EP2348833A2 - Liquid aqueous crop protection formulations - Google Patents

Abstract

The present invention relates to a novel liquid aqueous crop protection formulation which comprises a) at least one organic active crop protection ingredient with a water solubility of less than 5 g/l at 20°C; b) at least one organic solvent with a water solubility of more than 100 g/l at 20°C; c) at least one organic solvent with a water solubility of 2 to 100 g/l at 20°C; d) at least one organic solvent with a water solubility of less than 2 g/l at 20°C; e) at least one nonionic surfactant; f) at least one anionic surfactant; and g) water. The invention also relates to the use of the crop protection formulation for treatment of plants and seed, to corresponding methods and to treated seed.

Description

 Liquid, aqueous crop protection formulations

description

The present invention relates to liquid, aqueous crop protection formulations of one or more crop protection active ingredients, the use of the crop protection formulations for the treatment of plants and seeds, corresponding processes and treated seeds.

The protection of crops or crops against infestation with plant-damaging organisms, the targeted control of the growth of crops, but also the control of harmful plants by applying suitable pesticides are important instruments of yield increase and thus also the safeguard of plant food production.

In the phase before and during germination and sprouting, many plants, especially useful plants, are extremely susceptible to attack by phytopathogenic fungi, bacteria, viruses, nematodes and insects. This is partly due to the small size of the plant parts, which makes it difficult for the plant to compensate for damage. On the other hand, the natural defense mechanisms of the plant are often not developed at this early stage of growth. Protection of the plant before and during germination is therefore an important tool for reducing plant damage.

In order to avoid diseases of seeds and seedlings, seed is treated prior to seeding with seed stains containing plant protection agents, usually fungicides and often other pesticides, in particular insecticides. Organic chemical fungicides and insecticides are currently mostly used in the form of aqueous formulations, so that good interaction with the target organism is ensured. However, many of these agents are sparingly soluble or not at all soluble in water, i. H. they have a water solubility of less than 5 g / l, often less than 1 g / l and in particular less than 0.1 g / l at 25 ° C. Producing stable formulations of pesticide compounds that can be easily diluted with water is therefore a recurrent problem.

For seed treatment applications, besides the stability of the formulation, other factors are of high importance. The seed should have a good flow behavior after application of the stain, so that clumping or caking in the plant during pickling or sowing is prevented and thus high throughput rates are made possible. In addition, a low abrasion of the stain is advantageous because the concomitant reduced dust during pickling or seeding leads to improved Arbreitssicherheit and environmental compatibility. Organic pesticides with limited water solubility are often formulated for purposes of seed dressing as suspension concentrates or as emulsifiable concentrates used after dilution with water.

In emulsifiable concentrates, the active ingredient is present together with surface-active substances as a solution in an organic, water-immiscible solvent, typically a hydrocarbon mixture and / or a fatty acid methyl ester. Disadvantages are the use of large amounts of often toxic solvents and the low dilution stability.

Suspension concentrates are formulations in which the active ingredient is in the form of finely divided, for example finely ground, particles which are suspended in aqueous dispersion media with the aid of surface-active substances. The surface-active substances have the task of stabilizing the active substance particles in the dispersion medium. However, the use of suspension concentrates frequently involves problems associated with the fact that the particles settle on storage for prolonged periods or at elevated temperatures and then can hardly be resuspended, and that crystalline material forms during storage. As a result, these formulations are difficult to handle and their biological effectiveness may be inconsistent. In addition, suspension concentrates are limited to relatively high melting point active agents. Many crop protection ingredients are also partially "deactivated" by water when formulated as a suspension concentrate.

Commercially available seed pickling based on aqueous suspension concentrates are more environmentally friendly than emulsifiable concentrates, but do not have their good application properties.

An alternative to suspension concentrates and emulsifiable concentrates are microemulsions (ME). Microemulsions, also referred to as ME formulations in the case of active ingredient-containing microemulsions, are liquid multiphase systems composed of water and at least one water-immiscible or only slightly water-miscible organic solvent a disperse phase and a continuous phase, wherein the disperse phase forms droplets or vesicles or even complex

Structures can form. In microemulsions, the mean separation of phase boundaries, typically the mean particle size, or droplet size (Z = light scattering average diameter) of the disperse phase, is at least 5 times smaller and is generally not more than 500 in comparison to ordinary emulsions nm, in particular not more than 300 nm or even 200 nm, whereas the droplets in emulsions have a mean diameter in the micron range. As a further distinguishing feature, microemulsions are thermodynamically stable and form without the high energy input needed for emulsions. Due to the small particle size (droplet size) of the disperse phase or the complex channels, microemulsions are optically transparent.

Microemulsion formulations of organic pesticides are usually water based and additionally include at least one surfactant and at least one co-solvent, which is typically an organic solvent or a low molecular weight polyalkylene ether. Due to the high water content, the use of ME formulations reduces risks such as flammability, toxicity, environmental damage and costs compared with emulsifiable concentrates (EC). In addition, due to the small particle size of the disperse phase containing the active ingredient, increased bioavailability can be achieved in many cases. However, it is difficult to formulate microemulsions of poorly water-soluble active ingredients in such a way that they are permanently stable in terms of droplet size, uniformity and crystallization tendency of the active ingredient. In addition, the droplet size should remain stable even when diluted with water so as to preserve the biological effects of dilutions obtained from concentrated formulations.

EP 1 347 681 discloses microemulsion concentrates which comprise a hydrophobic agrochemical, an alkylalkanoate as a first solvent, a polyhydric alcohol or a condensate of polyhydric alcohols as a second solvent and a surfactant. The use of these concentrates in crop protection is claimed only in the general sense, without concrete applications are described, for example, for seed treatment.

WO 2006/030006 describes seed dressings based on microemulsions which contain the fungicide flutriafol, a surfactant system, an antifreeze and a water-insoluble liquid which is selected from alkyl lactates and dialkyl esters of adipic, glutaric and succinic acids. Compositions beyond this narrow range are not mentioned.

WO 2007/028382, WO 2007/028387 and WO 2007/028388 disclose liquid formulations of triazole fungicides which contain vegetable oil esters, at least one water-miscible polar aprotic co-solvent and at least one water-immiscible cosolvent.

It is therefore an object of the present invention to provide crop protection formulations which have seed treatment properties which are advantageous for a broad spectrum of active substances. In particular, they should be distinguished by high stability and a homogeneous distribution of active ingredients. additionally Seeds treated with these formulations should have good flowability and low abrasion of the stain.

This object has surprisingly been achieved by the liquid, aqueous crop protection formulations described below.

The present invention is a liquid aqueous crop protection formulation, preferably in form of an aqueous microemulsion comprising a) at least one organic crop protection agent having a solubility in water of less than 5 g / l at 20 ⁰ C; b) at least one organic solvent having a water solubility of more than 100 g / l, in particular at least 200 g / l or at least 300 g / l at 20 ^° C. (solvent b); c) at least one organic solvent having a water solubility of 2 to 100 g / l, in particular 3 to 90 g / l or 4 to 80 g / l at 20 ° C (solvent c); d) at least one organic solvent having a water solubility of less than 2 g / l, in particular not more than 1 g / l or not more than 0.5 g / l at 20 ^° C. (solvent d); e) at least one nonionic surfactant; f) at least one anionic surfactant; and g) contains water.

Accordingly, further articles of the present invention relate to the use of the crop protection formulations according to the invention for the treatment of plants or seeds and to corresponding processes. Another object of the present invention is a seed treated with such a crop protection formulation.

In particular, the formulations according to the invention provide stable aqueous formulations of organic, water-insoluble crop protection active ingredients, preferably fungicides, optionally in combination with further organic crop protection active ingredients, for the treatment of plants and seeds, preferably of seeds.

The formulations according to the invention are typically microemulsions, ie the constituents form a multiphase system comprising at least one organic phase and one aqueous phase, wherein the average distances of the phase boundaries, as a rule the average particle diameter or the average droplet size (Z = by specific light scattering average diameter) of the disperse phase, generally not more than 500 nm. Unlike in suspensory Onskonzentraten the active ingredient in the formulations according to the invention is not in solid but in dissolved form. Therefore, the formulations of the invention may also be referred to as ME formulations. The formulations of the invention are stable liquid formulations which are optically transparent and do not tend to form solids upon storage. In addition, they remain liquid at temperatures below -10 ⁰ C without losing their advantageous properties. Their freezing point is usually below -10 ⁰ C.

The dynamic viscosity of the formulations according to the invention is usually 0.5 Pa. s (at 20 ⁰ C) and is often in the range of 1 to 500 mPa.s and in particular in the range of 2 to 200 mPa.s at 20 ⁰ C.

The formulations of the invention can also be easily diluted with water. For example, prior to use, the formulations of the present invention may simply be diluted with water, for example with from 0.1 to 100 parts of water per part of the formulation, in particular from 0.5 to 50 parts of water per part of the formulation, without causing coarse material forms. Frequently, the formulations according to the invention are used undiluted or in dilution with comparatively small amounts of water, generally not more than 5 parts and preferably not more than 2 parts of water per part of the formulation. The quality of the water used for dilution is of secondary importance, d. H. that, for example, tap water or spring water can be used.

The average particle diameters reported here represent Z averages of the particle diameters that can be determined by light scattering. Corresponding methods familiar to the person skilled in the art are described, for example, in H. Wiese (D. Distler, Verf.), Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p. 40ff, and the literature cited therein; H. Auweter, D. Horn, J. Colloid Interf. Be. 105 (1985), p. 399; D. Lie, D. Horn, Colloid Polym. Be. 269 (1991), p. 704 and H. Wiese, D. Horn, J. Chem. Phys. 94 (1991), p. 6429. Due to the small particle size after dilution with water, the bioavailability and thus the biological activity is often increased over conventional formulations.

The formulations according to the invention are frequently oil-in-water emulsions, with water in which part of the solvent is dissolved (= aqueous phase) forming the continuous phase, while another part of the solvent and one or more crop protection agents (= Oil phase) are present in the disperse phase. In some cases, these are also water-in-oil emulsions, wherein Water in which a part of the solvent is dissolved (= aqueous phase) forming the discontinuous phase, while another part of the solvent and one or more crop protection active ingredients (= oil phase) are present in the continuous phase. The formulations according to the invention can also be present as bicontinuous phases, ie the aqueous phase and the oil phase form mutually penetrating phases.

The terms "alkyl", "alkenyl", "alkylene", "aryl" used hereinafter represent collective terms for particular organic radicals. In this context, the prefix C _n -C m in each case indicates the total number of carbon atoms of the respective organic radical. With respect to solvents, the prefix C _n -Cm indicates the total number of carbon atoms of each organic solvent, except for the N-methyl-substituted heterocyclic solvents such as N-methyllactams and N-methyl or N, N-dimethylureas, where the prefix C _n -Cm indicates the total number of carbon atoms of the heterocycle; also excluded are the trialkyl phosphates, where the prefix C _n -Cm indicates the number of carbon atoms of the individual alkyl radicals.

The term "alkyl" refers to saturated straight, branched or cyclic hydrocarbon radicals having the number of carbon atoms specified in the prefix. (C 1 -C 7) -alkyl accordingly denotes saturated straight-chain, branched-chain or cyclic hydrocarbon radicals having 1 to 7 carbon atoms, such as, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, cyclopentyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, cyclohexyl, methylcyclopentyl, heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 1,1,3-trimethylbutyl, 1, 2-dimethylpentyl, 1, 3-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 3,3-dimethylpentyl, 3,4- Dimethylpentyl, 1-ethylpentyl, 2-ethylpentyl, 1, 1 , 2-trimethyl-butyl, 1, 2,2-trimethylbutyl, 1-ethyl-1-methylbutyl, 1-ethyl-2-methylbutyl, methylcyclohexyl, 1, 2-dimethylcyclopentyl, 1, 3-dimethylcyclopentyl and ethylcyclopentyl.

The term "C 2 -C 4 -alkylene" denotes saturated, divalent straight- or branched-chain hydrocarbon radicals having 2, 3 or 4 carbon atoms, for example ethane-1, 2-diyl, propane-1, 3-diyl, propane-1, 2-diyl, 2-methylpropane-1, 2-diyl, butane-1, 4-diyl, butane-1, 3-diyl (= 1-methylpropane-1, 3-diyl), butane-1, 2-diyl, and butane-2,3-diyl. The term "aryl" refers to aromatic radicals including heteroaromatic radicals having 1 or 2 heteroatoms selected from O and N, such as phenyl, naphthyl, anthracenyl, pyridyl, pyrryl, pyrazinyl, pyrimidinyl, purinyl, indolyl, quinolyl, isoquinolyl, imidazolyl, pyrazolyl, Indazolyl, furyl, benzofuryl, isobenzofuryl, morpholinyl, oxazolyl, benzoxazolyl, isoxazolyl and benzisoxazolyl.

