and e4).

[0181] Further preferably, suitable surfactants are selected from surfactants e1), e2) and e3).

[0182] Even further preferably, suitable surfactants are selected from the group consisting of surfactants e1) and e2).

[0183] More preferably, suitable surfactants are selected from surfactants e1).

[0184] Very particular preference is given to surfactants selected from e1), which comprise: sodium salts of copolymers of maleic acid and olefins (e.g. Geropon T / 36 / Solvay; Duramax D-305 / Dow); 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).

[0185] WO 2008036865 A2 also describes suitable surfactants, such as Tersperse 2700.

[0186] The above surfactants can be used alone or in combination, preferably a combination of surfactants selected from the following: sodium salts of copolymers of maleic acid and olefins, and salts of sulfated formaldehyde condensation products and alkyl aromatic compounds, and lignin sulfonates and their salts.

[0187] f. Water-insoluble fillers

[0188] Suitable fillers are preferably selected from

[0189] f1) Modified natural silicates, such as chemically modified bentonite, hectorite, attapulgite, montmorillonite, or other silicate minerals, such as bentone (Elementis), Attagel (BASF), Agsorb (Oil-DriCorporation), Pangel B (Tolsa) or Hectorite (Akzo Nobel),

[0190] f2) Synthetic silicates and fumed silicas, for example the following silicates: Sipernat 、Aerosil or Durosil Series (Degussa), CAB-O-SIL series (Cabot) or Van Gel series (RTVanderbilt), and

[0191] f3) Fillers based on synthetic polymers, such as the following thickeners: Thixin or Thixatrol Series (Elementis).

[0192] The fillers of group f2 are more preferred.

[0193] Particular preference is given to fumed silica as filler f), for example the Aerosil products, Aerosil R products and Cab-O-Sil products, and also attapulgite, alone and in mixtures.

[0194] g.Solvent

[0195] The solvent g) is preferably selected from the group consisting of carbonates, further preferably from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and its isomers, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, glycerol carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate and octylene carbonate.

[0196] Even further preferably, g) is selected from cyclic carbonates, ie carbonates in which the diol is bridged, for example in the case of propane-1,3-diol, which with carbonic acid forms trimethylene carbonate, or in the case of propane-1,2-diol, which with carbonic acid forms propylene carbonate.

[0197] More preferably, g) is propylene carbonate.

[0198] h. Other additives

[0199] The compositions according to the invention optionally comprise further auxiliaries h), for example substances optionally selected from emulsifiers, wetting agents, foam inhibitors, preservatives, dyes, stabilizers and antioxidants.

[0200] Useful emulsifiers include all customary nonionic, anionic, cationic and zwitterionic substances with surface-active properties which are usually 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, mono- and diesters of phosphoric acid, and reaction products of ethylene oxide with propylene oxide, and further alkylsulfonates, alkyl sulfates, aryl sulfates, tetraalkylammonium halides, trialkylarylammonium halides, alkylamine sulfonates, end-capped and end-uncapped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxypolyethylene-propylene glycol), and polyethylene glycols and polypropylene glycols.

[0201] Emulsifiers can be used alone or in a mixture. 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 alcohols and ethylene oxide in a molar ratio of 1:5 to 1:50, reaction products of C6-C20 alcohols and propylene oxide and ethylene oxide in a molar ratio of 1:1:1 to 1:5:10, reaction products of fatty amines and ethylene oxide in a molar ratio of 1:2 to 1:25, reaction products of 1 mol phenol with 2 to 3 mol styrene and 10 to 50 mol ethylene oxide, reaction products of C8-C12-alkylphenols and ethylene oxide in a molar ratio of 1:5 to 1:30, alkyl glycosides, C8-C16-alkylbenzene sulfonates, such as calcium salts, monoethanolammonium salts, diethanolammonium salts and triethanolammonium salts.

[0202] Useful wetting agents are all substances which can usually be used for such purposes in agrochemical compositions. Preference is given to water-soluble liquids, examples of which include glycerol.

[0203] Useful foam inhibitors are all substances which can usually be employed for such purposes in agrochemical compositions. Preference is given to silicone oils (for example SAG 1572) and magnesium stearate.

[0204] Useful antioxidants are all substances which can usually be employed for such purposes in agrochemical compositions. Butylated hydroxytoluene is preferred.

[0205] Useful dyes are all substances which can usually be used for such purposes in agrochemical compositions. Examples include titanium dioxide, pigment black, zinc oxide and blue pigments, and also Permanent Red FGR.

[0206] The stabilizer that can be used may 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 monoalkyl or polyalkyl substituted amines.

