Insecticidal mixture formulations containing glycol ether solvents

Abstract

The invention relates to insecticidal active ingredient preparations comprising at least one dissolved active ingredient and one active ingredient 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 an insecticidal active ingredient preparation, which comprises at least one dissolved active ingredient and one active ingredient in solid form, which has good storage stability and high active ingredient permeability at high and low temperatures, and to a method for its preparation and 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 a formulation form that enables 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 available at any time.

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

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

[0005] As described 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 a dissolved form but in a solid particulate form, so these active ingredients in the formulation generally do not have good bioavailability. Here, the biological activity can be improved 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, can 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 storage stable over a relatively long period of time (12-24 months) and over a relatively wide temperature range (0 to 54° C.). This wide temperature range is required so that advantageously only a single formulation with the same active ingredient or combination of active ingredients can be used in different climatic regions.

[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] 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.

[0012] Furthermore, WO 2003 / 000053 describes specific alkylpolypropylene glycol-polyethylene glycols, for example Atlas G5000, as dispersants for organic crop protection products in oil.

[0013] The use of ammonium salts to enhance the effect of agrochemical active ingredients is known in the literature; for example, WO 2011 / 131623 (US2011 / 0281727 A1, Fischer et al.) records that insecticidal and / or herbicidal formulations based on heterocyclic tramic acid 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 combination of a single active ingredient selected from a material 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 preparations containing other active ingredients of the combination or about the physical and chemical stability of these mixture preparations. Suitable penetrants are described generally in paragraphs

[0111] to

[0171] and 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.

[0014] The preparation of the present invention having good permeability of dissolved active ingredients and undissolved active ingredients is neither described nor suggested in WO 2011 / 131623.

[0015] 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 2193712A1 records an oil-based agrochemical formulation, wherein the ammonium salt is in dispersed form. However, no suspension of the ammonium salt in a water-miscible solvent is recorded.

[0016] However, in summary, none of the above cited documents, taken individually or in combination, give any suggestion that alkyl polypropylene 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 glycol ethers), especially in combination with suspended and dissolved active ingredients.

[0017] Soluble water-based concentrates of tramic acid derivatives are known in the prior art, for example from WO 2009 / 115262. Due to solubility problems, they cannot be combined with certain crop protection products and formulation ingredients. In addition, these water-based SL formulations usually have a high pH value, which can also lead to incompatibility with certain alkali-sensitive crop protection products and formulation ingredients.

[0018] The problem to be solved is therefore 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.

[0019] This problem is solved by the formulations described below comprising a combination of active ingredients and an ammonium salt and a glycol ether as solvent.

[0020] Therefore, the present invention provides an insecticidal composition comprising:

[0021] 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),

[0022] b. at least one active ingredient other than a) which is soluble in an organic solvent,

[0023] c. at least one ammonium salt,

[0024] d. at least one dispersant selected from the group consisting of alkyl propoxylated ethoxylates,

[0025] e. optionally one or more surfactants,

[0026] f. at least one water-insoluble filler,

[0027] g. at least one solvent selected from glycol ethers, and

[0028] h. Other additives.

[0029] In a preferred embodiment, component e) is essential.

[0030] Furthermore, in a preferred embodiment, the composition is substantially free of water. The term "substantially free of water" refers to a composition containing less than 5% water, preferably less than 4% water, more preferably less than 3% water.

[0031] 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).

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

[0033] 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 a permuted manner, but in any case the same preference levels and in particular the most preferred embodiments / preferred levels can be combined with one another in each case and are indeed disclosed in such combinations.

[0034] Compositions described in this application consisting only of the essential components (and no optional components) should also be considered disclosed.

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

[0036] Component ah is 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 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).

[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 has 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.

[0040] 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), ingredients known as "mectins" (e.g. abamectin, emamectin benzoate, milbemectin; IRAC Group 6), ethiprole, triflumuron, deltamethrin, thiacloprid and tetronic acid and tramic acid derivatives (IRAC Group 23, including compounds of formula I and II described below).

[0041] In a preferred embodiment, component a) in the composition of the present invention is flucyanamide, cyantraniliprole, ethiprole, thiacloprid, spirotetramat, or

[0042] Keto-enols based on tramic acid, preferably compounds 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] R 1 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] Particular preference may be given to using the abovementioned tramic acid derivatives of the formula (I) 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 group,

[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 the tramic acid derivatives of the abovementioned formula (I) in which G = hydrogen (a).

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

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

[0070]

[0071]

[0072]

[0073] In a particularly preferred embodiment, component a) is a compound of the formula

[0074]

[0075] Compound I-2 is preferably used in its most thermodynamically stable polymorphic structure. The crystal structure and other physical data are determined as follows:

[0076] Sample preparation:

[0077] 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.

[0078] 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. Record (Figure 1).

[0079] As shown in FIG. 1 , 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:

[0080] Variant A of the invention is also characterized by the x-ray diffraction pattern shown in FIG. 1 .

[0081] 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.

[0082] Table 2: Crystallographic properties of modification A

[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]

[0091] The polymorphic form of modification A of I-1 can be determined by IR spectroscopy using the corresponding spectra, which have been determined at 25° C. using a diamond ATR instrument at 4 cm -1 As shown in Figure 2 and as recorded in Table 2c, variant A of the present invention shows at least 3, preferably at least 5, further preferably at least 7, and more preferably all spectral bands.