The formulations of the invention contain at least one solvent b) having a water solubility of more than 100 g / l, especially at least 200 g / l or at least 300 g / l at 20 ⁰ C. solvent b) may be selected from a wide variety of polar organic solvents. It is preferably chosen from hydroxylated (C ₄ -C 8) -alkanecarboxylic acid esters, aliphatic (C 2 -C 5) -di- and -triols, in particular aliphatic (Cs-Cs) -di- and -triols, (C 5 -C 5) -alkanecarboxylic alkoxyalkyl esters, Dimethyl sulfoxide (DMSO), tetrahydrofurfuryl alcohol, (C ₃ -C ₄ ) alkylene carbonates, N, N'-dimethyl (C ₃ -C ₄ ) alkylene ureas, (C ₃ -C ₅ ) lactones, N-methyl (C ₃ -C5) lactams and tri (C ₁ -C ₃ ) alkyl phosphates.

The term "hydroxylated (C ₄ -C 5) -alkanecarboxylic acid esters" in the context of this invention refers to esters of alkanecarboxylic acids which have been esterified with alkanols, where either the acid or the alcohol-derived alkyl radical is substituted by at least one hydroxyl group and the total number of Carbon atoms is 4 to 8. Examples of hydroxylated alkanecarboxylic acids are 5-hydroxyvaleric acid, 4-hydroxyvaleric acid, 2-hydroxyvaleric acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxypropionic acid, lactic acid and hydroxyacetic acid. Examples of hydroxylated alkanols are pentane-1, 5-diol, pentane-1, 3-diol, pentane-2,4-diol, cyclopentane-1, 2-diol, butane-1, 4-diol, butane-2,3 , -diol, propane-1, 2-diol, 2- (hydroxymethyl) -butanol, 2- (hydroxyethyl) propanol, 2- (hydroxymethyl) propanol and ethane-1,2-diol. Examples of hydroxylated (C5-Cs) -alkanecarboxylic acid esters are n-butyl-4-hydroxybutyrate, isobutyl-3-hydroxybutyrate, n-propyl-4-hydroxybutyrate, isopropyl-4-hydroxybutyrate, isopropyl-3-hydroxybutyrate, methyl-4-hydroxybutyrate Ethyl 4-hydroxybutyrate, 2-ethyl-propyl lactate, 2-methyl-propyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, ethyl lactate, methyl lactate, cyclopentyl lactate, n-hexyl hydroxyacetate, cyclohexyl hydroxyacetate, 3-methylcyclopentyl hydroxyacetate , n-pentyl-hydroxyacetate, 2-methylpentylhydroxyacetate, n-butylhydroxyacetate, tert-butylhydroxyacetate, n-propylhydroxyacetate, isopropylhydroxyacetate, 5-hydroxypentylacetate, 3-hydroxycyclopentylpropionate, 3-hydroxybutylacetate, 3-hydroxypropylacetate, 3- Hydroxypentylpropionate, 3-hydroxycyclopentylpropionate, 2-hydroxymethylbutylpropionate, 3-hydroxypropylpropionate, 2-hydroxyethylpropionate, 2-hydroxymethylpropylbutyrate, 3-hydroxypropylbutyrate, 2-hydroxyethylbutyrate, 3-hydroxypropylvalerate and 2-Hy droxyethylvaleriat.

In the context of this invention, aliphatic (C 2 -C 8) -di- and -triols are aliphatic straight-chain or branched-chain hydrocarbons having 2 to 8 and in particular especially 5 to 8 carbon atoms which carry 2 or 3 hydroxyl groups, for example 1, 5-pentanediol, 2,4-pentadiol, 2-methyl-2,4-pentanediol (hexylene glycol), 1,6-hexanediol, 2,5- Hexanediol, 3-methyl-2,4-hexanediol, 1, 7-heptanediol, 2,6-heptanediol, 1, 8-octanediol, 2,7-octanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cycloheptanediol, 1, 2,3-pentanetriol, 2,3,4-pentatriol,

1, 2,3-hexanetriol, 1, 2,5-hexanetriol, 1, 2,3-heptanetriol 1, 6,7-heptanetriol, 2,3,6-heptanetriol, 1, 2,3-octanetriol, 2,3 , 4-octanetriol 1, 2,8-octanetriol, 2,3,7-octanetriol, 1, 2,3-cyclohexanetriol, 1, 3,5-cyclohexanetriol, 1, 2,4-cyclohexanetriol, 1, 2,3- Cycloheptanetriol and 1, 2,6-cycloheptanetriol.

By (C5-C8) -alkanecarboxylic alkoxyalkyl ester is meant here an ester of an alkanecarboxylic acid with an alkoxyalkanol, the total number of carbon atoms being 5 to 8. Examples thereof are isopropoxymethyl formate, ethylene glycol ethyl ether formate, ethylene glycol butyl ether formate, ethylene glycol 2-methyl-butyl ether formate, ethylene glycol pentyl ether formate, isopropoxymethyl formate, isopropoxyethyl formate, isopropoxy-tert-butyl formate, ethoxymethyl acetate, isopropoxymethyl acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, Ethylene glycol butyl ether acetate, ethylene glycol tert-butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol isopropyl ether acetate, methoxypropyl acetate, ethoxypropyl acetate, propoxypropyl acetate, isopropoxypropyl acetate, ethylene glycol methyl ether butyrate, ethylene glycol ethyl ether butyrate, propylene glycol methyl ether butyrate, propylene glycol methyl ether 2-methylpropylate, isopropoxymethyl butyrate, propoxymethyl tert. butyrate, methoxypropyl butyrate, methoxypropyl 2-methylpropylate, ethylene glycol methyl ether pentanoate and ethylene glycol methyl ether 3-methyl butyrate.

(C3-C4) -Alkylencarbonate refer here in particular cyclic diesters of carbonic acid having a total of 3 to 4 carbon atoms, such as ethylene carbonate, 1, 3-propylene carbonate and 1, 2-propylene carbonate.

Tri- (C 1 -C 3) -alkyl phosphates are understood to mean the triesters of phosphoric acid having three independently selected (C 1 -C 5) -alkanols, for example trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-isopropyl phosphate, tri-n-butyl phosphate, Tri-isobutyl phosphate, methyl diethyl phosphate, dimethyl ethyl phosphate, methyl di-n-propyl phosphate, methyl ethyl n-propyl phosphate, ethyl 2-methylpropyl methyl phosphate and diethyl n-propyl phosphate.

By an N, N'-dimethyl- (C3-C4) -alkyleneurea is meant 2-fold N-methylated derivatives of cyclic ureas having 3 or 4 carbon atoms in the ring. An example of N, N'-dimethyl- (C ₃ -C 4) alkylene ureas is N, N'-dimethylethyleneurea (1,3-dimethylimidazolin-2-one). A (C3-Cs) lactone is understood as meaning a cyclic ester of a hydroxycarboxylic acid having 3, 4 or 5 carbon atoms in the ring. An example of (C3-Cs) lactones is γ-butyrolactone.

By an N-methyl- (C3-C5) -lactam is meant an N-methylated derivative of a lactam having 3, 4 or 5 carbon atoms in the ring. Examples of N-methyl- (C3-C5) -lactams are N-methylpyrrolidone and N-methylpiperidone.

According to a preferred embodiment, the formulations of the invention comprise at least one solvent b) which is selected from dimethylsulfoxide, hydroxylated (C 4 -C 8) -alkanecarboxylic acid esters, aliphatic (Cs-Cs) di- and triols, (Cs-Cs) alkanecarboxylic acid alkoxyalkyl esters , Tetrahydrofurfuryl alcohol, N-methyl- (C4-C5) -lactams and (C4-Cs) -lactones, and in particular selected from γ-butyrolactone, dimethylsulfoxide, methoxypropyl acetate, 2-methyl-2,4-pentanediol, hexylene glycol (1 , 6-hexanediol), tetrahydrofurfuryl alcohol and n-propyl lactate.

In a particularly preferred embodiment, the formulations according to the invention comprise as at least one solvent b) dimethyl sulfoxide.

According to a further particularly preferred embodiment, the formulations according to the invention comprise as a solvent b) dimethyl sulfoxide and at least one second solvent other than dimethylsulfoxide b), which is preferably selected from hydroxylated (C5-C8) -alkanecarboxylic acid esters, aliphatic (Cs-Cs) -di and triols, (C5-C8) -alkanecarboxylic acid alkoxyalkyl esters, (C3-C4) -alkylene carbonates, γ-butyrolactone, N-methyl- (C3-C5) -lactams and Tn- (CrCs) -alkylphosphates, especially under γ-butyrolactone, Methoxypropyl acetate, 2-methyl-2,4-pentanediol, hexylene glycol (1,6-hexanediol), tetrahydrofurfuryl alcohol and n-propyl lactate.

In a likewise preferred embodiment of the invention, the formulation contains no or less than 0.1% by weight of DMSO, based on the total weight of the formulation. Preferably, in this embodiment of the invention, the solvent b) is selected from hydroxylated (C 4 -C 8) -alkanecarboxylic acid esters, aliphatic (C 5 -C 6) -di- and triols, (C 5 -C 8) -alkanecarboxylic acid alkoxyalkyl esters, tetrahydrofurfuryl alcohol, (C 4 -C 8) Cs) -lactones and N-methyl- (C4-Cs) -lactams and in particular selected from γ-butyrolactone, dimethyl sulfoxide, methoxypropyl acetate, 2-methyl-2,4-pentanediol, hexylene glycol (1,6-hexanediol), tetrahydrofurfuryl alcohol and n -Propyllaktat.

The total amount of solvent b) contained in the formulations of the invention generally depends on the amounts of organic crop protection active ingredients a), surfactants e) and f), and solvents c) and d), as well as their properties. The weight ratio of solvent b) and the total amount of plant protective agents a) will usually be in the range of 0.05: 1 to 30: 1, preferably in the range of 0.1: 1 to 10: 1, and in particular in the range of 0.15: 1 to 5: 1. Based on the total weight of the undiluted formulations is the proportion of the solvents b) usually from 1 to 60 wt .-%, preferably from 10 to 40 wt .-% and in particular from 15 to 35 wt .-%. In the case of formulations containing DMSO as sole solvent b), the proportion of DMSO is preferably not more than 5 wt .-%, for example from 1 to 5 wt .-%, based on the total weight of the formulation. In the case of formulations which comprise DMSO in combination with at least one further solvent b), the weight ratio of DMSO to the further solvent b) is generally in the range from 1:20 to 1: 1, in particular in the range from 1 : 10 to 1: 2. In these formulations, the proportion of DMSO is preferably not more than 5 wt .-%, for example 0.5 to 5 wt .-%, based on the total weight of the formulation. The formulations of the invention contain at least one solvent c) having a water solubility of 2 to 100 g / l, especially 3 to 90 g / l or 4 to 80 g / l at 20 ⁰ C. solvents c) may be selected from a wide variety medium of polar organic solvents be. Preferably, it is selected from (C5-C9) -alkanecarboxylic acid alkyl esters, (C9-C12) -alkanecarboxylic acid alkoxyalkyl esters, (C5-C9) -dialkyldicarboxylic acid esters, (C5-Cg) -ketones, (Cs-C3-arylalkylalcohols, (C5-C9) - Aryloxyalkylalkoholen, (C ₅ -C ₉ ) -Cycloalkylalkoholen, (C ₅ -C ₉ ) -Alkandiolalkanolate, (C ₅ - C9) -Alkantriolalkanolate and

Alkyl (C 1 -C 4) -alkanecarboxylic acids are understood here to mean, in particular, alkanecarboxylic acids esterified with alkanols, the total number of carbon atoms being 5 to 9 and in particular 5, 6, 7 or 8. Examples of these are isopropyl acetate, n-propyl acetate, isobutyl acetate tert-butyl acetate, n-pentyl acetate, cyclopentyl acetate, n-hexyl acetate, 3-methylcyclopentyl acetate, cyclohexyl acetate, n-heptyl acetate, 3-methylcyclohexyl acetate, n-propyl propionate, isopropyl propionate, n-butyl propionate, tert-butyl propionate, n-pentyl propionate, n Propyl isopropionate, cyclopropyl propionate, cyclopropyl isopropionate, isopropyl isopropionate, n-butyl isopropionate, tert-butyl isopropionate, n-pentyl isopropionate, n-hexyl propionate, cyclohexyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, tert-butyl butyrate, ethyl tert. Butyrate, n-propyl-tert-butyrate, isopropyl-tert-butyrate, n-butyl-tert-butyrate, tert-butyl-tert-butyrate, n-pentyl butyrate, methyl pentanoate, ethyl pentano at, propylpentanoate, isopropyl pentanoate, n-butyl pentanoate, methylhexanoate, ethylhexanoate, isopro- pylhexanoate, methylheptanoate, ethyl heptanoate and methyl octanoate.