[0207] In a preferred embodiment, the present invention provides an insecticidal composition comprising:

[0208] a. Composition of formula (I)

[0209]

[0210] The compounds of formula (I) have the following definitions:

[0211] W is a methyl group,

[0212] X is chlorine or methyl,

[0213] Y is chlorine, bromine or methyl,

[0214] A, B together with the carbon atom to which they are bound are a saturated C6-cycloalkyl group substituted by an alkylenedioxy group, wherein the alkylenedioxy group together with the carbon atom to which it is bound forms a 5-membered or 6-membered ketal group,

[0215] G is hydrogen (a) or one of the following groups

[0216]

[0217] in

[0218] M is oxygen,

[0219] E is a monovalent metal ion or an ammonium ion,

[0220] R 1 is a straight-chain or branched C1-C4-alkyl group,

[0221] R 2 is a straight-chain or branched C1-C4-alkyl group,

[0222] b. At least one active ingredient is preferably selected from the group consisting of insecticides, which comprise nAChR agonists, flonicamid and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethylene

[0013] The compounds of the invention are 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0223] c. 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),

[0224] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0225] ROABH

[0226] (III-a)

[0227] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0228] 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,

[0229] 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 20-40 EO units and 0-8 PO units, more preferably 30-40 PO units and 0-5 PO units,

[0230]

[0231] and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId)

[0232] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0233] The groups and subscripts have the following definitions:

[0234] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0235] m is 2 or 3;

[0236] n is 2 or 3;

[0237] x is 5 to 150; and

[0238] y is 5 to 150,

[0239] One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

[0240] e. 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 their salts, sulfated alkylaryl sulfonates and their salts, di / tristyrylphenol ethoxylated phosphates and their salts, and alcohol ethoxylated phosphates.

[0241] f. At least one filler selected from the group consisting of modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite and synthetic polymer-based fillers.

[0242] g. at least one solvent selected from carbonates,

[0243] h. Optionally, other adjuvants.

[0244] In a further preferred embodiment, the present invention provides an insecticidal composition comprising:

[0245] a. a compound of formula (I) selected from the following compounds:

[0246]

[0247]

[0248] b. At least one active ingredient is preferably selected from the group consisting of insecticides, which include imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, sulfoxaflor, nitenpyram and flupyrazone, flunicromethamine and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one -3-yl)methyl](2-fluorovinyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0249] c. 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),

[0250] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0251] ROABH

[0252] (III-a)

[0253] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0254] 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,

[0255] 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 20-40 EO units and 0-8 PO units, more preferably 30-40 PO units and 0-5 PO units,

[0256]

[0257] and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId)

[0258] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0259] The groups and subscripts have the following definitions:

[0260] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0261] m is 2 or 3;

[0262] n is 2 or 3;

[0263] x is 5 to 150; and

[0264] y is 5 to 150,

[0265] One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

[0266] e. 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,

[0267] f. At least one filler selected from the group consisting of modified natural silicates, silicate minerals, synthetic silicates and fumed silica, attapulgite and synthetic polymer-based fillers.

[0268] g. at least one solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and isomers thereof, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, butylene carbonate, pentyl carbonate, hexylene carbonate and octyl carbonate,

[0269] h. Optionally, other adjuvants.

[0270] In a particularly preferred embodiment, the present invention provides an insecticidal composition comprising:

[0271] In a preferred embodiment, the present invention provides an insecticidal composition comprising:

[0272] a. A compound of formula (I-2) having the following structure:

[0273]

[0274] b. Fluoropyranone.

[0275] c. at least one ammonium salt selected from ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP),

[0276] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0277] ROABH

[0278] (III-a)

[0279] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0280] 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,

[0281] 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 20-40 EO units and 0-8 PO units, more preferably 30-40 PO units and 0-5 PO units,

[0282]

[0283] and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId)

[0284] RO-(C m H 2m O)x -(C n H 2n O) y -R' (IIId)

[0285] The groups and subscripts have the following definitions:

[0286] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0287] m is 2 or 3;

[0288] n is 2 or 3;

[0289] x is 5 to 150; and

[0290] y is 5 to 150,

[0291] One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

[0292] e. at least one surfactant selected from polycarboxylates,

[0293] f. at least one filler selected from fumed silica and attapulgite.

[0294] g. at least one solvent selected from propylene carbonate,

[0295] h. Optionally, other adjuvants.

[0296] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure.

[0297] Percentages - unless otherwise stated - are to be regarded as percentages by weight, wherein the % by weight of the composition total 100.

[0298] The proportions of the following components are each based on the total weight of the composition, wherein the balance to 1 liter of the total composition is composed of component h) (solvent). Therefore, the proportion of component h) is preferably 1% to 80% by weight, more preferably 20-60% by weight.

[0299] The proportion of solid active ingredients (component a) in the composition of the present invention is

[0300] Preferably 0.5-30% by weight,

[0301] More preferably, 1 to 20% by weight, and

[0302] More preferably, it is 1-15% by weight.

[0303] The proportion of the dissolved active ingredient (component b) in the composition of the present invention is

[0304] Preferably 1-30% by weight

[0305] More preferably, 2-20% by weight, and

[0306] More preferably, it is 2-15% by weight.

[0307] The proportion of ammonium salt (component c) in the composition of the present invention is

[0308] Preferably 1-40% by weight

[0309] More preferably, 5-35% by weight, and

[0310] More preferably, it is 15-30% by weight.