[0092] Table 2c) IR band [cm -1 ]

[0093]

[0094]

[0095]

[0096] In an alternative embodiment, component a) comprises tramic acid of formula (II)

[0097]

[0098] in

[0099] W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine,

[0100] X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine,

[0101] 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,

[0102] V 2 is hydrogen, halogen, C1-C6-alkyl or C1-C6-alkoxy,

[0103] V 3 is hydrogen or a halogen,

[0104] 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,

[0105] G is hydrogen (a) or one of the following groups

[0106]

[0107] in

[0108] E is a metal ion or an ammonium ion,

[0109] L is oxygen or sulfur, and

[0110] M is oxygen or sulfur,

[0111] R 1 is a straight-chain or branched C1-C6-alkyl group,

[0112] R 2 It is a straight-chain or branched C1-C6-alkyl group.

[0113] Particularly preferably used are the tramic acid derivatives of the abovementioned formula (I) in which the radicals are defined as follows:

[0114] W is more preferably hydrogen or methyl,

[0115] X is more preferably chlorine or methyl,

[0116] Y is more preferably hydrogen,

[0117] V 1 More preferably, it is fluorine or chlorine (especially fluorine or chlorine at the 4-position),

[0118] V 2 More preferably, it is hydrogen or fluorine (especially fluorine at the 3-position),

[0119] V 3 More preferably, it is hydrogen or fluorine (especially fluorine at the 5-position),

[0120] 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,

[0121] G is more preferably hydrogen (a) or one of the following groups

[0122]

[0123] in

[0124] More preferably, E is a monovalent metal ion or an ammonium ion (especially sodium or potassium),

[0125] R 1 More preferably, it is a straight-chain or branched C1-C4-alkyl group,

[0126] R 2 More preferred is a straight-chain or branched C1-C4-alkyl group.

[0127] Particularly useful are the tramic acid derivatives of the abovementioned formula (I) in which G = hydrogen (a).

[0128] Likewise particularly useful are the tramic acid derivatives of the abovementioned formula (I) in which G═E(d).

[0129] Particularly preferably used are the tramic acid derivatives of the abovementioned formula (II), in which the radicals are defined as follows:

[0130]

[0131]

[0132] In a particularly preferred alternative embodiment, a) is

[0133]

[0134] b. Soluble active ingredients

[0135] 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, and more preferably at least 40 g / l.

[0136] 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 methyl](2-fluorovinyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, or other insecticides as described in WO 2009 / 118025, for example 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0137] More preferably, the active ingredient b) is selected from imidacloprid, clothianidin, flupyradone, flonicamid and acetamiprid.

[0138] Most preferably, the active ingredient b) is flupyralidone.

[0139] In another embodiment, the active ingredient b) is flonicamid.

[0140] In yet another embodiment, the active ingredient b) is acetamiprid.

[0141] c. Ammonium salt

[0142] The ammonium salt is preferably selected from water-soluble inorganic ammonium salts.

[0143] Further preferably, c) is selected from ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0144] More preferably, c) is DAHP and AMS.

[0145] d. Dispersants

[0146] Component d) is preferably selected from alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a)

[0147] R——O——A——B——H

[0148] (III-a)

[0149] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0150] 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 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.

[0151]

[0152] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are:

[0153]

[0154] and a compound of formula (IIId)

[0155] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0156] The groups and subscripts have the following definitions:

[0157] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0158] m is 2 or 3;

[0159] n is 2 or 3;

[0160] x is 5 to 150; and

[0161] y is 5 to 150,

[0162] One of the groups n or m has a meaning of 2 and the other group n or m has a meaning of 3.

[0163] 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.

[0164] In the context of the present invention, branched C3 to C4-alkyl is understood to mean isopropyl, isobutyl or tert-butyl.

[0165] In a preferred embodiment, the R and R' groups are independently selected from methyl, n-butyl and hydrogen.

[0166] In an even more preferred embodiment, the R and R' groups are independently selected from n-butyl and hydrogen.

[0167] Regarding the arrangement of polyethylene and polypropylene units,

[0168] (a) The value of m can be set to 2, and the value of n to 3;

[0169] (b) Or the value of m can be set to 3 and the value of n can be set to 2.

[0170] Configuration (b) in which m=3 and n=2 is preferred.

[0171] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of the formula (IIId) in which

[0172] m is 3,

[0173] n is 2,

[0174] x is 5 to 80,

[0175] y is 5 to 80,

[0176] R is n-butyl or hydrogen, and

[0177] R' is hydrogen.

[0178] e. In the context of the present invention, suitable surfactants e) are selected from :

[0179] 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

[0180] 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

[0181] e3) a surfactant selected from the group consisting of lignin sulfonates and salts thereof, preferably selected from the group consisting of the following lignin sulfonates and salts thereof: Borresperse NA, Borresperse 3A, Ultrazine NA, Ufoxane 3A, Vanisperse CB, Marasperse AG, MARASPERSE N 22, MARASPERSE C 21, MARASPERSE CBOS-4, WAFEX CA122 and Borresperse CA from Borregaard; KRAFTSPERSE EDF-350, KRAFTSPERSE 25M, KRAFTSPERSE EDF-450, REAX 100M, REAX 83A, REAX 85A, REAX 88A, REAX 88B, REAX 907, REAX 910, POLYFON H, POLYFON O and POLYFON T from Ingevity; AGRINOL DN 19 and Agrinol C12, and

[0182] 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

[0183] e5) a surfactant selected from di / tristyrylphenol ethoxylated phosphates and salts thereof, DISPERSOGEN LFH, DISPERSOGEN TP 160 (available from Clariant);

[0184] LUCRAMUL PPS16, LUCRAMUL PPS K 16 (available from Levaco);

[0185] 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 ethoxylated phosphate esters, such as 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).

[0186] Further preferably, suitable surfactants are selected from surfactants e1), e2), e3) and e4).

[0187] Further preferably, suitable surfactants are selected from surfactants e1), e2) and e3).

[0188] Even further preferably, suitable surfactants are selected from the group consisting of surfactants e1) and e2).