Under (C9-Ci2) -Alkancarbonsäurealkoxyalkylester is here an ester of an alkane carboxylic acid with an alkoxyalkanol understood, wherein the total number of carbon atoms is 9 to 12. Examples thereof are isopropoxybutyl acetate, ethylene glycol propyl ether butyrate, ethylene glycol pentyl ether propionate, ethylene glycol 2-methyl-butyl ether formate, propylene glycol ethyl ether pentanoate, propylene glycol butyl ether 2-methyl propylate, isopropoxypropyl butyrate, propoxypentyl tert-butyrate, ethoxypropyl butyrate, ethoxypropyl 2-ethylpropylate, ethylene glycol ethyl ether hexanoate, ethylene glycol propyl ether 3-methyl pentanoate, ethoxymethyl heptanoate, ethoxybutyl hexanoate and methoxypropyl 3-ethyl butyrate.

By (C 1 -C 12 -dialkyldicarboxylic acid esters herein is meant a diester of an alkanedicarboxylic acid having two independently selected alkanols, the total number of carbon atoms being 5 to 9 and in particular 5, 6, 7 or 8. Examples of these are ethylmethyloxalate, diethyl oxalate , Ethylpropyloxalat, Ethylisopro- pyloxalat, dipropyl oxalate, Propylisoproyloxalat, Ethylbutyloxalat, Methylpentyloxalat, Propylbutyloxalat, dimethyl, Methylethylmalonat, diethylmalonate, malonate Propylethyl-, pylmalonat Isopropylethylmalonat, Methylpropylmalonat, Methylisopropylmalonat, Dipro-, dimethyl succinate, glycinate Ethylmethylsuccinat, diethyl, Methylpropylsuc-, Methylisopropylsuccinat, Ethylproylsuccinat Dimethyl glutarate, ethyl methyl glutarate, diethyl glutarate, dimethyl adipate, ethyl methyl adipate and dimethyl pimelate.

For the purposes of the present invention, the term "(C 1 -C 4) -ketones" includes optionally alkoxylated aliphatic, cycloaliphatic and araliphatic ketones having 5 to 9 carbon atoms, including, for example, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone , 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 4-methyl-2-pentanone, 5-methyl-2-hexanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone , Cyclohexylcarboxymethane, acetophenone and methoxyacetophenone.

By a (C 1 -C 4 -arylalkyl alcohol (= (C 1 -C 12 -arylalkanol) is meant an alkanol which is substituted by an aryl radical, the (C 1 -C 4 -arylalkyl alcohol comprising a total of 5 to 9 carbon atoms, examples of which are Benzyl alcohol, 2-phenylethanol, 1-phenylethanol, phenylpropanol, pyridin-1-ylmethanol, pyridin-3-ylmethanol, 1-pyridin-3-ylethanol, pyridinylbutanol, pyrimidin-1-ylmethanol, pyrimidin-1-ylethanol, 2-pyrimidin 3-yl-propanol, furan-2-ylmethanol, 2-furan-2-yl-ethanol, 3-furan-3-yl-propanol and 4-furan-2-yl-butanol.

By a (C 1 -C 8 -aryloxyalkyl alcohol (= (C 1 -C 12 -aryloxyalkanol) is meant herein an alkanol substituted with an aryloxy radical, the (C 5 -C 9) aryloxyalkyl alcohol comprising from 5 to 9 carbon atoms, examples of which are Phenoxy- methanol, phenoxyethanol and phenoxyisopropanol.

(C 5 -C 9) -cycloalkyl alcohols here denote cyclic alkanols having 5 to 9 carbon atoms, such as, for example, cyclopentanol, cyclohexanol, cycloheptanol and cyclooctanol. By a (C 1 -C 4 -alkanediolalkanoate is meant here an alkanediol esterified with two alkanoic acids, the (C 1 -C 4 -alkanediol) alkoxide comprising 5 to 9 carbon atoms, examples being diacetin, glycol diacetate, glycol dipropionate, glycerol dipropionate and propylene glycol diacetate.

By a (C 1 -C 4 -alkantriolalkanoate is meant herein an alkanetriol esterified with three alkanoic acids, the (C 1 -C 4 -alkanetriolalkanolate comprising 5 to 9 carbon atoms, an example of which is triacetin.

(C 5 -C 6) -Alkylencarbonates refer here in particular to cyclic diesters of carbonic acid having 5 to 6 carbon atoms, such as, for example, 1, 2-butylene carbonate and 2,3-butylene carbonate.

According to a preferred embodiment, the formulations according to the invention comprise at least one solvent c) selected from (C5-C9) ketones, (Cs-C3-arylalkyl alcohols, (Cs-C3-aryloxyalkyl alcohols (C5-C9) -alkanetriolalkanoates and and especially selected from acetophenone, benzyl alcohol, cyclohexanone, 2-heptanone, triacetin, butylene carbonate and 2-phenoxyethanol.

The total amount of solvent c) present in the formulations of the invention generally depends on the amounts of organic crop protection active ingredients a), surfactants e) and f), and solvents b) and d), as well as their properties. The weight ratio of solvent c) and the total amount of crop protection active ingredients a) will usually be in the range of 0.05: 1 to 30: 1, preferably in the range of 0.1: 1 to 20: 1, and in particular in the range of 0.5: 1 to 10: 1. Based on the total weight of the undiluted formulations, the proportion of solvents c) is generally from 1 to 60% by weight, preferably from 10 to 40% by weight and in particular from 15 to 35% by weight.

The formulations of the invention contain at least one solvent d) with a water solubility of less than 2g / l, preferably a maximum of 1 g / l and in particular at most 0.5 g / l at 20 ⁰ C. solvents d) may be selected from a wide variety of nonpolar solvents such as aliphatic or aromatic hydrocarbons, vegetable oils, fatty acids and their derivatives. Preferably, the solvent d) is selected from aliphatic, aromatic and cycloaliphatic hydrocarbons having boiling points of 100-310 ⁰ C, (C8-C20) - alkyl phenols, (C8-C2o) alkanols, (Cio-C2o) -Alkancarbonsäurealkylestern, ( C9-C20) - hydroxyalkanecarboxylic acid alkyl esters, (C12-C28) -cycloalkanecarboxylic acid alkyl esters, (C12-C28) -cycloalkanedicarboxylic acid dialkyl esters, (Cio-C15) -dialkyldicarboxylic acid esters, (C25-C35) -alkanetriolalkanoates, N- (C6-C18) -alkyl- (C9-C18) -alkyl- C3-C5) -Iactamen, (Cs-C26) fatty acids, especially Ci2-C2o-fatty acids, dialkylamides, such as the di-CrC ₄ - Alkylamides such as the dimethylamides, and their alkyl esters, for example their Ci-Cs alkyl esters such as the methyl and ethyl esters.

Aliphatic hydrocarbons having boiling points of from 100 to 310 ^° C., in particular from 120 to 280 ^° C. (at normal pressure), denote in particular linear and branched alkanes or alkenes having from 7 to about 18 carbon atoms which have a boiling point in the stated range at normal pressure, as in particular also mixtures of these aliphatic hydrocarbons. Commercially, such blends are available, for example, under the trade name Exxsol, which are products mainly containing petroleum whose aromatic constituents have been depleted, such as Exxsol D30, Exxsol D40, Exxsol D80, Exxsol D100, Exxsol D120 and Exxsol D220 / 230 ,

Among aromatic hydrocarbons with boiling points of 100-310 ° C, in particular from 120 to 280 ⁰ C (at atmospheric pressure) of this invention are turned under and understood polynuclear aromatics which optionally one or more aliphatic or araliphatic substituents, in particular alkyl - Bear or arylalkyl radicals and have a boiling point in the stated range at atmospheric pressure. Preferably, here under mixtures of such aromatic hydrocarbons were comparable, which are obtained as fractions in the distillation particular of petroleum products in the designated boiling range, such as the commercial products ^® under the trade names Solvesso ^®, especially Solvesso ^® 100, Solvesso ^® 150, Solvesso 200, Solvesso ^® 150 ND, Solvesso ^® 200 ND, Aromatic ^®, in particular Aromatic ^® 150 and Aromatic 200 ^®, hydrosol ^®, in particular hydrosol ^® A 200 and hydrosol ^® A 230/270, Caromax ^®, in particular Caromax ^® 20 and Caromax ^® 28, Aromat K 150, Aromat K 200, Shellsol ^®, in particular Shellsol ^® A 100 and Shellsol ^® A 150, and Fin FAS-TX, in particular Fin FAS-TS 150 and Fin FAS-TX 200 have been released. Particularly preferred are the mixtures of Solvesso ^® 150 and Solvesso ^® 200 ND ND (Exxon Mobil Chemical) in which the potential carcinogen naphthalene was depleted are. For example, Solvesso ^® 150 ND contains predominantly aromatic hydrocarbons of 10 or 1 1 carbon, boiling in the range of 175 to 209 ⁰ C, most of which are alkylbenzenes, while Solvesso ^® 200 ND mainly contains aromatic hydrocarbons of 10 to 14 carbons which boil in the range of 235 to 305 ⁰ C and which are mainly alkylnaphthalenes. Another example of the aromatic hydrocarbons referred to herein is a product sold under the trade name Hisol SAS-296, which is a mixture of 1-phenyl-1-xylylethane and 1-phenyl-1-ethylphenylethane.

Cycloaliphatic hydrocarbons having boiling points of from 100 to 310 ° C., in particular from 120 to 280 ° C. (at atmospheric pressure), are understood in the context of this invention to mean saturated and unsaturated hydrocarbons which have a non-hydrocarbon content. aromatic carbocycle and mixtures of such hydrocarbons. An example of this is limonene.

The term (C 8 -C 20) -alkylphenol denotes a phenol which is substituted with at least one alkyl radical on the ring, the (C 8 -C 20) -alkylphenol comprising 8 to 20 carbon atoms. Examples of these are ethylphenol, 2-methyl-4-ethylphenol, diheptylphenol and dodecylphenol.

Under (C 8 -C 20) -alkanols are here alkanols having 8 to 20 and especially 8 to 14 carbon atoms (= (C8-Ci4) alkanols) understood. Examples of these are octanol, decanol, dodecanol, tridecanol, nonanol, isononanol, 2-propylheptanol, iso-tridecanol and ethylhexanol.

Under (Cio-C2o) -Alkancarbonsäurealkylestern be understood here in particular alkanols esterified (Ci-C9) alkanecarboxylic acids, wherein the total number of carbon atoms is 10 to 20. Examples of these are ethylhexyl acetate, n-nonyl acetate, isobornyl acetate, propyl heptyl isopropionate, n-decyl butyrate, tert-butyl hexanoate, n-pentyl-4-ethyloctanoate and ethyl nonanoate.

By (C9-C20) -Hydroxyalkancarbonsäurealkylestern be here in particular alkanols esterified hydroxylated alkanecarboxylic acids, in particular esterified lactic acid (lactates) understood, wherein the total number of carbon atoms is 9 to 20. The alkyl radical often has 3 to 10 carbon atoms. Examples of these are tert-butyl 3-hydroxydecanoate, n-propyl 4-hydroxyoctanoate, isopropylhexyl 4-hydroxyoctanoate, ethyl 3-propyl-4-hydroxylhexanoate, n-pentyl-4-hydroxybutyrate, ethylhexyl-3-hydroxy butyrate, 2-ethyl-pentyl lactate, decyl lactate, ethyl hexyl lactate, n-heptyl hydroxyacetate, cyclohexyl ethyl hydroxyacetate and 3-isopropylcyclopentyl hydroxyacetate.