[0311] The proportion of the dispersant (component d) in the composition of the present invention is

[0312] Preferably 0.5-40% by weight

[0313] More preferably, 2.5-35% by weight, and

[0314] More preferably, it is 5-30% by weight.

[0315] The ratio of surfactant (component e) in the composition of the present invention is

[0316] Preferably 0-10% by weight

[0317] More preferably, 0.3-8% by weight, and

[0318] More preferably, it is 0.5-2.5% by weight.

[0319] The proportion of filler (component f) in the composition is

[0320] Preferably 0.1-10% by weight

[0321] More preferably, 0.5-10% by weight, and

[0322] More preferably, it is 2-10% by weight.

[0323] The proportion of other adjuvants (component h) in the composition of the present invention (if any) is

[0324] Preferably 0-10% by weight

[0325] More preferably, 0.01 to 8% by weight, and

[0326] More preferably, it is 0.05-6% by weight.

[0327] A preferred embodiment of the present invention is a composition comprising the following components:

[0328] a) 1-30 wt %

[0329] b) 1-30% by weight

[0330] c) 1-40% by weight

[0331] d) 1-40% by weight

[0332] e) 0-10% by weight

[0333] f) 0.1-15% by weight

[0334] h) 0-10% by weight

[0335] g) to 1 liter.

[0336] A further preferred embodiment of the present invention is a composition comprising the following components:

[0337] a) 2-20 wt%

[0338] b) 2-20% by weight

[0339] c) 5-35% by weight

[0340] d) 5-35% by weight

[0341] e) 0.3-8% by weight

[0342] f) 0.5-12.5 wt %

[0343] h) 0.01-8% by weight

[0344] g) to 1 liter.

[0345] An even further preferred embodiment of the present invention is a composition comprising the following components:

[0346] a) 2-15 wt%

[0347] b) 2-15% by weight

[0348] c) 15-30% by weight

[0349] d) 10-30% by weight

[0350] e) 0.5-2.5 wt %

[0351] f) 1-10% by weight

[0352] h) 0.05-6% by weight

[0353] g) to 1 liter.

[0354] The invention further relates to an adjuvant composition for insecticidal active ingredient formulations having at least one dissolved active ingredient and one active ingredient in solid form, for improving the penetration of both active ingredients, comprising

[0355] c. at least one ammonium salt, and

[0356] d. at least one dispersant from the class of alkyl propoxylated ethoxylates.

[0357] In a preferred embodiment, the adjuvant composition further comprises

[0358] g. at least one solvent derived from carbonates.

[0359] The ammonium salt from the auxiliary composition is preferably selected from water-soluble inorganic ammonium salts.

[0360] Further preferably, c) is selected from ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0361] More preferably, b) is DAHP and AMS.

[0362] Component d) of the adjuvant composition (dispersant) is preferably selected from alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a)

[0363]

[0364] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0365] A is a polypropylene glycol fragment, which is composed of 10 to 40 propylene oxide (PO) units (Formula III-b), preferably composed of 15-35 PO units, and more preferably composed of 20-30 PO units. B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment, 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 PO units and 0-5 PO units.

[0366]

[0367] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are:

[0368]

[0369]

[0370] and a compound of formula (IIId)

[0371] RO-(C m H 2m O) x -(Cn H 2n O) y -R' (IIId)

[0372] The groups and subscripts have the following definitions:

[0373] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0374] m is 2 or 3;

[0375] n is 2 or 3;

[0376] x is 5 to 150; and

[0377] y is 5 to 150,

[0378] One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

[0379] 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.

[0380] In the context of the present invention, branched C3 or C4-alkyl is understood to mean isopropyl, isobutyl or tert-butyl.

[0381] In a preferred embodiment, the R and R' groups are independently selected from methyl, n-butyl and hydrogen.

[0382] In an even more preferred embodiment, the R and R' groups are independently selected from n-butyl and hydrogen.

[0383] Regarding the arrangement of polyethylene and polypropylene units,

[0384] (a) The value of m can be set to 2, and the value of n to 3;

[0385] (b) Or the value of m is 3 and the value of n is 2.

[0386] Configuration (b) in which m=3 and n=2 is preferred.

[0387] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of the formula (IIId) in which

[0388] m is 3,

[0389] n is 2,

[0390] x is 5 to 80,

[0391] y is 5 to 80,

[0392] R is n-butyl or hydrogen, and

[0393] R' is hydrogen.

[0394] The solvent g) used together with the auxiliary composition is preferably selected from the group consisting of carbonates, more preferably from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and its isomers, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, butylene carbonate, pentyl carbonate, hexylene carbonate and octylene carbonate.

[0395] Even further preferably, g) is selected from cyclic carbonates, ie carbonates in which the diol is bridged, for example in the case of propane-1,3-diol, which forms trimethylene carbonate with carbonic acid.

[0396] More preferably, g) is propylene carbonate.

[0397] A preferred embodiment of the invention is an auxiliary composition in which the ratio of c) to d) (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.