[0189] More preferably, suitable surfactants are selected from surfactants e1).

[0190] Very particular preference is given to surfactants from e1), which comprise: 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).

[0191] WO 2008036865 A2 also describes suitable surfactants, such as Tersperse 2700.

[0192] The above surfactants can be used alone or in combination, preferably a combination of surfactants selected from the following: sodium salt of copolymer of maleic acid and olefin, salt of sulfated formaldehyde condensation product and alkyl aromatic compound, and lignin sulfonate and its salt.

[0193] f. Water insoluble fillers

[0194] Suitable fillers are preferably selected from

[0195] f1) Modified natural silicates, such as chemically modified bentonite, hectorite, attapulgite, montmorillonite, or other silicate minerals, such as (Elementis), (BASF), (Oil-Dri Corporation), Pangel B (Tolsa) or (Akzo Nobel),

[0196] f2) Synthetic silicates and fumed silicas, for example the following silicates: or Series (Degussa), series (Cabot) or Van Gel series (RTVanderbilt), and

[0197] f3) Fillers based on synthetic polymers, for example the following thickeners: or Series (Elementis).

[0198] The fillers of group f2 are more preferred.

[0199] 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.

[0200] g. Solvents

[0201] The solvent g) is selected from a compound or a mixture of compounds represented by formula 4, wherein

[0202]

[0203] y=1-9

[0204] A, B═H or linear C1-C4-alkyl, independently of one another, and

[0205] M=H or C1-C2-alkyl.

[0206] This refers to all definitions of g) in the present invention, with the exception of 1,2-propanediol which is explicitly excluded from the definition according to g).

[0207] In a more preferred embodiment, g) is selected from a compound or a mixture of compounds represented by formula 4, wherein

[0208] y=1-5

[0209] A, B═H or linear C1-C4-alkyl, independently of one another, and

[0210] M = H;

[0211] or g) a compound or a mixture of compounds selected from formula 4, wherein

[0212] y=1-5

[0213] A, B═H or linear C1-C4-alkyl, independently of one another, and

[0214] M = C1-C2-alkyl;

[0215] The exception is 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0216] Even further preferably, g) is selected from compounds represented by formula 4, wherein

[0217] y=1-3

[0218] A, B = H or methyl, independently of each other, and

[0219] M = methyl;

[0220] The exception is 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0221] Most preferably, g) is selected from dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol.

[0222] In a preferred embodiment, the solvent g) of the present invention may be present in the form of a mixture. The mixture of any one of g) may be present in a ratio of 1:50 to 50:1, preferably in a ratio of 1:25 to 25:1, more preferably in a mixture of 1:10 to 10:1, for example 1:10, 1:8, 1:6, 1:5, 1:2, 1:1, 2:1, 5:1, 6:1, 8:1 or 10:1. Yet another preferred embodiment comprises a mixture of any one of g) in a ratio range of 1:8 to 1:1, or in a ratio range of 1:1 to 8:1. Examples of solvents g) are Dowanol glycol ether products from Dow or different grades of polyethylene glycol ethers (e.g. ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol monobenzyl ether),

[0223] Or different grades of polypropylene glycol ethers (such as 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)

[0224] h. Other additives

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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 and 1,2-propylene glycol.

[0229] 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.

[0230] Useful antioxidants are all substances which can usually be employed for such purposes in agrochemical compositions. Butylated hydroxytoluene is preferred.

[0231] 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.

[0232] 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.

[0233] In a preferred embodiment, the present invention provides an insecticidal composition comprising:

[0234] a. Compounds of formula (I)

[0235]

[0236] The compounds of formula (I) have the following definitions:

[0237] W is a methyl group,

[0238] X is chlorine or methyl,

[0239] Y is chlorine, bromine or methyl,

[0240] 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,

[0241] G is hydrogen (a) or one of the following groups

[0242]

[0243] in

[0244] M is oxygen,

[0245] E is a monovalent metal ion or an ammonium ion,

[0246] R 1 is a straight-chain or branched C1-C4-alkyl group,

[0247] R 2 It is a straight-chain or branched C1-C4-alkyl group.

[0248] b. At least one active ingredient is preferably selected from the following insecticides: 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,

[0249] 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluorovinyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one and 4-[methyl[(6-chloropyridin-3-yl)methyl](amino)]furan-2(5H)-one.

[0250] 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),

[0251] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0252] R——O——A——B——H

[0253] (III-a)

[0254] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0255] A is a polypropylene glycol segment, 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 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,

[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 has a meaning of 2 and the other group n or m has a meaning of 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, lignin sulfonates and their salts, sulfated alkylaryl sulfonates and their salts, di / tristyrylphenol ethoxylated phosphates and their salts, and alcohol ethoxylated phosphates.

[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 a compound or a mixture of compounds represented by formula 4, wherein

[0269] y=1-5

[0270] A, B═H or linear C1-C4-alkyl, independently of one another, and

[0271] M = H;

[0272] or g) a compound or a mixture of compounds selected from formula 4, wherein

[0273] y=1-5

[0274] A, B=H or straight chain C1-C4-alkyl

[0275] M = C1-C2-alkyl;

[0276] The exception is 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0277] h. Other additives.

[0278] In a further preferred embodiment, the present invention provides an insecticidal composition comprising:

[0279] a. a compound of formula (I) selected from the following compounds:

[0280]

[0281]

[0282]

[0283] b. At least one active ingredient is preferably selected from the following insecticides: imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, sulfoxaflor, nitenpyram and flupyrazone, flonicamid and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E / Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one -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.