Under (Ci2-C28) -Cycloalkancarbonsäurealkylestern or (Ci2-C28) -Cycloalkan dicarbonsäuredialkylestern are here understood as having one or two carboxyl-substituted cycloalkanes, which are esterified with one or two alkanols, wherein the total number of carbon atoms is 12 to 28 , Examples of these are cyclopentanecarboxylic acid hexyl esters, cyclohexanecarboxylic acid pentyl esters, cyclohexanecarboxylic acid 3-isopropylhexyl esters, 1,2-cyclopentanedicarboxylic acid dibutyl ester, 1, 3-cyclopentanedicarboxylic acid ethylbutyl ester, 1,2-cyclohexanedicarboxylic acid dodecyl ester,

1, 4-Cyclohexandicarbonsäuremethyloctylester and Cyclohexandicarbonsäurediisono- nylester.

Under (Cio-Ci5) -Dialkyldicarbonsäureestern is here a diester of a Alkandicar- bonsäure understood with two alkanols, wherein the total number of carbon atoms is 10 to 15. The alkyl radicals frequently each have 2 to 8 carbon atoms. Examples include butyl hexyloxalate, diphenyl oxalate, diisobutyl malonate, dihexyl malonate, ethyl pentylmalonate, dipropylsuccinate, diisopropylsuccinate, diisobutylsuccinate, dipentylsuccinate, diisopropylglutarate, diisobutylglutarate, ethylpentylglutarate, dicyclopentylglutarate, diisobutyladipate, ethylpropyl adipate, diisobutylpimelate and diethylpimelate.

By (C25-C35) alkanetriolalkanoates is meant here an alkanetriol esterified with three alkanoic acids, the (C25-C35) -alkanetriolalkanolate comprising from 25 to 35 carbon atoms. An example is Myritol ^® 312 (Cognis), which is a mixture of triglycerides (C8-Cio) fatty acid.

N- (C6-C18) -alkyl- (C3-C5) -lactams are here understood to mean N-alkylated derivatives of lactams having 3, 4 or 5 carbon atoms in the ring, where the N-alkyl radicals comprise 6 to 18 carbon atoms. An example of this is N-octylpyrrolidone.

By (C8-C26) fatty acids are understood to mean fatty acids having 8 to 26 carbon atoms. Examples of these are the saturated fatty acids caprylic, capric, lauric, myristic, palmitic, margaric, stearic, arachidic, behenic, lignoceric and cerotic; and the monounsaturated fatty acids undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid and nervonic acid; and the polyunsaturated fatty acids linoleic acid, α-linolenic acid, γ-linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid. Examples of dialkylamides of (C 8 -C 26) fatty acids are their di-C 1 -C 4 -alkylamides, e.g. the dimethylamides, diethylamides, dipropylamides, diisopropylamides, dibutylamides, diisobutylamides, methylethylamides, methylproylamides, methylisobutylamides, methyl-tert-butylamides, ethylpropylamides, ethylisopropylamides, ethylbutylamides, ethylisobutylamides, propylisopropylamides, propylbutylamides and propylisobutylamides of the abovementioned fatty acids, the dimethylamides are particularly preferred. Examples of alkyl esters of (Cs-C26) fatty acids are their C 1 -C 8 -alkyl esters, e.g. the methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters, tert-butyl esters, 1-methylpropyl esters, pentyl esters, 1-methylbutyl esters, 2-methylbutyl esters, 3-methylbutyl esters, hexyl esters, 1-

Methylpentylester, 2-methylpentylester 1-ethylbutylester and 1, 2, -dimethylbutylester, heptylester, 1-methylhexylester, 2-methylhexylester, 3-methylhexylester, 4-methylhexylester, 5-methylhexylester, 1-ethylpentylester, 2-ethylpentylester, 3-ethylpentylester, 4-Ethylpentylester, 1, 2-Dimethylpentylester, 1, 3-Dimethylpentylester, 1, 4-Dimethylpentylester, 2,3-Dimethylpentylester and ethyl 2-methylbutylester of the aforementioned fatty acids, wherein the methyl and ethyl esters are particularly preferred.

According to a preferred embodiment, the formulations of the invention comprise at least one solvent d) selected from (C8-C26) fatty acids whose di-C 1 -C 4 -alkylamides, e.g. Dimethylamides, (C10-C15) -

Dialkyldicarboxylic acid esters, (C9-C2o) -Hydroxyalkancarbonsäurealkylestern, in particular lactates having a total of 9 to 20 carbon atoms and aromatic hydrocarbons having a boiling point at atmospheric pressure in the range 100-310 ⁰ C. According to a very preferred embodiment, formulations of the invention comprise at least one solvent d) which is selected from a group consisting of Ci2-C2o-fatty acids, for example the commercial product Edenor ^® Tl 05 (Cognis), which is a mixture of fatty acids with a high Ölsäurean- in part by the manufacturer, dimethyl amides of Ci2-C2o-fatty acids, such as the commercial product Agnique ^® KE 3658, (Cognis) which is a mixture of is lamiden Fettsäuredimethy-, (C8-Ci4) alkanols such as dodecanol, aromatic hydrocarbons having a boiling point at atmospheric pressure in the range from 120 to 280 ⁰ C, such as Solvesso ^® 150 and Solvesso ^® 200 ND ND, and similar products, Cβ -Cio-

Alkyl lactates having a total of 9 to 13 C atoms, such as 2-ethylhexyl lactate, and diisobutyldicarboxylic acid esters having a total of 10 to 15 C atoms, e.g. technical mixtures of diisobutyl esters of succinic acid, glutaric acid and adipic acid.

The total amount of solvent d) contained in the formulations of the invention generally depends on the amounts of organic crop protection active ingredients a), surfactants e) and f), and solvents b) and c), as well as their properties. The weight ratio of solvent d) and the total amount of crop protection active ingredients a) will usually be in the range from 0.05: 1 to 30: 1, preferably in the range from 0.1: 1 to 20: 1, and in particular in the range of 0.5: 1 to 15: 1. Based on the total weight of the undiluted formulations, the proportion of solvents d) is generally from 1 to 60% by weight, preferably from 5 to 45% by weight and in particular from 10 to 35% by weight.

In a preferred embodiment, the formulations according to the invention each contain only one solvent b), c) and d); and according to another preferred embodiment, they additionally contain only one further solvent b) or c).

The formulations according to the invention contain at least one nonionic surfactant e) and at least one anionic surfactant f). The term surfactant refers to surface-active substances, which are also referred to below as emulsifiers or detergents. The surfactant mixture serves to reduce the surface tension between the continuous and the disperse phase and thereby stabilize the particles / droplets of the disperse phase. The surfactants also support the solubilization of the at least one organic plant active substance a). Suitable surfactants for formulating microemulsions are known to those skilled in the art, for example, by McCutcheon, Detergents and Emulsifiers, Int. Ed., Ridgewood, New York. The surfactants may be polymeric or non-polymeric surfactants. Preferably, the majority, in particular at least 90% and in particular the total amount of the surfactant present in the microemulsion is selected from the group of non-polymeric surfactants, which are also called emulsifiers become. Non-polymeric surfactants (emulsifiers) usually have a number average molecular weight of up to 2000 daltons, more preferably from 150 to 2000 daltons, and preferably from 200 to 1500 daltons.

The group of nonionic surfactants includes in particular:

Homo- or cooligomers of (C2-C4) -alkylene oxides such as ethylene oxide, propylene oxide (= 1-methyloxirane), 1, 2-butylene oxide (= 1-ethyloxirane) and 2-methylpropylene oxide (= 1, 1-Dimethyloxiran), in particular homo-oligomers of Ethylene oxide, homo-oligomers of propylene oxide and ethylene oxide-propylene oxide cooligomers; - Oligo (C2-C4) alkylene oxide (C8-C22) alkyl ethers, in particular oligoethoxylates and oligoethoxylates co-propoxylates of linear and branched (C8-C22) alkanols, preferably oligoethoxylates of fatty alcohols and oligoethoxylates of oxo alcohols, such as Lauryl alcohol oligoethoxylate, isotridecanol oligoethoxylate, cetyl alcohol oligoethoxylate, stearyl alcohol oligoethoxylate and their esters such as the acetates;

Oligo- (C 2 -C 4) -alkylene oxide aryl ethers and oligo- (C 2 -C 4) -alkylene oxide (C 1 -C 6) -alkyl aryl ethers, such as, for example, oligo- (C 2 -C 4) -alkylene oxide (C 1 -C 22) -alkyl benzene ethers, in particular oligoethoxylates of (C 1 -C 16) -alkylphenols, such as, for example, the oligoethoxylate of nonylphenol, decylphenol, isodecylphenol, dodecylphenol or isotridecylphenol;

Oligo (C2-C4) alkylene oxide mono-, di- or tristyrylphenyl ethers, in particular oligoethoxylates of mono-, di- and tristyrylphenols, as well as their condensates with formaldehyde and their esters, such as, for example, the acetates; (C6-C22) -alkyl glucosides and (C6-C22) -alkyl oligoglucosides; Oligoethoxylates of (C 6 -C 22) -alkyl glucosides and oligoethoxylates of (C 6 -C 22) -alkyl oligoglucosides;

Oligoethoxylates of fatty acids and oligoethoxylates of hydroxy fatty acids; Partial esters of polyols with (C 6 -C 22) -alkanoic acids, in particular mono- and diesters of glycerol and mono-, di- and triesters of sorbitan, such as, for example, glycerol monostearate, sorbitan monododecanoate, sorbitan dioleate and sorbitan tristearate;

Oligoethoxylates of the partial esters of polyols with (C 6 -C 22) -alkanoic acids, in particular oligoethoxylates of the mono- and diesters of glycerol and oligoethoxylates of the mono-, di- and triesters of sorbitan, such as, for example, oligethoxylates of glycerol monostearate, oligoethoxylates of sorbitan monooleate,

Oligoethoxylates of sorbitan monostearate and oligoethoxylates of sorbitan tristearate;

Oligoethoxylates of vegetable oils or animal fats, such as corn oil ethoxylate, castor oil ethoxylate, tall oil ethoxylate; Acetylene glycols such as 2,4,7,9-tetramethyl-4,7-dihydroxy-5-decyne; Oligooxyethylene oligooxypropylen-blockcooligomere; and oligoethoxylates of fatty amines or of fatty acid diethanolamides. The term oligo- (C 2 -C 4) -alkylene oxide or oligo- (C 2 -C 4) -alkylene oxide denotes oligoether radicals which are derived from (C 2 -C 4) -alkylene oxides, such as ethylene oxide, propylene oxide (= 1-methyloxirane), 1, 2 Derive butylene oxide (= 1-ethyloxirane) and 2-methylpropylene oxide (= 1, 1-dimethyloxirane). The term oligo- (C 2 -C 5) -alkylene oxide ethers accordingly denotes oligoether radicals which are derived from (C 2 -C 3) -alkylene oxides, such as ethylene oxide and propylene oxide. The term ethoxylate refers to Oligoetherreste derived from ethylene oxide. Likewise, the term oligoethylene oxide-co-oligopropylene oxide refers to polyether radicals derived from mixtures of ethylene oxide and propylene oxide. The number of repeating units in the oligoether residues is generally between 2 and 120, often between 4 and 80, and especially between 5 and 60.

Of the abovementioned nonionic surfactants, the following are preferred: homo- or cooligomers of (C ₂ -C 3) -alkylene oxides, oligo- (C ₂ -C ₄ ) -alkylene oxide (C ₈ -C 22) -alkyl ethers, oligo- (C 2 -C 3) -alkyl ethers; C 2 -C 4) -alkylene oxide (C 1 -C 16) -alkyl benzene ethers, oligo- (C 2 -C 4) -alkylene oxide mono-, -di- or -tristyrylphenyl ethers, oligo- (C 2 -C 4) -alkylene oxide mono- or -distyrylphenyl ether-formaldehyde condensates .

Partial esters of glycerol or sorbitan with fatty acids, and acetylene glycols, and mixtures thereof.

Among the nonionic surfactants particularly preferred in the context of this invention are oligo- (C 2 -C 3) -alkylene oxide (C 8 -C 22) -alkyl ethers, homo- or cooligomers of

(C 2 -C 3) -alkylene oxides and oligo- (C 2 -C 3) -alkylene oxide mono-, -di- or -tristyrylphenyl ethers and mixtures thereof.