[0398] The proportion of the auxiliary composition based on the weight of the total formulation is preferably

[0399] c) 1-40% by weight

[0400] d) 1-40% by weight

[0401] Further optimization

[0402] c) 5-35% by weight

[0403] d) 5-35% by weight, and

[0404] Even further optimization

[0405] c) 15-30% by weight

[0406] d) 10-30% by weight.

[0407] The application rate of the preparations according to the invention can be varied within a relatively wide range. This is determined by the active ingredients and their content in the composition.

[0408] With the aid of the compositions according to the invention, the insecticidal active ingredient mixtures can be applied in a particularly advantageous manner to plants and / or their habitat.

[0409] Compositions of the present invention can be used for processing all plants and plant parts. In the context of the present invention, plants are understood to include all plants and plant populations, such as required 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 methods and genetic engineering methods or a combination of these methods, including transgenic plants and including plant cultivars that may or may not be protected by plant breeders' rights. Plant parts are understood to mean all positions and organs above and below the ground of plants, such as buds, leaves, flowers and roots, and the examples shown are leaves, needles, stems, branches, flowers, fruit bodies, fruits and seeds, as well as tubers, roots and rhizomes. Plant parts also include harvested materials and asexual and sexual propagation materials, such as cuttings, tubers, rhizomes, buds and seeds.

[0410] Preferably, the formulations according to the invention are used by spray application against animal pests of the following pest families:

[0411] Preference is given to Pemphigidae: Eriosoma spp., Pemphigus spp. in crops such as citrus fruits, pome fruits, stone fruits, leafy vegetables, root and tuber vegetables and ornamental plants.

[0412] Preference is given to grape lice family (Phylloxeridae): Phylloxera spp. in grapes, nuts, citrus fruits.

[0413] Psyllidae: Psylla spp., Paratrioza spp., Tenalapharaspp., Diaphorina spp., Trioza spp. in tropical crops such as pome fruits, stone fruits, citrus fruits, vegetables, potatoes are preferred.

[0414] Preferred are Coccidae: Ceroplastes spp., Drosicha spp., Pulvinaria spp., Protopulminaria spp., Saissetia spp., Coccus spp. in perennial crops such as citrus fruits, pome fruits, drupes, olives, grapes, coffee, tea, tropical crops, ornamentals, vegetables.

[0415] Preference is given to the family of shield 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. in crops such as citrus fruits, pome fruits, drupes, almonds, pistachios, nuts, olives, tea, ornamentals, grapes, tropical crops.

[0416] Preferred are ensign scales family (Ortheziidae): Orthezia spp. in citrus fruits, pome fruits, drupes.

[0417] Preference is given to 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.

[0418] Also preferred are the family Aleyrodidae: Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleurodes spp., Dialeurodes spp., Parabemisia myricae in crops such as vegetables, melons, potatoes, tobacco, soft fruit, citrus fruits, ornamentals, cotton, soybeans and tropical crops.

[0419] Also preferred are the family Aphidae:

[0420] Myzus spp. in tobacco, stone fruits, soft fruits, fruiting vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamentals, spices,

[0421] Acyrthosiphon onobrychis in vegetables,

[0422] Aphis spp. in tobacco, citrus fruits, pome fruits, stone fruits, melons, strawberries, soft fruits, fruiting vegetables, leafy vegetables, tubers, stem and root vegetables, ornamental plants, potatoes, pumpkins, spices,

[0423] Yellow rose aphid (Rhodobium porosum) in strawberries,

[0424] Nasonovia ribisnigri in leafy vegetables

[0425] Macrosiphumspp. in ornamental plants, potatoes, leafy and fruiting vegetables, strawberries,

[0426] Phorodon humuli in hops,

[0427] Cabbage aphid (Brevicoryne brassicae) in leafy vegetables,

[0428] Toxoptera spp. in citrus fruits, drupes, almonds, nuts, spices,

[0429] Aulacorthum spp. in citrus fruits, potatoes, fruiting vegetables and leafy vegetables.

[0430] Anuraphis cardui in vegetables,

[0431] Brachycaudus helycrisii in sunflower,

[0432] Acyrthosiphon onobrychis in vegetables.

[0433] Likewise preferred are the Thripidae: Anaphothrips spp., Baliothrips spp., Caliothrips spp., Frankliniella spp., Heliothrips spp., Hercinothrips spp., Rhipiphorothrips spp., Scirtothrips spp., Kakothrips spp., Selenothrips spp. and Thrips spp. in crops such as fruit, cotton, grapes, tea, nuts, tropical crops, ornamentals, conifers, tobacco, spices, vegetables, soft fruit, melons, citrus fruits and potatoes.

[0434] Furthermore, preference is given to the families Agromyzidae and root-maggot flies (Anthomyiidae): Agromyza spp., Amauromyza spp., Atherigona spp., Chlorops spp., Liriomyza spp., Oscinella spp., Pegomyia spp. in crops such as vegetables, melons, potatoes, nuts, ornamental plants.

[0435] Preference is given to the families Cicadellidae and 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, fruits, grapes, potatoes, vegetables, ornamentals, conifers, melons, soft fruit, tea, nuts, rice and tropical crops.