[0284] 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),

[0285] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0286] R——O——A——B——H

[0287] (III-a)

[0288] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0289] A is a polypropylene glycol segment, 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 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,

[0290]

[0291] and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId)

[0292] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0293] The groups and subscripts have the following definitions:

[0294] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0295] m is 2 or 3;

[0296] n is 2 or 3;

[0297] x is 5 to 150; and

[0298] y is 5 to 150,

[0299] One of the groups n or m has a meaning of 2 and the other group n or m has a meaning of 3,

[0300] 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,

[0301] 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.

[0302] g. at least one solvent selected from a compound or a mixture of compounds represented by formula 4, wherein

[0303] y=1-3

[0304] A, B = H or methyl, independently of each other, and

[0305] M = methyl;

[0306] The exception is 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0307] h. Other additives.

[0308] In an even further preferred embodiment, the present invention provides a pesticidal composition comprising:

[0309] a. A compound of formula (I-2) having the following structure:

[0310]

[0311] b. Flupyralidone,

[0312] c. at least one ammonium salt selected from ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP),

[0313] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0314] R——O——A——B——H

[0315] (III-a)

[0316] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0317] A is a polypropylene glycol segment, 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 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,

[0318]

[0319] and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId)

[0320] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0321] The groups and subscripts have the following definitions:

[0322] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0323] m is 2 or 3;

[0324] n is 2 or 3;

[0325] x is 5 to 150; and

[0326] y is 5 to 150,

[0327] One of the groups n or m has a meaning of 2 and the other group n or m has a meaning of 3,

[0328] e. at least one surfactant selected from polycarboxylates,

[0329] f. at least one filler selected from the group consisting of fumed silica and attapulgite.

[0330] g. at least one solvent selected from a compound or a mixture of compounds represented by formula 4, wherein

[0331] y=1-3

[0332] A, B = H or methyl, independently of each other, and

[0333] M = methyl; except for 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0334] h. Other additives.

[0335] In the most preferred embodiment, the present invention provides an insecticidal composition comprising:

[0336] a. A compound of formula (I-2) having the following structure:

[0337]

[0338] b. Flupyralidone,

[0339] c. at least one ammonium salt selected from ammonium sulfate (AMS) and diammonium hydrogen phosphate (DAHP),

[0340] d. At least one dispersant selected from the following: alkyl polypropylene glycol-polyethylene glycol compound of general formula (III-a)

[0341] R——O——A——B——H

[0342] (III-a)

[0343] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0344] A is a polypropylene glycol segment, 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 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,

[0345]

[0346] and an alkyl polypropylene glycol-polyethylene glycol compound of formula (IIId)

[0347] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0348] The groups and subscripts have the following definitions:

[0349] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0350] m is 2 or 3;

[0351] n is 2 or 3;

[0352] x is 5 to 150; and

[0353] y is 5 to 150,

[0354] One of the groups n or m has a meaning of 2 and the other group n or m has a meaning of 3,

[0355] e. at least one surfactant selected from polycarboxylates,

[0356] f. at least one filler selected from the group consisting of fumed silica and attapulgite.

[0357] g. at least one solvent or solvent mixture selected from the group consisting of dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol

[0358] h. Other additives.

[0359] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure.

[0360] Percentages - unless otherwise stated - are to be regarded as percentages by weight, wherein the % by weight of the composition total 100.

[0361] 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.

[0362] The proportion of solid active ingredients (component a) in the composition of the present invention is

[0363] Preferably 0.5-30% by weight,

[0364] More preferably, 1 to 20% by weight, and

[0365] More preferably, it is 1-15% by weight.

[0366] The proportion of the dissolved active ingredient (component b) in the composition of the present invention is preferably 1-20% by weight,

[0367] More preferably, 1 to 16% by weight, and

[0368] More preferably, it is 1-12% by weight.

[0369] The proportion of ammonium salt (component c) in the composition of the present invention is preferably 1-40% by weight.

[0370] More preferably, 5-35% by weight, and

[0371] More preferably, it is 15-30% by weight.

[0372] The proportion of the dispersant (component d) in the composition of the present invention is preferably 0.5-40% by weight,

[0373] More preferably, 2.5-35% by weight, and

[0374] More preferably, it is 5-30% by weight.

[0375] The proportion of surfactant (component e) in the composition of the present invention is preferably 0-10% by weight.

[0376] More preferably, 0.3-8% by weight, and

[0377] More preferably, it is 0.5-2.5% by weight.

[0378] The proportion of filler (component f) in the composition is

[0379] Preferably 0.1-10% by weight

[0380] More preferably, 0.5-10% by weight, and

[0381] More preferably, it is 2-10% by weight.

[0382] The proportion of other auxiliary agents (component h) in the composition of the present invention is preferably 1-20% by weight,

[0383] More preferably, 2.5-17.5% by weight, and

[0384] More preferably, it is 5-15% by weight.

[0385] A preferred embodiment of the present invention is a composition comprising the following components: a) 1-30 wt. %

[0386] b) 1-20% by weight

[0387] c) 1-40% by weight

[0388] d) 1-40% by weight

[0389] e) 0-10% by weight

[0390] f) 0.1-15% by weight

[0391] h) 1-20% by weight

[0392] g) to 1 liter.

[0393] A further preferred embodiment of the present invention is a composition comprising the following components:

[0394] a) 2-20% by weight

[0395] b) 1-60% by weight

[0396] c) 5-35% by weight

[0397] d) 5-35% by weight

[0398] e) 0.3-8% by weight

[0399] f) 0.5-12.5 wt %

[0400] h) 2.5-17.5% by weight

[0401] g) to 1 liter.

[0402] An even further preferred embodiment of the present invention is a composition comprising the following components:

[0403] a) 2-15 wt%

[0404] b) 1-12 wt%

[0405] c) 15-30% by weight

[0406] d) 10-30% by weight

[0407] e) 0.5-2.5 wt %

[0408] f) 1-10% by weight

[0409] h) 5-15% by weight

[0410] g) to 1 liter.