In a preferred embodiment of the invention, component e) of the formulations comprises at least two nonionic surfactants having different HLB values. According to a particularly preferred embodiment, the at least two nonionic surfactants are: e.1) at least one surfactant having an HLB value of not more than 13, in particular of

5 to 13 and especially from 6 to 12; and e.2) at least one surfactant having an HLB value greater than 13, especially from 13.5 to 18 and especially from 14 to 17.

The term "HLB value" (derived from the term "hydrophilic-lipophilic balance") in the context of this invention provides a measure of the degree of hydrophilicity or lipophilicity of a surfactant. The HLB value can be used to determine the surfactant properties of a surfactant Predict the molecule. According to the Davies method (Davies, JT, Proceedings of the International Congress of Surface Activity, 1957, 426-438), this value is determined by the following formula:

HLB = 7 + m * H ^h + n * H '

where m is the number of hydrophilic groups of the molecule, H ^{h is} a value corresponding to the specific hydrophilic character of the hydrophilic groups, n is the number of lipophilic groups of the molecule, and H ^{1 is} a value corresponding to the specific hydrophilic character corresponding to the lipophilic groups.

The nonionic surfactant e.1) having an HLB value of at most 13 can be selected from any of the aforementioned nonionic surfactants having an HLB value of at most 13, especially from 5 to 13 or from 6 to 12. Suitable surfactants e.1) include, in particular, oligo- (C 2 -C 4) -alkylene oxide (C 8 -C 22) -alkyl ethers, oligo- (C 2 -C 4) -alkylene oxide (C 8 -C 22) -alkyl benzene ethers, monofatty acid esters of sorbitan and Oligo (C2-C4) alkylene oxide mono-, di- or tristyrylphenyl ether. The at least one nonionic surfactant e.1) is preferably an oligo- (C 2 -C 4) -alkylene oxide (C 8 -C 22) -alkyl ether, in particular an oligo- (C 2 -C 4) -alkylene oxide (C 8 -C 4) -alkyl ether. C22) alkyl ethers having an HLB value in the range from 4 to 12. Particular preference is given to nonionic surfactants e.1) which are selected from oligoethoxylates and oligourethoxylate-co-propoxylates of linear or branched (Cs-C22) alkanols. Examples of such preferred surfactants are ethoxylates of branched Ci3-alcohols, which are commercially available under the trade names Lutensol ^® TO3, Lutensol TO5 ^® and Lutensol ^® TO7.

The nonionic surfactant e.2) having an HLB of more than 13 can be selected from any of the aforementioned nonionic surfactants having an HLB of more than 13, especially 13.5 to 18 or 14 to 17 to have. Suitable surfactants e.2) include in particular homo- and cooligomers of (C ₂ -C ₃ ) -alkylene oxides, oligo- (C ₂ -C ₃ ) -alkylene oxide (C ₈ -C 22) -alkyl ethers, oligo- (C ₂ -C ₃ ) - alkylene oxide (C ₈ -C 22) alkyl benzene ethers and oligo- (C 2 -C 3) alkylene oxide mono-, di- or tristyrylphenyl ethers. Preferably, the at least one nonionic surfactant e.2) is selected from homo- and cooligomers of the (C 2 -C 3) -alkylene oxides and oligo- (C 2 -C 3) -alkylene oxide mono-, -di- or -tristyrylphenyl ethers, in particular from homo- and copolymers of the (C2-C3) alkylene oxides and oligo- (C2-C3) alkylene oxide mono-, di- and tristyrylphenyl ethers having HLB values in the range of 13.5 to 18, especially 14 to 17. Particularly preferred Surfactants e.2) which are selected from propylene oxide-ethylene oxide block co-oligomers and oligoethylene oxide tristyrylphenyl ethers. Examples of such preferred surfactants are tristyrylphenol ethoxylates, which are commercially available under the trade name Soprophor ^®, in particular Soprophor ^® S 25 and S 40 Soprophor ^®, or propylene oxide-ethylene oxide Blockcooligomere, which are commercially available under the trade names Pluronic ^® PE, in particular pluronic ^® PE 6200 and Pluronic ^® 6400, or ethoxylates of branched Ci3-alcohols, which are commercially available under the trade names Lutensol ^® TO15.

Anionic surfactants f) include in particular the sodium, potassium, calcium and ammonium salts of

(C6-C22) alkyl sulfonates such as lauryl sulfonate and isotridecyl sulfonate;

(C6-C22) -alkyl sulfates, such as, for example, lauryl sulfate, isotridecyl sulfate, cetyl sulfate and stearyl sulfate;

Arylsulfonates, in particular (C 1 -C 16) -alkylbenzenesulfonates, such as, for example, cumylsulfonate, octylbenzenesulfonate, nonylbenzenesulfonate and dodecylbenzenesulfonate, naphthylsulfonate, mono- and di (C 1 -C 6) -alkylnaphthylsulfonates, such as, for example, dibutylnaphthylsulfonate; Mono- and di (Ci-Ci6) -alkyldiphenyl ether (di) sulfonates, such as, for example, dodecyldiphenyl ether disulfonate;

Sulfates and sulfonates of fatty acids and fatty acid esters; Oligo- (C 2 -C 3) -alkylene oxide (C 8 -C 22) -alkyl ether sulfates, in particular sulfates of the ethoxylates of (C 8 -C 22) -alkanols, such as, for example, sulfates of the ethoxylates of lauryl alcohol;

Oligo- (C 2 -C 3) -alkylene oxide (C 1 -C 16) -alkylbenzene ether sulfates, in particular sulfates of the ethoxylates of (C 1 -C 16) -alkylphenols;

Di (C4-C18) alkyl esters of sulfosuccinic acids (= (C4-C18) dialkyl sulfosuccinates) such as dioctyl sulfosuccinate; - condensates of naphthalenesulfonic acid, (Ci-Ci6) -alkylnaphthalenesulfonic acid or phenol sulfonic acid with formaldehyde (= (Ci-Ci6) -naphthalenesulfonate-formaldehyde condensates, (Ci-Ci6) -alkylnaphthalenesulfonate-formaldehyde condensates and phenolsulfonate-formaldehyde condensates); Oligo- (C 2 -C 3) -alkylene oxide mono-, di- and tristyrylphenyl ether sulfates, in particular oligoethoxylates of mono-, di- and tristyrylphenol;

Mono and di (C 8 -C 22) alkyl sulfates; Oligo (C2-C3) -alkylenoxid- (C8-C22) -alkyletherphosphaten; Oligo (C2-C3) -alkylenoxid- (Ci-Ci6) -alkylbenzoletherphosphaten; Oligo (C2-C3) alkylene oxide mono-, di- and tristyrylphenyl ether phosphates; Oligoethylenoxidpolycarboxylaten, in particular homo- and cooligomers of monoethylenically unsaturated mono- or dicarboxylic acids having from 3 to 8 carbon atoms, wherein the cooligomers also Oligoethylenoxid side chains have; Fatty acids, such as stearic acid; and - oligophosphates, such as hexametaphosphates and triphosphates (or tripolyphosphates). Of the aforementioned anionic surfactants, the sodium, potassium, calcium and ammonium salts of the following are preferred:

(Ci-Ci6) alkyl benzene sulfonates;

(Ci-Ci6) -Alkylnaphthalinsulfonate; - Naphthalinsulfonat-formaldehyde condensates and (Ci-Ci6) -alkylnaphthalenesulfonate-formaldehyde condensates;

Oligo (C2-C3) -alkylenoxid- (C8-C22) alkyl ether sulphates;

Oligo (C2-C3) -alkylenoxid- (C8-C22) alkyl ether;

Oligo (C2-C3) alkylene oxide (Ci-Ci6) alkylbenzene ether sulfates; - Oligo (C2-C3) -alkylene oxide (Ci-Ci6) -alkylbenzoletherphosphate,

(C ₈ -C ₂₂ ) -alkyl sulfates,

(C4-CI8) dialkyl sulfosuccinates,

Oligo (C2-C3) alkylene oxide mono-, di- and tristyrylphenyl ether sulfates,

Oligo (C2-C3) alkylene oxide mono-, di- and tristyrylphenyl ether phosphates, - Oligoethylenoxidpolycarboxylate and

Polyphosphates, and mixtures thereof.

Particularly preferred anionic surfactants f) include the salts, in particular the sodium, potassium, calcium and ammonium salts of the oligo- (C 2 -C 3) -alkylene oxide mono-, di- and tristyrylphenyl ether sulfates.

The weight ratio of anionic surfactants f) and nonionic surfactants e) of the surfactant mixtures in the formulations according to the invention is preferably in the range from 0.05: 1 to 10: 1, and particularly preferably in the range from 0.1: 1 to 4: 1 ,

According to a particularly preferred embodiment, component e) is two nonionic surfactants having different HLB values, in particular a surfactant e.1) and a surfactant e.2), and component f) is an anionic surfactant ,

The total amount of surfactant contained in the formulations of the invention generally depends on the amounts of organic crop protection active ingredients a) and of solvents b), c) and d), as well as their properties. The weight ratio of the total amount of surfactants e) and f) to the total amount of crop protection active ingredients a) will usually be in the range from 0.3: 1 to 30: 1, preferably in the range from 0.5: 1 to 20: 1, and in particular Range from 1: 1 to 7: 1. Based on the total weight of the undiluted formulations, the surfactant content is generally from 1 to 35% by weight, preferably from 5 to 25% by weight and in particular from 10 to 25% by weight. %. Based on the total weight of the undiluted formulations, the proportion of nonionic surfactants e) is generally from 0.5 to 30% by weight, preferably from 4 to 24% by weight and in particular from 5 to 20% by weight.

Based on the total weight of the undiluted formulations, the proportion of anionic surfactants d) is generally from 0.5 to 25% by weight, preferably from 1 to 20% by weight and in particular from 5 to 15% by weight.

The total amount of surfactants e) and f) present in the formulations of the invention and solvents b), c) and d) (= organic solvents) generally depends on the nature and amount of the organic crop protection active ingredients a). The weight ratio of surfactants e) + f) plus organic solvents b) + c) + d) to crop protection active ingredients a) will usually be in the range from 75: 1 to 0.5: 1, preferably in the range from 50: 1 to 1: 1, and in particular in the range of 30: 1 to 2: 1. Based on the total weight of the undiluted formulations, the proportion of surfactant plus solvents is generally from 10 to 95 wt .-%, preferably from 20 to 85 wt .-% and in particular from 40 to 75% by weight.

According to the invention, the active ingredient compositions comprise at least one organic crop protection active ingredient. The term "crop protection agent" is to be understood broadly in this context and includes both substances which protect plants from infestation with harmful organisms, substances which kill or prevent the development of plant-damaging organisms and substances which influence the growth of the crop, ie increase or decrease growth, including substances used to improve plant health.

Fungicides, i. Active substances which kill phytopathogenic fungi or prevent their growth or reduce the infestation of the useful plant with such plant-pathogenic fungi;

Insecticides, acaricides and nematicides, d. H. Active substances which kill plant-destructive arthropods or nematodes or reduce their development in a manner which effectively prevents the crop from infesting or reduces the infestation of a plant with those harmful organisms; - herbicides, d. H. Active substances which kill a harmful plant or their

Reduce or prevent growth;

Growth regulators, ie agents that promote or reduce plant growth; Safeners, ie active substances which reduce or prevent a phytotoxic effect on the useful plants, which is triggered by the abovementioned substances; as well as fertilizers. The organic crop protection active ingredient is preferably a low molecular weight organic crop protection active, ie a low molecular weight organic compound having a molecular weight in the range from 150 to 500 DaIton.

Preferably, the crop protection agent is solid at room temperature or a non-volatile oil, i. H. he has at 25 ° C to a vapor pressure of less than 0.1 mbar.

Preferably, the crop protection active ingredient in the solvent b) or in the mixture of the solvents b), c) and d) at 25 ° C has a solubility of at least 1 g / l, in particular at least 10 g / l.

Suitable crop protection active ingredients are, for example, W. Krämer and U. Schirmer (Ed.) "Modern Crop Protection Compounds" Vol. 2, Wiley-VHC 2007;

C. D.S. Tomlin, "The Pesticide Manual", 13th Edition, British Crop Protection Council (2003); and from "The Compendium of Pesticide Common Names," http://www.alanwood.net/pesticides/.