[0436] Gracilariidae are preferred:

[0437] 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.

[0438] Cecidomyiidae is preferred:

[0439] 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, spices, soft fruits, conifers, hops.

[0440] Also preferred are the family Tephritidae:

[0441] 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.

[0442] Furthermore, preference is given to mites from the families Tetranychidae and Eriophydae:

[0443] Tetranychus spp., Panonychus spp., Aculops spp. in crops such as vegetables, potatoes, ornamentals, citrus fruits, grapes, conifers.

[0444] The treatment of plants and plant parts with the compositions according to the invention is carried out directly or by allowing the compositions to act on their habitat, environment or storage space by customary treatment methods, for example by drenching, impregnation, spraying, evaporation, misting, broadcasting, painting and, in the case of propagation materials, in particular seeds, also by applying one or more coatings.

[0445] Preferably, the plants to be treated are selected from the group consisting of cotton, soybeans, tobacco, vegetables, spices, ornamentals, conifers, citrus, fruits, tropical crops, nuts and grapes.

[0446] Preferably, the composition of the invention is used to combat pests from the following families: wool aphids, grape lice, psyllids, scale insects, shield scale insects, flag scale insects, mealybugs, whiteflies, aphids, thrips, leafhoppers, planthoppers, leafminers, gall midges, fruit flies, moths, spider mites, gall mites.

[0447] It has also been found that the composition of the present invention can be prepared by a process having the following steps:

[0448] 1) Mixing of components (a) to (h), followed by homogenization and bead milling. The relevant equipment for homogenization and bead milling is known to those skilled in the art.

[0449] This method also forms part of the subject matter of the present invention.

[0450] Finally, it has been found that the compositions according to the invention are very suitable for applying the agrochemical active ingredients present to plants and / or their habitat. 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 invention.

[0451] Substances used in the examples:

[0452]

[0453] Embodiment 1

[0454] All formulation ingredients according to the experiment described in Table 1a-c are combined in a 25ml PE screw bottle, and 10g of glass beads (1-1.25 mm in size) are added. The bottle is closed, clamped in a stirrer device (Retsch MM301), and processed for 40 minutes at 30Hz; in the process, the sample heats up. After this time has passed, the sample is cooled to room temperature, and the consistency of the preparation is evaluated. Subsequently, by a microscope (Zeiss transmitted light microscope, magnified 40 times), the particle size is measured, and the properties of the dispersion are evaluated. The particle size is very small, indicating good grindability, while the presence of agglomerates indicates poor dispersion characteristics.

[0455] Table 1a: (Values ​​are in % by weight)

[0456]

[0457] * Embodiment of the present invention

[0458] Table Ib: (Values ​​are in % by weight)

[0459]

[0460]

[0461] * Embodiment of the present invention

[0462] Table Ic: (Values ​​are in % by weight)

[0463]

[0464] * Embodiment of the present invention

[0465] Experimental evaluation:

[0466] The preparations based on fluopyrrolone, ammonium salt and propylene carbonate without added surfactant (experiments I-1, I-2) show the basic grindability of the ammonium salt under the specified experimental conditions, but under the microscope, significantly agglomerated salt crystals in the concentrate are observed, which means that the individual particles are very poorly dispersed in the liquid phase or even not dispersed at all. If a large amount of penetration aid, such as Lucramul HOT 5902, is added, the poor dispersion characteristics remain unchanged compared to the experiments without penetration aid (experiments I-3, I-4). In contrast, if a different surfactant, such as Antarox B / 848, is used to replace Lucramul HOT 5902 in the same amount, the grindability of the ammonium salt is just as good (experiments I-5, I-6), but fewer and smaller agglomerates are observed under the microscope, which indicates that the dispersibility of the salt crystals is significantly improved. By adding smaller amounts of specific dispersants, the dispersibility of the salt crystals in the liquid phase can be improved even further (experiments I-7, I-8, I-9, I-10, I-16), so that under the microscope, almost no agglomerates, if any, can be observed. Depending on the dispersing aid, differences in the ammonium salts used can be seen (experiment I-11 compared to I-12; experiment I-13 compared to I-14). In contrast, if small amounts of specific other adjuvants are added, in some cases no improvement effect is achieved, or even an opposite effect is achieved (experiments I-15 and I-17 to I-24). In these cases, more and larger agglomerates can be observed under the microscope compared to the samples containing only Antarox B / 848 as dispersant (see experiments I-5 and I-6 compared to experiments I-19 to I-24), and the consistency and overall grindability are also worse (experiments I-20, I-23 and I-24).

[0467] Example II

[0468] In order to test the grindability and dispersibility of specific solid active ingredients, such preparations are selected so that they do not contain any other crystalline solids (such as ammonium salts) except the corresponding active ingredients. All formulation ingredients in Table II are combined in 25ml HDPE screw-capped bottles, and 10g glass beads (size 1-1.25mm) are added. The bottle is closed, clamped in a stirrer device (Retsch MM301), and processed for 40 minutes at 30Hz. After this time has passed, the warm sample is cooled to room temperature, and the consistency of the test preparation is tested. Subsequently, by microscope (Zeiss transmitted light microscope, magnification 40 times), particle size and dispersion properties are determined. Particle size is very small to show good grindability, while the presence of agglomerates shows that dispersion characteristics are poor.