[0411] 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

[0412] c. at least one ammonium salt, and

[0413] d. at least one dispersant from the class of alkyl propoxylated ethoxylates.

[0414] In a preferred embodiment, the adjuvant composition further comprises

[0415] g. A solvent selected from a compound or a mixture of compounds represented by formula 4, wherein

[0416]

[0417] y=1-9

[0418] A, B═H or linear C1-C4-alkyl, independently of one another, and

[0419] M=H or C1-C2-alkyl;

[0420] The exception is 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0421] The ammonium salt from the auxiliary composition is preferably selected from water-soluble inorganic ammonium salts.

[0422] Further preferably, c) is selected from ammonium carbonate, ammonium bisulfate, ammonium sulfate (AMS), ammonium bicarbonate, ammonium carbonate and diammonium hydrogen phosphate (DAHP).

[0423] More preferably, b) is DAHP and AMS.

[0424] Component d) of the adjuvant composition (dispersant) is preferably selected from alkyl polypropylene glycol-polyethylene glycol compounds of the general formula (III-a)

[0425] R——O——A——B——H

[0426] (III-a)

[0427] wherein R is a C1-C4 fragment, preferably a C3-C4 fragment, more preferably a C4 fragment,

[0428] 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 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.

[0429]

[0430] Examples of "alkyl polypropylene glycol-polyethylene glycol compounds" are:

[0431]

[0432]

[0433] and a compound of formula (IIId)

[0434] RO-(C m H 2m O) x -(C n H 2n O) y -R' (IIId)

[0435] The groups and subscripts have the following definitions:

[0436] R and R' are independently hydrogen, linear C1 to C5-alkyl or branched C3 or C4-alkyl;

[0437] m is 2 or 3;

[0438] n is 2 or 3;

[0439] x is 5 to 150; and

[0440] y is 5 to 150,

[0441] One of the groups n or m has a meaning of 2 and the other group n or m has a meaning of 3.

[0442] 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.

[0443] In the context of the present invention, branched C3 or C4-alkyl is understood to mean isopropyl, isobutyl or tert-butyl.

[0444] In a preferred embodiment, the R and R' groups are independently selected from methyl, n-butyl and hydrogen.

[0445] In an even more preferred embodiment, the R and R' groups are independently selected from n-butyl and hydrogen.

[0446] Regarding the arrangement of polyethylene and polypropylene units,

[0447] (a) The value of m can be set to 2, and the value of n to 3;

[0448] (b) Or the value of m is 3 and the value of n is 2.

[0449] Configuration (b) in which m=3 and n=2 is preferred.

[0450] Very particular preference is given to alkylpolypropylene glycol-polyethylene glycol compounds of the formula (IIId) in which

[0451] m is 3,

[0452] n is 2,

[0453] x is 5 to 80,

[0454] y is 5 to 80,

[0455] R is n-butyl or hydrogen, and

[0456] R' is hydrogen.

[0457] The solvent g) used together with the auxiliary composition is further preferably selected from the compound or mixture of compounds represented by formula 4, wherein

[0458] y=1-5

[0459] A, B═H or linear C1-C4-alkyl, independently of one another, and

[0460] M = H;

[0461] or g) a compound or a mixture of compounds selected from formula 4, wherein

[0462] y=1-5

[0463] A, B=H or straight chain C1-C4-alkyl

[0464] M = C1-C2-alkyl;

[0465] The exception is 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0466] Even further preferably, g) is selected from compounds represented by formula 4, wherein

[0467] y=1-3

[0468] A, B = H or methyl, independently of each other, and

[0469] M = methyl; except for 1,2-propylene glycol, which is explicitly excluded from the definition according to g).

[0470] Most preferably, g) is selected from dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol.

[0471] In a preferred embodiment, the solvent g) of the present invention may be present in the form of a mixture. The mixture of any one of g) may be present in a ratio of 1:50 to 50:1, preferably in a ratio of 1:25 to 25:1, more preferably in a mixture of 1:10 to 10:1, for example 1:10, 1:8, 1:6, 1:5, 1:2, 1:1, 2:1, 5:1, 6:1, 8:1 or 10:1. Yet another preferred embodiment comprises a mixture of any one of g) in a ratio range of 1:8 to 1:1, or in a ratio range of 1:1 to 8:1.

[0472] 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.

[0473] The proportion of the auxiliary composition based on the weight of the total formulation is preferably

[0474] c) 1-40% by weight

[0475] d) 1-40% by weight

[0476] Further optimization

[0477] c) 5-35% by weight

[0478] d) 5-35% by weight, and

[0479] Even more preferably

[0480] c) 15-30% by weight

[0481] d) 10-30% by weight.

[0482] The application rate of the preparation according to the invention can vary within a relatively wide range. This is determined by the active ingredients and their content in the composition. The application volume of the preparation according to the invention in the aqueous spray solution can also vary within a relatively wide range, which means that the applicable spray volume can vary between 10 and 500 l / ha.

[0483] 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.

[0484] Composition of the present invention can be used for processing all plants and plant parts.In the context of the present invention, plant should be 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 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 above and below the ground of plant, such as buds, leaves, flowers and roots, and the examples shown are leaves, needles, stems, branches, flowers, fruit bodies, fruits and seeds, and tubers, roots and rhizomes.Plant parts also include harvesting materials and asexual and sexual propagation materials, such as cuttings, tubers, rhizomes, buds and seeds.

[0485] Preferably, the formulations according to the invention are used by spray application against animal pests of the following pest families:

[0486] 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.

[0487] Preference is given to grape lice family (Phylloxeridae): Phylloxera spp. in grapes, nuts, citrus fruits.