The following are examples of fungicidal active ingredients in Groups A.1 to A.6:

A.1. Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, methyl (2-chloro-5- [1- (3-methylbenzyloxyimino) ethyl] benzyl) carbamate, Methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate, methyl 2- (ortho - ((2,5-dimethyl-phenyloxymethylene) -phenyl) -3 methoxyacrylate;

A.2 carboxylic acid amides such as

• carboxylic acid anilides: benalaxyl, benalaxyl-M, benodanil, carboxin, mebenil, mepronil, fenfuram, fenhexamide, flutolanil, furalaxyl, furcarbanil, furamet-pyr, metalaxyl, metalaxyl-M (mefenoxam), methfuroxam, metsulfovax, ofurace, oxadixyl, oxycarboxin, Penthiopyrad, pyracarbolide, salicylanilides, tecloftalam, thifluzamides, tiadinil, 3,4-dichloroisothiazole-5-carboxylic acid (2-cyanophenyl) amide (isotianil);

N-biphenylamides: bixafen, boscalid, 4-difluoromethyl-2-methylthiazole-5-carboxylic acid (4'-bromobiphenyl-2-yl) -amide, 4-difluoromethyl-2-methylthiazole-5-carboxylic acid (4'-trifluoromethylbiphenyl-2-yl) -amide, 4-difluoromethyl-2-methylthiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl - pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid (3', 4 ', 5'-trifluorobiphenyl -2-yl) -amide; • Carboxylic acid morpholides: dimethomorph, flumorph;

Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, silthiofam, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-ethanesulfonylamino-3-methylbutyramide;

A.3. Azoles such as

• triazoles: bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, fistulafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tet - raconazole, triadimenol, triadimefon, triticonazole;

Imidazoles: cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole; Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

• Other: Ethaboxam, Etridiazole, Hymexazole;

A.4. Nitrogen-containing heterocyclyl compounds such as

Pyridines: Fuazinam, Pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] -pyridine;

• pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;

• piperazine: triforin;

Pyrroles: fludioxonil, fenpiclonil; • morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph;

Dicarboximides: iprodione, procymidone, vinclozolin;

• Other: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomethine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole, proquinazide, pyroquilon, quinoxyfen, tricyclazole, 5-chloro-7- ( 4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyimidine, 2-

Butoxy-6-iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide;

A.5. Carbamates and dithiocarbamates such as, for example, dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb,

Thiram, Zineb, Ziram;

Carbamates: Diethofencarb, Flubenthiavalicarb, Iprovalicarb, Propamocarb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionic acid methyl ester, N- (1- (1 - (4-cyanophenyl) ethanesulfonyl) but -2-yl) carbamic acid 4-fluorophenyl ester;

A.6. Other fungicides such as • guanidines: dodine, iminoctadine, guazatine;

• Antibiotics: Kasugamycin, Polyoxins, Streptomycin, Validamycin A;

Organometallic compounds: fentin salts;

Sulfur-containing heterocyclyl compounds: isoprothiolane, dithianone; Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenefos, pyrazophos or tolclofos-methyl;

Organochlorine compounds: thiophanate methyl, chlorothalonil, dichlofluanid, tolylfluanid, flusulfamide, phthalide, hexachlorobenzene, pencycuron, quintozene;

Nitrophenyl derivatives: binapacryl, dinocap, dinobuton; • Other: Spiroxamine, Cyflufenamid, Cymoxanil, Metrafenon.

Examples of active ingredients having insecticidal, acaricidal and / or nematicidal activity are mentioned in Groups B.1 to B.24:

B.1. Organo (thio) phosphates: acephate, azamethiphos, azinphos-ethyl, azinphos-

Methyl, chloroethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos (DDVP), dicrotophos, dimethoate, dimethylvinphos, disulphoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion , Fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathione, malathion, mecarbam, methamidophos,

Methidathion, Methyl Parathion, Mevinphos, Monocrotophos, Naled, Omethoat, Oxydemeton-Methyl, Paraoxone, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidone, Phoxim, Pirimiphos-Methyl, Profenofos, Pro- petamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Sulprophos, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon,

Triazophos, trichlorofon, vamidothion;

B.2. Carbamates: Aldicarb, Alanycarb, Bendiocarb, Benfuracarb, Butocarboxime, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Piricimarb, Propoxur, Thiodicarb, Thiofanox, trimethacarb, XMC, xylylcarb, triazamate;

B.3. Pyrethroids: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin , Alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin , Profuthrin, Pyrethrin

(Pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin; B.4. Mimics of Juvenile Hormones: Hydroprene, Kinoprene, Methoprene, Fenoxycarb, Pyriproxyfen;

B.5. Compounds of Nicotine Receptor Agonists / Antagonists: Acetamiprid, Bensul-tap, Cartap hydrochloride, Clothianidin, Dinotefuran, Imidacloprid, Thiamethoxam, Nitenpyram, Nicotine, Spinosad (allosteric agonist), Spinetoram, Thiacloprid, Thiocyclam, Thiosultap Sodium and AKD1022.

B.6. Compounds of GABA-driven chloride channel antagonists: chlordane, endosulfan, gamma-HCH (lindane); Acetoprol, Ethiprol, Fipronil, Pyrafluprol, Pyriprol, Vaniliprol;

B.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, lepimetin;

B.8. METI I compounds: Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad, Flufenerim, Rotenone;

B.9. METI II and III Compounds: Acequinocyl, Fluacyprim, Hydramethylnone;

B.10. Compounds that Decouple Oxidative Phosphorylation: Chlorfenapyr, DNOC;

B.11. Compounds which inhibit oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fenbutatin oxide, propargite, tetradifon;

B.12. Anti-skinning compounds: cyromazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide;

B.13. Synergistic compounds: piperonyl butoxide, Tribufos;

B.14. Sodium channel blocking compounds: indoxacarb, metaflumizone;

B.15. Compounds for selective edema inhibition: Crylotie, Pymetrozin, Flonicamid;

B.16. The mite growth inhibiting compounds: clofentezine, hexythiazox, etoxazole;

B.17. Compounds Inhibiting Chitin Synthesis: Buprofezin, Bistrifluron, Chlorofluoronon, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron, Triflumuron; B.18. Fatty biosynthesis inhibiting compounds: spirodiclofen, spiromesifen, spirotetramat;

B.19. Compounds of octapaminergic agonists: amitraz;

B.20. Ryanodine receptor modulating compounds: flubendiamide, (R) - and (S) -3-chloro-N1- {2-methyl-4- [1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} - N2- (1-methyl-2-methylsulfonylethyl) phthalamide;

B.21. Various: amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, cyenopopyrene, cyflumetofen, quinomethionate, dicofol, fluoroacetate, phosphine, pyralidyl, pyrifluquinazone, organic sulfur compounds, sulfoxaflor, 4-but-2-ynyloxy-6- (3,5-dimethyl) piperidin-1-yl) -2-fluoropyrimidine, 3-benzoylamino-N- [2,6-dimethyl-4- (1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl) -phenyl] -2-fluorobenzamide , 4-

[5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] -2-methyl-N-pyridin-2-ylmethyl-benzamide, 4- [5- (3,5 Dichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] -2-methyl-N- (2,2,2-trifluoroethyl) -benzamide, 4- [5- (3,5-dichlorophenyl) -5 -trifluoromethyl-4,5-dihydro-isoxazol-3-yl] -2-methyl-N-thiazol-2-ylmethylbenzamide (M22.5), 4- [5- (3,5-dichloro-phenyl) - 5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl] -2-methyl-N- (tetrahydrofuran-2-ylmethyl) -benzamide, 4 - {[(6-bromopyrid-3-yl) methyl] (2 -fluoroethyl) amino} furan-2 (5H) -one, 4 - {[(6-fluoropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one, 4- { [(2-chloro-1,3-thiazolo-5-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one, 4 - {[(6-chloropyrid-3-yl) methyl] ( 2-fluoroethyl) amino} furan-2 (5H) -one,

4 - {[(6-chloropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one, 4 - {[(6-chloro-5-fluoropyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one, 4 - {[(5,6-dichloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one, 4 - {[(6-chloro-5-fluoropyrid-3-yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one, 4 - {[(6-chloropyrid-3-yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one,

4 - {[(6-chloropyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one, cyclopropaneacetic acid 1, 1 '- [(3S, 4R, 4aR, 6S, 6aS, 12R, 12aS, 12bS) -4 - [[(2-cyclopropylacetyl) oxy] methyl] -1, 3,4,4a, 5,6,6a, 12,12a, 12b-decahydro-12-hydroxy-4,6a, 12b trimethyl-1 1-oxo-9- (3-pyridinyl) -2H, 1 H -naphtho [2,1-b] pyrano [3,4-e] pyran-3,6-diyl] ester, 8- (2-cyclopropylmethoxy-4-methylphenoxy) -3- (6-methylpyridazin-3-yl) -3-azabicyclo [3.2.1] octane (M22.18);

B.22. N-R'-2,2-dihalo-1-R "-cyclopropanecarboxamide-2- (2,6-dichloro-α, α, α-trifluoro-p-tolyl) hydrazone or N-R'-2,2- di-R '"- Propionamide-2- (2,6-dichloro-α, α, α-trifluoro-p-tolyl) -hydrazone, wherein R' is methyl or ethyl, Halo for chloro or bromo, R" for

Hydrogen or methyl and R '"are methyl or ethyl; B.23. Anthranilamide compounds: chloranthraniliprole, cyantraniliprole,

5-Bromo-2- (3-chloro-pyridin-2-yl) -2H-pyrazole-3-carboxylic acid [4-cyano-2- (1-cyclopropyl-ethylcarbamoyl-O-methyl-phenyl-amide,

5-Bromo-2- (3-chloropyridin-2-yl) -2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6- (1-cyclopropyl-ethylcarbamoyl-O-phenoxy-amide,

5-Bromo-2- (3-chloropyridin-2-yl) -2H-pyrazole-3-carboxylic acid [2-bromo-4-cyano-6- (1-cyclopropyl-ethylcarbamoyl) -phenyl] -amide,

5-Bromo-2- (3-chloropyridin-2-yl) -2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6- (1-cyclopropyl-ethylcarbamoyl-phenoxy-amide, 5-bromo-2 (3-chloropyridin-2-yl) -2H-pyrazole-3-carboxylic acid [2,4-dichloro-6- (1-cyclopropyl-ethylcarbamoyl) -phenyl] -amide,

5-Bromo-2- (3-chloropyridin-2-yl) -2H-pyrazole-3-carboxylic acid [4-chloro-2- (1-cyclopropyl-ethylcarbamoyl-O-methyl-phenyl-amide,

B.24. Malononitrile Compounds: CF ₂ HCF ₂ CF ₂ CF ₂ CH ₂ C (CN) ₂ CH ₂ CH ₂ CF ₃ (2- (2,2,3,3,4,4,5,5-octafluoropentyl) -2- (3,3,3-trifluoro-propyl) malononitrile), CF ₃ (CH ₂ ) ₂ C (CN) ₂ CH ₂ (CF ₂ ) ₅ CF ₂ H (2- (2,2,3,3,4, 4,5,5,6,6,7,7-dodecafluoroheptyl) - 2- (3,3,3-trifluoro-propyl) -malononitrile), CF ₃ (CH ₂ ) ₂ C (CN) ₂ (CH ₂ ) ₂ C (CF ₃ ) ₂ F (2- (3,4,4,4-tetrafluoro-3-trifluoromethyl-butyl) -2- (3,3,3-trifluoro-propyl) -malononitrile), CF ₃ (CH _{2) 2} C (CN) ₂ (CH _{2) 2} (CF _{2) 3} CF ₃ (2- (3,3,4,4,5,5,6,6,6-nonafluoro-hexyl) -2-

(3,3,3-trifluoro-propyl) -malononitrile), CF ₂ H (CF ₂ ) ₃ CH ₂ C (CN) ₂ CH ₂ (CF ₂ ) ₃ CF ₂ H (2,2-bis- (2, 2,3,3,4,4,5,5-octafluoro-pentyl) malononitrile)

CF ₃ (CH ₂ ) ₂ C (CN) ₂ CH ₂ (CF ₂ ) ₃ CF ₃ (2- (2,2,3,3,4,4,5,5,5-nonafluoropentyl) -2- (3,3,3-trifluoro-propyl) -malononitrile), CF ₃ (CF ₂ ) ₂ CH ₂ C (CN) ₂ CH ₂ (CF ₂ ) ₃ CF ₂ H (2- (2,2,3,3 , 4,4,4-heptafluoro-butyl) -2- (2,2,3,3,4,4,5,5-octafluoro-pentyl) -malononitrile), CF ₃ CF ₂ CH ₂ C (CN) ₂ CH ₂ (CF ₂ ) SCF ₂ H (2- (2,2,3,3,4,4,5,5-octafluoropentyl) -2- (2,2,3,3,3-pentafluoro-propyl ) malononitrile)

CF ₂ HCF ₂ CF ₂ CF ₂ CH ₂ C (CN) ₂ CH ₂ CH ₂ CF ₂ CF ₃ (2- (2,2,3,3,4,4,5,5-octafluoropentyl) -2- (3 , 3,4,4,4-pentafluorobutyl) -malonodinitrile), CF ₃ (CH ₂ ) ₂ C (CN) ₂ CH ₂ (CF ₂ ) ₃ CF ₂ H (2- (2,2,3,3,4 , 4,5,5-Octafluoropentyl) -2- (3,3,3-trifluoro-butyl) -malononitrile);

The commercially available compounds of group B, among other publications, for example, in "The Pesticide Manual", thirteenth edition, British Crop Protection Council (2003), recorded.