[0469] Table II (Values ​​are in % by weight)

[0470]

[0471]

[0472] Experimental evaluation:

[0473] In all examples (II-1 to II-7), it can be seen that the combination of Antarox B / 848 and Geropon T / 36 is suitable as a dispersing aid for dispersing various solid active ingredients in the formulations of the present invention without forming agglomerates of the active ingredient particles.

[0474] Example III

[0475] To test suitable thickeners in the presence of suitable dispersing aids, all formulation ingredients shown in Table III were combined and homogenized under stirring. Bead milling (Dispermat SL50, 80% 2 mm beads, 4000 rpm, 40 minutes of cycle milling) was then performed and the resulting formulations were analyzed. Subsequently, storage tests were performed at elevated temperatures and then after storage, the properties (e.g., appearance, consistency, and redispersibility) were qualitatively evaluated and the phase separation was quantitatively evaluated.

[0476] The phase separation occurring directly after storage is recorded as the sediment content and is calculated as the quotient of H1 [the level of the interface layer between the sediment phase and the supernatant] divided by H0 [the total filling height of the sample], or in this case as the supernatant content:

[0477] Sediment content = (H1 / H0)*100[%] or

[0478] Supernatant content = 100 – sediment content [%]

[0479] The redispersibility or re-homogenization of the sample is determined qualitatively by shaking the sample and subsequently evaluating the bottom of the sample container. A pronounced phase separation after a short storage time indicates limited storage stability and a clear tendency to form sediments which are difficult to disperse during storage, or even not dispersed at all.

[0480] The evaluation of the properties is similar to DIN 10964 "Sensory analysis-simple descriptive test". For this purpose, the shape, material state and color of the sample to be tested are checked visually - if necessary by shaking and tilting - as well as other properties (in particular, e.g. lumps, agglomerations, sediment formation, subsequent thickening, marbling of the sediment, etc.).

[0481] Table IIIa (Values ​​in g / l)

[0482]

[0483] * Embodiment of the present invention

[0484] Table IIIb (Values ​​in g / l)

[0485]

[0486]

[0487] * Embodiment of the present invention

[0488] # Results determined after 2 weeks of storage

[0489] Experimental evaluation:

[0490] Without using additional dispersing aids, using specific insoluble fillers such as Attagel 50, Aerosil 200, Aerosil 1812S or Bentone EW and specific combinations thereof, stable formulations with different viscosities can be prepared (III-1 & III-10 low viscosity; III-4, III-7 & III-13 high viscosity). After two or four weeks of storage under different conditions, these formulations have only low phase separation and, in some cases, good redispersibility. By using additional dispersing aids such as Geropon T / 36 (III-2, III-5, III-8, III-11, III-14), a full range of low viscosity formulations are obtained, whose sedimentation and redispersibility are at least equal or even better under the same conditions. In contrast, for example, the use of Soprophor 3D33 as an additional dispersing aid (III-3, III-6, III-9, III-12) resulted in formulations with some undesirable properties, such as marbling (III-3), sticky sediments (III-6, III-9, III-12) or extreme phase separation (III-6).

[0491] Example IV

[0492] In order to test suitable filler / dispersion system compositions, all formulation ingredients shown in Table IV were combined and homogenized under stirring. Subsequently, bead milling (Dispermat SL50, 80% 2 mm beads, 4000 rpm, 40 minutes of circulation milling) was performed and the resulting formulations were analyzed. Subsequently, storage tests were performed at high temperatures, and the appearance, consistency and phase separation after storage were then evaluated, and the viscosity (CIPAC MT192; "Viscosity of Liquids by rotationalviscometry") and the dispersion stability in a 2% aqueous dilution were determined. When qualitatively determining the dispersion stability, the time for the aqueous dispersion to produce a constant homogenization effect was recorded.

[0493] Table IV (Values ​​in g / l)

[0494]

[0495]

[0496] * Embodiment of the present invention

[0497] TC = Thermal Cycling Conditions (-10°C to +30°C Cycling Temperature Program)

[0498] Experimental evaluation:

[0499] By using different amounts of Aerosil 200, while using Geropon T / 36 as a dispersing aid, a low viscosity stable formulation can be prepared (IV-1). Although the use of a larger amount of Aerosil 200 (IV-2) leads to an increase in viscosity, the formulation solidifies during storage at 54° for 2 weeks. In contrast, the use of a composition of Aerosil 200 and Aerosil R812S can produce a more viscous stable formulation (IV-3). In addition, if a combination of Geropon T / 36 and another dispersing aid is used, the formulation properties can be further improved; thus, in the case of Soprophor FLK, the viscosity remains almost unchanged (IV-4), while the use of Morwet D-425 (IV-5) leads to an increase in viscosity. In experiments where Geropon T / 36 was omitted and no dispersing aid or only different dispersing aids were used (IV-6 to IV-8), it was found that the use of Morwet D-425 alone produced a sufficiently stable formulation.