[0488] 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.

[0489] 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.

[0490] 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.

[0491] Preferred are ensign scales family (Ortheziidae): Orthezia spp. in citrus fruits, pome fruits, drupes.

[0492] 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.

[0493] 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.

[0494] Also preferred are the family Aphidae:

[0495] Myzus spp. in tobacco, stone fruits, soft fruits, fruiting vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamentals, spices,

[0496] Acyrthosiphon onobrychis in vegetables,

[0497] 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,

[0498] Yellow rose aphid (Rhodobium porosum) in strawberries,

[0499] Nasonovia ribisnigri in leafy vegetables

[0500] Macrosiphumspp. in ornamental plants, potatoes, leafy and fruiting vegetables, strawberries,

[0501] Phorodon humuli in hops,

[0502] Cabbage aphid (Brevicoryne brassicae) in leafy vegetables,

[0503] Toxoptera spp. in citrus fruits, drupes, almonds, nuts, spices,

[0504] Aulacorthum spp. in citrus fruits, potatoes, fruiting vegetables and leafy vegetables.

[0505] Anuraphis cardui in vegetables,

[0506] Brachycaudus helycrisii in sunflower,

[0507] Acyrthosiphon onobrychis in vegetables.

[0508] 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.

[0509] 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.

[0510] 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.

[0511] Gracilariidae are preferred:

[0512] 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.

[0513] Cecidomyiidae is preferred:

[0514] 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.

[0515] Also preferred are the family Tephritidae:

[0516] 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.

[0517] Furthermore, preference is given to mites from the families Tetranychidae and Eriophydae:

[0518] Tetranychus spp., Panonychus spp., Aculops spp. in crops such as vegetables, potatoes, ornamentals, citrus fruits, grapes, conifers.

[0519] 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.

[0520] Preferably, the plants to be treated are selected from cotton, soybeans, tobacco, vegetables, spices, ornamental plants, conifers, citrus plants, fruits, tropical crops, nuts and grapes.

[0521] Preferably, the compositions of the present invention are used to combat pests from the following families: woolly aphids, grape lice, psyllids, scale insects, armored scale insects,旌蚧 (no English equivalent provided), mealybugs, whiteflies, aphids, thrips, leafhoppers, planthoppers, leaf miners, gall midges, fruit flies, leafminers, spider mites, eriophyid mites.

[0522] It has also been found that the compositions of the present invention can be prepared by a method having the following steps:

[0523] 1) Mix 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.

[0524] This method also forms part of the subject matter of the present invention.

[0525] Finally, it has been found that the compositions of the present invention are very suitable for applying the existing agrochemical active ingredients 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 it.

[0526] Materials and methods:

[0527]

[0528] The following tests and methods apply:

[0529] Rotational viscosity Measured according to CIPAC MT 192. Stable and convenient formulations are expected to show a medium range of viscosities for easy emptying and cleaning of bottles.

[0530] Rheology Measured using a Bohlin Gemini rheometer. At room temperature, using a frequency sweep program with ether strain or stress control, G' (elastic modulus), G'' (viscous modulus) and phase angle are measured at different frequencies (0.01 - 5 Hz), and values are reported at 0.5 Hz. It is generally recognized by those skilled in the art that a small phase angle and large values of G' (> G'') indicate a high probability of a stable formulation, while a large phase angle and small values of G' (< G'') indicate a high probability of a less stable formulation.

[0531] Particle sizeDetermined by laser diffraction (according to CIPAC MT 187 Malvern Mastersizer, medium: propylene glycol) or using an optical microscope (40x magnification).A stable and convenient formulation is expected to contain small particles to ensure good storage stability in concentrates and good suspension stability in aqueous dilutions.

[0532] Suspension stability The evaluation is carried out according to the simplified method of CIPAC MT 180 and is measured in a 2% aqueous dilution in CIPAC D water, after a 1 hour standing time. Stable and convenient formulations are expected to have no or very little sediment formation at the bottom of the test container to ensure uniform application of the spray solution.

[0533] Storage test Perform at different temperatures for a given number of weeks (w), such as 0°C, 20°C, 30°C, 40°C, 54°C or freeze-thaw cycles (or temperature cycling; continuous temperature changes from -15°C to +30°C and back within one week).

[0534] The redispersibility of the sample was determined qualitatively by shaking the sample and subsequently evaluating the bottom of the sample container.

[0535] Evaluation of formulation properties Analogous 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.).

[0536] Directly after storage Phase separation is recorded as the sediment fraction and is calculated by dividing H1 [the level of the interface layer between the sediment phase and the supernatant] by H0 [the total fill height of the sample], or in this case as the supernatant fraction:

[0537] Sediment fraction = (H1 / H0)*100[%] or

[0538] Supernatant fraction = 100 - sediment content [%]

[0539] A stable and convenient formulation would be expected to show no or only minimal phase separation upon prolonged storage at elevated temperatures and to be easily rehomogenizable. Significant phase separation after short storage times indicates limited storage stability and a significant tendency to form deposits which are difficult, if not impossible, to disperse during storage.

[0540] Embodiment 1

[0541] All formulation ingredients according to the experiments described in Table I are combined in a suitable container and homogenized under stirring. Subsequently, bead milling (e.g., Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation milling) is performed until a particle size of 10-15 μ is reached (determined by microscopy). The resulting formulation is analyzed by, for example, suspension stability and rotational viscosity. Subsequently, a storage test is performed at high temperature, and then the phase separation after storage is quantitatively evaluated.