Lepimectin is from Agro Project, PJB Publications Ltd, November 2004 known. Benzothiaz and its representation has been described in EP-A1 454621. Methadathion and paraoxon and their presentation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprol and its presentation have been described in WO 98/28277. Metaflumizone and its presentation has been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. py rafluprol and its illustration has been described in JP 2002193709 and in WO 01/00614. Pyriprole and its presentation has been described in WO 98/45274 and in US 6,335,357. Amidoflumet and its presentation has been described in US 6,221,890 and JP 21010907. Flufenerim and its depiction has been described in WO 03/007717 and in WO 03/007718. AKD 1022 and its illustration have been described in US 6300348. Chloroanthra- niliprol has been described in WO 01/70671, WO 03/015519 and WO 05/1 18552. Cyantraniliprole has been described in WO 01/70671, WO 04/067528 and WO 05/118552. Further anthranilamide derivatives have been described in WO 01/70671, WO 04/067528 and WO 05/118552. Cyflumetofen and its representation has been described in WO 04/080180. The aminoquinazolinone compound pyrifluquinazone has been described in EP A 109 7932. Sulfoximine derivatives such as sufloxaflor and analogs thereof have been described including their presentation in WO 2006/060029 and WO 2007/149134. The alkynyl ether compounds have been described, for example, in JP 2006131529. Organic sulfur compounds have been described in WO 07/060839. The malononitrile compounds are described in WO 02/089579, WO 02/090320, WO 02/090321, WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694 Service.

Examples of herbicidal active ingredients are mentioned in groups C.1 to C.15:

C.1 Lipid biosynthesis inhibitors such as, for example, chloroazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, fenoxaprop-p, fenthiaprope, fluazifop, fluazipop-P, haloxyfop, haloxyfop-P, isoxapyrifop, metamifop, propaquizafop, quizalobium fop, quizalofop-P, trifop, alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim, butylate, cycloate, di-allat, dimepiperate, EPTC, esprocarb, ethiolate, isopolinate, methiobencarb, molinate, Orbencarb, pebulate, prosulfocarb, sulfallate, thiobencarb, tiocarbazil, triallate,

Vernolate, benfuresate, ethofumesate and benzenside;

C.2 ALS inhibitors such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, lodosulfuron, mesosulfuron, metsulfuron, nicosulfuron, oxasulfuron, primisulfuron Prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, cloransulam, diclosulam, florasulam, flumetsulam, metosulam, Pennoxsulam, bispyribac, pyrimi- nobac, propoxycarbazone, flucarbazone, pyribenzoxime, pyriftalid and pyrithiobac; C.3 photosynthesis inhibitors such as atraton, atrazine, ametryn,

Aziprotryn, Cyanazine, Cyanatryn, Chlorazine, Cyprazin, Desmetryn, Dimethetrim, Dipropetryn, Eglinazine, Ipazine, Mesoprazine, Methometon, Methoprotryn, Procyazine, Proglinazine, Prometon, Prometry, Propazine, Sebuthylazine, Secbumeon, Simazine, Simeton, Simetryn, Terbumeton, Terbuthylazine, Tterbutryn, Trietazine, Ametridione, Amibuzin, Hexazinone, Isomethiozine, Metamitron, Metribuzin, Bromacil, Isocil, Lenacil, Terbacil, Brompyrazone, Chloridazon, Dimidazone, Desmedipham, Phenisopham, Phenmedipham, Phenmedipham-Ethyl, Benzothiazine. ron, buthiuron, ethidimuron, isourone, methabenzthiazuron, monoisouron, terbuthuron, thiazafluron, anisuron, buturon, chlorobromuron, chlororeturon, chlorotoluron, chloroxuron, difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluothiuron, isoproturon, linuron, methuron, Metobenzuron, Metobromuron, Metaboluron, Monolinuron, Monuron, Neburon, Parafluron, Phenobenzuron, Siduron, Tetrafluron, Thidiazuron, Cyperquat, Diethamquat, Difenzoquat, Diquat,

M; orfamquat, paraquat, bromobonil, bromoxynil, chloroxynil, iodobonil, loxynil, amicarbazone, bromofenoxime, flumezine, methazole, bentazone, propanil, penta-norlor, pyridate and pyridafol;

C.4 protoporphyrinogen IX oxidase inhibitors such as, for example, acifluorfen, biphenyl, chlomethoxyfen, chlornitrofen, ethoxyfen, fluorodifen, fluoroglycofen, fluronitrofen, fomesafen, furyloxyfen, halosafen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen, fluazolates, pyraflufen, Cinidonethyl, flumiclorac, flumioxazine, fiumipropyne, fluthiacet, thidiazimine, oxadiazone, oxadiargyl, azafenidine, carfentrazone, sulfentrazone, pentoxazone, benzfendizone, butafenacil, pyraclonil, profluazole,

Flufenpyr, Flupropacil, Nipyraclofen and Etnipromide;

C.5 bleacher herbicides such as metflurazon, norflurazon, flufenican,

Diflufenican, picolinafen, beflubutamide, fluridone, flurochloridone, flurtamone, mesotrione, sulcotrione, isoxachlorotol, isoxaflutole, benzofenap, pyrazolynate, pyrazoxyfen, benzobicyclone, amitrole, clomazone, aclonifen, 4- (3-trifluoromethylphenoxy) -2- (4 -trifluoromethylphenyl) pyrimidine and 3-heterocyclyl-substituted benzoyl derivatives of the formula II (see WO 96/26202, WO 97/411 16, WO 97/411 17 and WO 97/411 18)

in which the variables R ⁸ to R ^{13 have} the following meanings: R ⁸ , R ^{10 are} hydrogen, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C -haloalkoxy, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylsulfinyl or C ₁ -C ₆ -alkyl C ₆ -Alkylsu If onyl;

R ^{9 is} a heterocyclic radical selected from the group of thiazol-2-yl, thiazole

4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl and 4, 5-dihydroisoxazol-5-yl, where the nine radicals mentioned may be unsubstituted or mono- or polysubstituted, for example mono-, di-, tri- or tetrasubstituted by halogen, C 1 -C ₄ -alkyl, C 1 -C ₄ Alkoxy, C 1 -C ₄ haloalkyl, C 1 -C ₄ haloalkoxy or C 1 -C ₄ alkylthio;

R ^{11 is} hydrogen, halogen or C ₁ -C ₆ -alkyl;

R ^{12 is} C 1 -C 6 -alkyl;

R ^{13 is} hydrogen or CrCβ-alkyl.

C.6 EPSP synthase inhibitors such as glyphosate;

C.7 glutamine synthase inhibitors such as glufosinate and bilanaphos;

C.8 DHP synthase inhibitors such as asulam;

C.9 mitosis inhibitors such as, for example, benfluralin, butraline, dinitramine, ethalfluran-Nn, fluchloralin, isopropalin, methalpropaline, nitralin, oryzalin, pendimethalin, propiamine, profluralin, trifluralin, amiprofosmethyl, butamifos, dithiopyr, thiazopyr, propyzamide, tebutam, Chlorthal, Carbetamide, Chlorobufam, Chlorpropham and Propham;

C.10 VLCFA inhibitors such as acetochlor, alachlor, butachlor, butenochlor, delachlor, diethatyl, dimethachlor, dimethenamid, dimethenamid-P, metazo-chloro, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, Pry- nachlor, terbuchlor, thenylchlor, xylachlor, allidochlor, CDEA, epronaz, diphenylamide, napropamide, naproanilide, pethoxamide, flufenacet, mefenacet, fentrazamide, anilofos, piperophos, cafenstrol, indanofan and tridiphan;

C.1 1 cellulose biosynthesis inhibitors such as dichlobenil, chlorthiamide,

Isoxaben and flupoxam;

C.12 decoupling herbicides such as, for example, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinofen and medinoterb; C.13 auxin herbicides such as clomeprop, 2,4-D, 2,4,5-T, MCPA, MCPA thioethyl, dichlorprop, dichlorprop-P, mecoprop, mecoprop-P, 2,4-DB, MCPB, Chloramben , Dicamba, 2,3,6-TBA, tricamba, quinclorac, quinmerac, clopyralid, fluroxypyr, picloram, triclopyr and benazoline;

C.14 auxin transport inhibitors such as naptalam and diflufenzopyr;

C.15 benzoylprop, flamprop, flamprop-M, bromobutide, chlorofluorol, cinmethylin, methyldymron, etobenzanide, fosamine, metam, pyributicarb, oxaziclomefone,

Dazomet, triaziflam and methyl bromide.

Suitable safeners can be selected from the following list: Benoxacor, Cloquintocet, Cyometrinil, Dichlormid, Dicyclonon, Dietholate, Fenchlorazole, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen, Mefenpyr, Mephenate, Naphthalene Anhydride, 2,2,5-Trimethyl-3 (dichloroacetyl) -1,3-oxazolidine (R-29,148), 4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane (AD-67, MON 4660) and oxabetrinil.

Examples of growth regulators are 1-naphthylacetamide, 1-naphthylacetic acid, 2-Naphthyloxyessisgsäure, 3-CPA, 4-CPA, Ancymidol, anthraquinone, BAP, Butifos; Tribufos, butralin, chlorofluorol, chlormequat, clofencet, cyclanilides, daminozides, dicamba, dikegulac sodium, dimethipine, chlorfenethol, etacelasil, ethephon, ethychlozate, fenoprop, 2,4,5-TP, fluoride amide, flurprimidol, flutriafol, gibberellin acid, Gibberellin, guazatine, indolebutyric acid, indoleacetic acid, karetazan, kinetin, lactidichloroethyl, maleic hydrazide, mefluidides, mepiquat chloride, naptalam, paclobutrazoles, prohexadione-calcium, quinmerac, tin-oven, tetcyclacis, thidiazuron, triiodobenzoic acid, tri-penthenol, triazethane , Tribufos, Trinexapac-ethyl and Uniconazole.

With regard to seed treatment, the crop protection active ingredients are preferably selected from organic active substances which have a fungicidal, insecticidal, acaricidal and / or nematicidal action. In particular, this is one or more of the following substances:

Substances having a fungicidal action, for example fungicides of the group A.1, in particular azo-xystrobin, kresoxim-methyl, orysastrobin, pyraclostrobin or trifloxystrobin, fungicides from the group A.2, in particular dimethomorph, carboxin, silthiofam, as well as N-biphenylamides such as boscalid , Bixafen or 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid (3 ', 4', 5'-trifluorobiphenyl-2-yl) -amide, fungicides from the group A.3, in particular benomyl, carbendazim, hymexazole , Imazalil, prochloraz, thiabendazole, as well as triazoles such as difenoconazole, epoxiconazole, fluquinconazole, flutriafol, metconazole, prothioconazole, tebuconazole, triadimenol or triticonazole. laxyl, metalaxyl-M (mefenoxam), oxadixyl, guazatine, pyrimethanil, streptomycin, iprodione, fludioxonil or captan.