[0500] Another factor determining the stability of a formulation is the dispersion stability of the formulation in an aqueous diluent. It has been found that, in particular, a combination of Geropon T / 36 and another dispersing aid (e.g., Soprophor FLK or Morwet D-425) has better dispersion stability than when only a single dispersing aid is used or when no dispersing aid is used at all.

[0501] Example V

[0502] Epidermal penetration of flupyralidone and I-2

[0503] Experimental steps:

[0504] The test measures the penetration of active ingredients through the enzymatically isolated apple tree leaf cuticle.

[0505] Use apples that have been cut from apple trees in a developing state and have been and Riederer ( , J., Riederer, M. (1986)). Only the epidermis of the top side of the leaf blade without stomata and hairs was used further.

[0506] For membrane transport studies, the epidermal membranes thus obtained are placed in a stainless steel diffusion cell (= transport chamber). To this end, the epidermis is placed with tweezers in the middle of the silicone-greased edge of the diffusion cell and sealed with a ring that is also greased. The chosen arrangement is such that the morphological exterior of the epidermis faces outwards, i.e. towards the air, while the original interior faces the interior of the diffusion cell. The diffusion cell is filled with water or a mixture of water and solvent and buffered to a physiologically relevant pH of 5.5. The culture medium in the diffusion cell should simulate the apoplast, i.e. the natural absorption medium in the leaf. This method is well suited to systemic and mechanistic studies with the aim of understanding the effects of formulations, adjuvants and solvents on the permeability of crop protection compositions.

[0507] To determine the penetration, in each case, 5 μl of a spray solution containing the active ingredients flupyralidone and I-2 was applied to the outside of the epidermis in the specified formulation (see Table V) in the following. The active ingredient concentration corresponds to the field application rate commonly used in practice. To prepare the spray solution, the given amount of the corresponding ingredient was added to tap water and homogenized by mixing.

[0508] After application of the spray solution, the water was allowed to evaporate in each case, the chambers were then turned upside down and placed in a thermostatic bath, in which air was blown onto the outside of the epidermis at a defined air humidity and temperature in each case. Thus, at a relative air humidity of 56% and a set temperature of 25°C, penetration began to occur. Samples were taken regularly using an automatic sampler and the content of the active ingredient that penetrated was measured by HPLC. The values ​​reported are in each case the average of 5 to 10 individual measurements.

[0509] Table V: Penetration test results

[0510]

[0511] Experimental evaluation:

[0512] The two active substances tested, flupyralidone and 1-2, by themselves, showed hardly any, if any, epidermal penetration when used without additives or in the presence of propylene carbonate (Table V, rows 1, 2). In the presence of diammonium hydrogen phosphate (DAHP), in particular Antarox B / 848, the application of the active ingredients independently led to improved epidermal permeability of the two active ingredients tested; here, the presence of propylene carbonate actually seemed to have a negative effect (Table V rows 3-6). The maximum penetration potential was found once all components were used in combination, which was an additive combination of the individual effects of the two active ingredients in the formulation.

Claims

1. A composition comprising: a) at least one active ingredient which is solid at room temperature and is selected from tetramic acid derivatives of formula (I-2) b) at least one active ingredient other than a) which is soluble in an organic solvent, selected from insecticides including fluopyridine and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluoro 3-Chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-Chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one; c) at least one ammonium salt selected from diammonium hydrogen phosphate (DAHP); d) at least one dispersant; e) one or more surfactants selected from the group consisting of polycarboxylates, salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, and combinations thereof; f) at least one water-insoluble filler which is a mixture of hydrophilic fumed amorphous silica and partially hydrophobic fumed amorphous silica; g) at least one solvent selected from propylene carbonate; and h) optionally other auxiliaries; wherein the active ingredient a) is insoluble or only slightly soluble in the selected solvent g); The components are as follows: a) 0.5-15 wt% b) 1-15% by weight c) 15-30% by weight d) 5-30% by weight e) 0.3-10% by weight f) 0.5-10% by weight h) 0-10% by weight g) up to 1 litre; Wherein component d) is selected from alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): Where R is a C1-C4 fragment, A is a polypropylene glycol segment consisting of 10 to 40 propylene oxide (PO) units (Formula III-b), 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, and an alkyl polypropylene glycol-polyethylene glycol compound of 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, One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

2. The composition according to claim 1, characterized in that a) selected insecticidal active ingredients, the solubility of which in the selected solvent g) is not more than 5 g / l.

3. The composition according to claim 2, characterized in that a) selected insecticidal active ingredients, the solubility of which in the selected solvent g) is not more than 4 g / l.

4. The composition according to claim 3, characterized in that a) selected insecticidal active ingredients, the solubility of which in the selected solvent g) is not more than 2.5 g / l.