[0542] Table I (values ​​in grams / L)

[0543]

[0544] *Examples of the present invention. DAHP = diammonium hydrogen phosphate; DOM = date of manufacture

[0545] discuss: As shown in Table 1, the preparations prepared according to Examples I-1 to I-3 showed suitable particle size and excellent suspension stability as well as low to moderate viscosity and very low phase separation after storage for 2 weeks under different conditions. The preparation prepared according to Example I-4 showed high viscosity combined with coarse particles and therefore did not conform to the present invention. In this case, since high viscosity had accumulated after grinding for a few minutes and the grinding process was stopped at this time, samples with smaller particle sizes were not prepared further.

[0546] Example II

[0547] All formulation ingredients according to the experiments described in Table II are combined in a suitable container and homogenized under stirring. Subsequently, bead milling (e.g., Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding) is performed until a particle size of 10-15 μ is reached (determined by microscopy). The resulting formulation is analyzed by, for example, suspension stability, rotational viscosity and rheology (determination of phase angle, G' and G "). Subsequently, storage tests are performed at high temperatures and then the phase separation after storage is quantitatively evaluated.

[0548] Table II (Values ​​in grams / L)

[0549]

[0550] *Examples of the present invention; DAHP = diammonium hydrogen phosphate

[0551] discuss:

[0552]

[0553] *Embodiment of the present invention; DoM = Day of Manufacturing

[0554] All formulations according to the invention exhibited a viscosity lower than or approximately equal to 1000 mPa*s@7.5 1 / s, which can be considered to be practically useful (Table II, Examples II-1; II-3 to II-5; II-8; II-9). All examples exhibited a small phase angle of 30° or approximately 30°, which is attributed to good storage stability. However, all examples according to the invention exhibited an elastic modulus G' of approximately equal to or lower than 100 Pa and a corresponding viscous modulus G" that was significantly lower than G'. With regard to phase separation, all formulations according to the invention exhibited no or only a low level of supernatant after storage for 4, 8 or 16 weeks at 20°C / room temperature, 40°C or temperature cycling. Thus, a maximum phase separation between 0-10% was observed after storage for 8 weeks or 16 weeks at 40°C, respectively. Formulations containing large amounts of propylene glycol exhibited higher viscosities and / or higher levels of supernatant of up to 14% (Table I, Examples II-2; II-6; II-7) and were therefore not in accordance with the invention.

[0555] Example III

[0556] In order to test different levels of carrier liquid g), auxiliary agent h) and water-insoluble filler f), all formulation ingredients according to the experiment described in Table III are combined in a suitable container and homogenized under stirring. Subsequently, bead milling (e.g., Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation milling) is performed until a particle size of 10-15 μ is reached (determined by microscopy). The resulting formulation is analyzed by suspension stability, rotational viscosity and rheology. Subsequently, a storage test is performed at high temperature and the suspension stability after storage is then quantitatively evaluated.

[0557] Table 3 (Values ​​in grams / L)

[0558]

[0559] *Examples of the present invention; DAHP=diammonium hydrogen phosphate; # Determination after 2 weeks

[0560] discuss:The preparations prepared according to Examples III-1 and III-2 showed moderate viscosity and good suspension stability even after storage; in addition, Example III-1 showed a small phase angle, an elastic modulus G' approximately equal to or lower than 100 Pa, and a corresponding viscous modulus G' significantly lower than G'. Therefore, III-1 and III-2 are examples of the present invention. Compared with III-1, the preparation prepared according to Example III-3 had a slightly higher viscosity and showed similar G', which can be attributed to the increase in the amount of propylene glycol in the formula. The preparations prepared according to Examples III-4 and III-5 showed increased and high viscosity and elastic modulus G', which can also be attributed to the increase in the amount of propylene glycol in the formula.

[0561] Example IV

[0562] In order to test different combinations of at least one active ingredient a) that is solid at room temperature and at least one active ingredient b) while keeping the formulation unchanged, the appropriate active ingredients were selected as specified in Table IV, combined and homogenized under stirring. Subsequently, bead milling (Dispermat SL50, 80% 2 mm beads, 4000 rpm, cycle milling 40 min) was performed and the resulting formulation was analyzed by, for example, suspension stability, rotational viscosity and particle size evaluation. Subsequently, storage tests were performed at high temperatures and the samples were further evaluated, including phase separation determination after storage.

[0563] Table IV (Values ​​in grams / L)

[0564]

[0565]

[0566] *Examples of the present invention; DAHP = diammonium hydrogen phosphate; DoM = day of manufacture

[0567] discuss: Examples IV-1 to IV-7 show rotational viscosities of 850 to 1500 mPa*s at 7.5 1 / s and particle sizes d90 (Malvern results) of 3 to 6 μm and excellent suspension stability after 1 h. After 2 weeks of storage, hardly any phase separation was detected, only minor changes in the particle size were visible (except for Example IV-4, where some crystal growth was visible after storage at 54° C.), which shows that the formulations according to the invention are stable. In addition, the suspension stability after storage continued to be good, in some cases even very good.

[0568] Example V

[0569] Epidermal penetration of flupyralidone and I-2

[0570] Experimental steps:

[0571] The test measures the penetration of active ingredients through the enzymatically isolated apple leaf cuticle.

[0572] Use apples that have been cut from the tree in a fully developed state and and Riederer ( The leaves were separated by the method described in J., Riederer, M. (1986). Only the epidermis of the top of the leaves without pores and hairs was used further.

[0573] For membrane transport studies, the epidermal membranes thus obtained are placed in a stainless steel diffusion cell (= transport chamber). For this purpose, 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 arrangement is chosen so 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 system and mechanism studies with the aim of understanding the effect of formulations, adjuvants and solvents on the permeability of crop protection compositions.