5. The composition according to claim 4, characterized in that a) selected insecticidal active ingredients, the solubility of which in the selected solvent g) is not more than 1 g / l.

6. A composition according to claim 1 or 2, characterized in that In the general formula (III-a), R is a C3-C4 fragment.

7. A composition according to claim 6, characterised in that In the general formula (III-a), R is a C4 fragment.

8. The composition according to claim 1, characterized in that In the general formula (III-a), A is a polypropylene glycol segment consisting of 15 to 35 propylene oxide (PO) units (Formula III-b).

9. A composition according to claim 8, characterised in that In the general formula (III-a), A is a polypropylene glycol segment consisting of 20 to 30 propylene oxide (PO) units (Formula III-b).

10. The composition according to claim 1, characterized in that In the general formula (III-a), B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment, which is composed of 20-40 ethylene oxide (EO) units (Formula III-c) and 0-8 propylene glycol (PO) units.

11. A composition according to claim 10, characterised in that In the general formula (III-a), B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment, which is composed of 30-40 ethylene oxide (EO) units (Formula III-c) and 0-5 propylene glycol (PO) units.

12. The composition according to claim 1 or 2, characterized in that The components are present as follows: a) 2-15 wt% b) 2-15% by weight c) 15-30% by weight d) 10-30% by weight e) 0.5-2.5 wt % f) 1-10% by weight h) 0.05-6% by weight g) to 1 liter.

13. The composition according to claim 1 or 2, comprising a) A compound of formula (I-2) having the following structure: b) fluopyrrolidone, c) at least one ammonium salt selected from diammonium hydrogen phosphate (DAHP), d) at least one dispersant selected from the group consisting of: alkyl polypropylene glycol-polyethylene glycol compounds of formula (III-a) Where R is a C1-C4 fragment, A is a polypropylene glycol segment consisting of 10 to 40 propylene oxide (PO) units (Formula III-b), 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. and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId) RO-(C m A 2m o) x -(C n A 2n o) y -R'(IIId) The 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, One of the groups n or m is defined as 2, and the other group n or m is defined as 3, e) at least one surfactant selected from the group consisting of polycarboxylates, f) at least one water-insoluble filler which is a mixture of hydrophilic fumed amorphous silica and partially hydrophobic fumed amorphous silica; g) at least one solvent selected from propylene carbonate, h) optionally further auxiliaries.

14. A composition according to claim 13, characterised in that In the general formula (III-a), R is a C3-C4 fragment.

15. A composition according to claim 14, characterised in that In the general formula (III-a), R is a C4 fragment.

16. The composition according to claim 13, characterized in that In the general formula (III-a), A is a polypropylene glycol segment consisting of 15 to 35 propylene oxide (PO) units (Formula III-b).

17. A composition according to claim 16, characterised in that In the general formula (III-a), A is a polypropylene glycol segment consisting of 20 to 30 propylene oxide (PO) units (Formula III-b).

18. The composition according to claim 13, characterized in that In the general formula (III-a), B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment, which is composed of 20-40 ethylene oxide (EO) units (Formula III-c) and 0-8 propylene glycol (PO) units.

19. A composition according to claim 18, characterised in that In the general formula (III-a), B is a randomly copolymerized polyethylene glycol-polypropylene glycol segment, which is composed of 30-40 ethylene oxide (EO) units (Formula III-c) and 0-5 propylene glycol (PO) units.

20. The composition according to claim 1, characterized in that f) is a mixture of Aerosil 200 and Aerosil R812S.

21. Use of a composition according to any one of claims 1 to 20 for controlling insects.

22. A composition comprising: a) at least one active ingredient which is solid at room temperature and is selected from tetramic acid derivatives of formula (I-2) b) at least one active ingredient other than a) which is soluble in an organic solvent, selected from insecticides including fluopyridine and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluoro 3-Chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-Chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one; c) at least one ammonium salt selected from diammonium hydrogen phosphate (DAHP); d) at least one dispersant; e) one or more surfactants selected from the group consisting of polycarboxylates, salts of sulfated formaldehyde condensation products with alkyl aromatic compounds, and combinations thereof; f) at least one water-insoluble filler which is a hydrophilic fumed amorphous silica; g) at least one solvent selected from propylene carbonate; and h) optionally other auxiliaries; wherein the active ingredient a) is insoluble or only slightly soluble in the selected solvent g); The components are as follows: a) 0.5-15 wt % b) 1-15% by weight c) 15-30% by weight d) 5-30% by weight e) 0.3-10% by weight f) 0.1-2% by weight h) 0-10% by weight g) up to 1 litre; Wherein component d) is selected from alkyl polypropylene glycol-polyethylene glycol compounds of general formula (III-a): Where R is a C1-C4 fragment, A is a polypropylene glycol segment consisting of 10 to 40 propylene oxide (PO) units (Formula III-b), 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, and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId) RO-(CmH2mO)x-(CnH2nO)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, One of the groups n or m is defined as 2, and the other group n or m is defined as 3.

23. A composition according to claim 22, characterised in that f) is Aerosil 200.

Images