[0574] To determine the penetration, in each case, 5 μl of a spray solution containing the active ingredients flupyralidone and I-1 in the specified formulation (see Table V) was applied to the outside of the epidermis. The active ingredient concentrations corresponded to the field application rates customary in practice. To prepare the spray solution, the given amounts of the corresponding ingredients were added to tap water and homogenized by mixing.

[0575] 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 at a defined air humidity and temperature was blown onto the outside of the epidermis 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 penetration content of the active ingredient was measured by HPLC. The values ​​reported are in each case the average of 5 to 10 individual measurements.

[0576] Table V: Penetration test results

[0577]

[0578] *DAHP = diammonium hydrogen phosphate, $ :A=dipropylene glycol monomethyl ether,

[0579] B = propylene glycol monomethyl ether, C = propylene glycol, D = dipropylene glycol

[0580] Experimental evaluation:

[0581] The two active substances tested, flupyralidone and 1-2, when used alone without additives, showed hardly any, if any, epidermal penetration by themselves (Table V, row 1). In the presence of diammonium hydrogen phosphate (DAHP) and especially Antarox B / 848, the application of the active ingredients independently led to an improvement in the epidermal permeability of both active ingredients tested (Table V rows 2-3). The greatest penetration potential was found once Antarox B / 848 and DAHP were used in combination, which was an additive combination of the effects of the two active ingredients in the formulation (Table V, row 4). Very similar effects were observed in the presence of different solvent combinations (Table V, rows 5-8) and in the combination of Antarox B / 848 and DAHP; although flupyralidone showed an increased permeation behavior, the permeation of 1-2 was slightly reduced, but still at a very high level and certainly superior to the use of Antarox B / 848 or DAHP alone.

Claims

1. A composition comprising: a) 2-15% by weight of at least one active ingredient which is solid at room temperature and is selected from flucyanamide, cyantraniliprole, ethiprole, thiacloprid, spirotetramat or a compound of formula (I-2), b) 1 to 12% by weight of at least one active ingredient other than a) which is soluble in an organic solvent and which is selected from flupyralid or acetamiprid, c) 15 to 30% by weight of at least one ammonium salt selected from ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate, ammonium hydrogen carbonate and diammonium hydrogen phosphate, d) 10-30 wt% of at least one dispersant selected from the group consisting of an alkyl polypropylene glycol polyethylene glycol compound of the general formula (III-a) and an alkyl polypropylene glycol polyethylene glycol compound of the general formula (IIId); R——O——A——B——H (III-a) Where R is the C4 fragment, A is a polypropylene glycol segment consisting of 20 to 30 propylene oxide (PO) units (Formula III-b), 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 oxide (PO) units. 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 has a meaning of 2 and the other group n or m has a meaning of 3, e) 0.5-2.5% by weight of a combination of a sodium salt of a copolymer containing maleic acid and an olefin and a salt of a sulfated formaldehyde condensation product with an alkyl aromatic compound, f) 1-10% by weight of fumed silica, g) at least one solvent selected from dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol, and h) 5-15% by weight of other auxiliaries, wherein the active ingredient a) is insoluble or only slightly soluble in the selected solvent g); wherein g) is added to make up the volume of the composition to 1 liter.

2. The composition according to claim 1, characterized in that Component a) is a compound of formula (I-2) 3. The composition according to claim 1, characterized in that Component a) is a compound of formula (I-2), and component b) is flupyralidone 4. The composition according to claim 1, characterized in that Component c) is selected from ammonium sulfate and ammonium salts of diammonium hydrogen phosphate.

5. The composition according to claim 1, characterized in that Component d) is at least one dispersant selected from the group consisting of alkyl polypropylene glycol polyethylene glycol compounds of the 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, One of the groups n or m has a meaning of 2 and the other group n or m has a meaning of 3.

6. The composition according to claim 1, characterized in that Component d) was Antarox B / 848.

7. The composition according to claim 1, characterized in that Component e) is a combination of: a sodium salt of a copolymer of maleic acid and an olefin selected from Geropon T / 36, and a salt of a sulfated formaldehyde condensation product and an alkyl aromatic compound selected from Morwet D-425.

8. The composition according to claim 1, characterized in that Component f) is Aerosil R812S.

9. The composition according to claim 1, characterized in that Component h) is selected from emulsifiers, wetting agents, foam inhibitors, preservatives, dyes, stabilizers and antioxidants.

10. The composition according to claim 1, characterized in that Component h) is selected from 1,2-propylene glycol and silicone oils.

11. A composition according to any one of claims 1 to 10, comprising a) 2-15% by weight of a compound of formula (I-2): b) 1 to 12% by weight of flupyralidone, c) 15-30% by weight of at least one ammonium salt selected from ammonium sulfate and diammonium hydrogen phosphate, d) 10-30 wt% of at least one dispersant selected from the group consisting of an alkyl polypropylene glycol polyethylene glycol compound of the general formula (III-a) and an alkyl polypropylene glycol polyethylene glycol compound of the general formula (IIId): R——O——A——B——H (III-a) Where R is the C4 fragment, A is a polypropylene glycol segment consisting of 20 to 30 propylene oxide (PO) units (Formula III-b), 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 oxide (PO) units. 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 has a meaning of 2 and the other group n or m has a meaning of 3, e) 0.5-2.5% by weight of a combination of a sodium salt of a copolymer containing maleic acid and an olefin and a salt of a sulfated formaldehyde condensation product with an alkyl aromatic compound, f) 1-10% by weight of fumed silica, g) at least one solvent selected from dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol, and h) 5-15% by weight of other additives; wherein g) is added to make up the volume of the composition to 1 liter.

12. The composition according to claim 11, characterized in that Component d) is at least one dispersant selected from the group consisting of alkyl polypropylene glycol polyethylene glycol compounds of the general 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 has a meaning of 2 and the other group n or m has a meaning of 3.

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

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