Substances having insecticidal or acaricidal or nematicidal activity, e.g. Acetamidipride, alpha-cypermethrin, beta-cypermethrin, bifenthrin, carbofuran, carbosulfan, clothianidin, cycloprothrin, cyfluthrin, cypermethrin, deltamethrin, diflubenzuron, dinotefuran, etofenprox, fenbutatin oxide, fenpropathrin, fipronil, flucythrinate, imidaclidride, lambda Cyhalothrin, nitenpyram, pheromones, spinosad, teflubenzuron, tefluthrin, terbufos, thiacloprid, thiamethoxam, thiodicarb, tralomethrin, triazamate, zeta-cypermethrin, spirotetramat, flupyrazofos, NC 512, tolfenpyrade, flubendiamide, bistrifluron, benclothiaz, DPX-E2Y45, HGW86, pyrafluprol , Pyriprol, F-7663, F-2704, Amidoflumet, Flufenerim or Cyflumetofen.

The abovementioned crop protection active ingredients can be used alone or in combination with one another.

In a preferred embodiment of the invention, the at least one crop protection agent a) has a melting point of at most 120 ^° C., preferably at most or less than 100 ^° C.

In a further preferred embodiment, the formulations according to the invention comprise at least one crop protection agent a), which is a fungicide selected according to a particularly preferred embodiment from prochloraz, boscalid, pyraclostrobin, triticonazole, pyrimethanil, fluquinconazole and 3-difluoromethyl-1 -methylpyrazole-4-carboxylic acid (3 ', 4', 5'-trifluorobiphenyl-2-yl) -amide.

In a particularly preferred embodiment, the formulation according to the invention comprises at least one fungicidal active ingredient from group A.1, for example at least one of azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cremoxime-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, oryssastrobin, Methyl (2-chloro-5- [1 - (3-methylbenzyloxyimino) ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate and Methyl 2- (ortho - ((2,5-dimethylphenyloxymethylene) phenyl) -3-methoxyacrylate, and especially pyraclostrobin.

In a further, particularly preferred embodiment, the formulation according to the invention contains at least one fungicidal active ingredient from group A.3, in particular at least one triazole and / or imidazole, for example at least one of bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole , Fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, Prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, cyazofamide, imazalil, pefurazoate, prochloraz and triflumizole selected drug.

In a further, likewise particularly preferred embodiment, the formulation according to the invention contains at least one fungicidal active ingredient from group A1, which is preferably selected from azoxystrobin, dimoxystrobin, enestroburin, fi oxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, Orysastrobin, methyl (2-chloro-5- [1 - (3-methylbenzyloxyimino) ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] - benzyl) carbamate and methyl 2- (ortho - ((2,5-dimethylphenyloxymethylene) phenyl) -3-methoxyacrylate and which is preferably pyraclostrobin, and at least one further active compound from the group A.3, in particular at least one Triazole and / or imidazole, for example at least one of bitertanol, bromonuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbiconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole , Metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, cyazofamide, imazalil, pefurazoate, prochloraz and triflumizole, in particular triticonazole or prochloraz or a mixture of triticonazole and prochloraz.

The formulations according to the invention comprise the at least one organic crop protection active substance a), as a rule in a concentration of 0.1 to 40% by weight, frequently 1 to 30% by weight, in particular 2 to 25% by weight or 5 to 20% by weight %, based on the total weight of the formulation. In the case of several crop protection agents a) the total concentration of the crop protection active ingredients is generally in the range of 0.1 to 40 wt .-%, often in the range of 1 to 30 wt .-% and in particular in the range of 2 to 25 wt .-% or in the range of 5 to 20% by weight, based on the total weight of the formulation.

The formulations of the invention also contain water. With regard to the total weight of the undiluted formulation, the water content is usually in the range of 1 to 80 wt .-%, often in the range of 5 to 50 wt .-%, in particular in the range of 10 to 40 wt .-% and preferably in the range from 15 to 30% by weight. It is obvious that the water content and the proportions of the remaining constituents add up to 100% by weight.

In a preferred embodiment of the invention, the aqueous formulations comprise: a. from 0.1 to 40% by weight, often from 1 to 30% by weight, in particular from 2 to 25% by weight or from 5 to 20% by weight, of at least one organic plant protection product Active substance having a water solubility of less than 5 g / l at 20 ^° C., as defined above, in particular at least one of the preferred or particularly preferred plant active ingredients a); b. from 1 to 60% by weight, frequently from 10 to 40% by weight, in particular from 15 to 35% by weight, of at least one solvent b) as defined above, in particular at least one of the preferred or particularly preferred solvent b) ; c. from 1 to 60% by weight, often from 10 to 40% by weight, in particular from 15 to 35% by weight, of at least one solvent c) as defined above, in particular at least one of the solvents indicated as being preferred or particularly preferred c) ; d. from 1 to 60% by weight, often from 5 to 45% by weight, in particular from 10 to 35% by weight, of at least one solvent d) as defined above, in particular at least one of the solvents indicated as being preferred or particularly preferred d); e. from 0.5 to 30 wt .-%, often 2 to 25 wt .-% or 4 to 24 wt .-%, in particular 5 to 20 wt .-% of at least one nonionic surfactant e) as defined above, in particular at least one of the preferred surfactants or particularly preferred surfactants e); f. from 0.5 to 25 wt .-%, often 1 to 25 wt .-% or 1 to 20 wt .-%, in particular 5 to 15 wt .-% of at least one anionic surfactant f) as defined above, in particular at least one of preferred or particularly preferred surfactants f); and G. Water ad 100 wt .-%, for example in an amount of 1 to 80 wt .-%, often in the range of 5 to 50 wt .-%, in particular in the range of 10 to 40 wt .-% and especially in the range from 15 to 30% by weight.

The data in% by weight relate in each case to the total weight of the formulation according to the invention.

With regard to the proportions of components a) -f), in particular with respect to the total amount of surfactants e) + f), with respect to the total amount of solvent b) + c) + d), with respect to the total amount of surfactants e + f) plus solvent b) + c) + d), with respect to the ratio of the total amount of surfactants e) + f) to crop protection agent a), with respect to the ratio of the total amount of surfactants e) + f) to the total amount of solvent b) + c) + d) as well as with respect to the ratio of the total amount of surfactants e + f) plus solvent b) + c) + d) to crop protection active substance a) the above applies. The formulations of the invention may further contain conventional adjuvants, such as defoamers (defoamers), preservatives (bactericides), colorants, stabilizers, thickeners, adhesives, antifreeze agents and other substances commonly used in aqueous pesticide formulations. The total amount of these auxiliaries will generally not be more than 20% by weight, in particular not more than 15% by weight, of the weight of the undiluted formulation. The amount of a single adjuvant will usually not exceed, except for antifreezes and colorants, 5% by weight and especially 3% by weight.

Suitable defoamers include polysiloxanes, such as polydimethylsiloxane, long-chain alcohols, fluoroorganic compounds, fatty acids and their salts, and mixtures thereof. Defoamers are usually used in amounts of from 0.1 to 5 grams per liter of the formulations.

Suitable preservatives for preventing bacterial attack of the compositions of the invention include formaldehyde, alkyl esters of para-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, ortho-phenylphenol, dichlorophene, benzyl alcohol hemiformal, thiazolinone and isothiazolinone derivatives. te, such as alkylisothiazolinones and benzisothiazolinones, 5-chloro-2-methyl-4-isothiazolinone, pentachlorophenol, 2,4-dichlorobenzyl alcohol and mixtures thereof. Examples piele of suitable commercially available bactericidal products are Proxel ^® (ICI), Acetide ^® RS (Thor Chemie), Kathon ^® (Rohm & Haas) and Acetide MBS (Thor Chemie). In general, the level of preservative will be from 0.1 to 10 grams per liter of the formulations.

Examples of colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned under the names rhodamine B, Cl. Pigment Red 112 and Cl. Solvent Red 1 known dyes, as well as pigment blue 15: 4, pigment blue 15: 3, pigment blue 15: 2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 1 12, pigment red 48: 2, pigment red 48: 1, pigment red 57: 1, pigment red 53: 1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic purple 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108, acid red 18, food red 1, food red 2 and food red 7th

Suitable stabilizers include, for example, UV absorbers such as cinnamic acid esters, 3,3-diphenyl-2-cyanoacrylates, hydroxy- and / or alkoxy-substituted benzophenones, N- (hydroxyphenyl) benzotriazoles, hydroxyphenyl-s-triazines, oxalic acid amides and salicylates such as Uvinul ^® 3000, 3008, 3040, 3048, 3049, 3050,

3030, 3035, 3039, 3088, UVINUL ^® MC80 and radical scavengers, such as ascorbic acid, citric acid, sterically hindered amines (HALS-compounds) such as UVINUL ^® 4049H, 4050H, 5050H, and the like, as well as antioxidants such as vitamin E. In a preferred embodiment the stabilizer is citric acid or ascorbic. Usually, the amount of stabilizer will be in the range of 0.01 to 10 grams per liter of formulation.

Examples of thickeners (ie compounds which impart to the formulation modified flow properties, ie, high viscosity at rest and low viscosity in motion) are polysaccharides, such as Xanthan Gum (Kelzan ^®, Kelco), rhodium dopol ^® 23 (Rhone Poulenc) or Veegum ^® (RT Vanderbilt) as well as organic and inorganic layered minerals such as Attaclay ^® (Engelhardt).

Examples of adhesives and adhesives are ethylene oxide or propylene oxide block polymer surfactants and also polyvinyl alcohols, polyvinyl acetates, partially hydrolyzed polyvinyl acetates, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutenes, polystyrenes, polyethyleneamines, polyethylene amides, Polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from the aforementioned polymers.

Suitable antifrost agents are, for example, (C 1 -C 4) -alkanols, such as ethanol, isopropanol, n-butanol, isobutanol, and (C 2 -C 6) -polyols, such as glycerol, ethylene glycol, hexylene glycol and propylene glycol, and mixtures thereof.

These conventional auxiliaries can be added already in the preparation of the compositions according to the invention, or alternatively mixed only during or after dilution with water for the preparation of the ready-to-use composition.

The formulations of the present invention can generally be prepared simply by mixing the ingredients until an apparently homogeneous liquid has formed. The order in which the ingredients are added is usually of lesser importance. For example, the ingredients may be added to a container and the resulting mixture homogenized, for example by stirring, until a homogeneous liquid has formed. However, it is also possible first to dissolve the organic crop protection active ingredients in at least one of the solvents b), c) and / or d), or a mixture of these solvents with at least one of the surfactants e) and the resulting solution with water and the other ingredients to mix, for example, by adding the solution to the water or adding the water to the solution. The temperature during mixing and the other mixing conditions are of secondary importance. Usually, the mixing of the ingredients takes place at temperatures of 10 ⁰ C to 90 ⁰ C, in particular from 10 ° C to 60 ⁰ C. Higher temperatures, for example 35 ° C or 40 ° C or higher, may be useful to the formation of the Speed up formulation. On the other hand, the mixing in de rule also at lower temperatures, for example at 10 ⁰ C to 35 ° C are performed.

Depending on the nature of the crop protection active used, the formulations according to the invention are useful for controlling a large number of pests and can be used both for the treatment of plant crops and of seed but also of inanimate matter and in the household.

By "pests" or "harmful organisms" is meant herein all species of pests that are contaminated with organic crop protection agents, i. Pesticides, especially fungicides and mixtures of fungicides with other pesticides, can be controlled or kept under control. The term pest therefore includes plant-damaging organisms, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants. The term "control" includes both the curative treatment, i. the treatment of infested plants with a formulation according to the invention, as well as the protective treatment, i. the treatment of plants for protection against pest infestation.

The present invention thus also relates to:

Use of pest control formulations described herein, especially plant pests; and

A method for controlling harmful organisms, in particular plant-damaging organisms, comprising contacting the harmful organisms, their habitat, their hosts, such as plants and seeds, and the

Soil, the area and the environment in which they could grow or grow, but also of materials, plants, seeds, soil, surfaces or spaces to be protected from attack or infestation by plant-damaging organisms, with an effective amount of erfindungsge - Maßen formulations.

Another aspect of the invention relates to the use of the formulations described herein for the protection of plants, including seeds, in particular to protect crops from attack by harmful organisms. The present invention thus also relates to the use of the formulations for controlling plant-damaging organisms such as, for example, harmful fungi, insects, arachnids, nematodes and harmful plants. According to a preferred embodiment, the invention relates to the use of the formulations for the protection of seeds from attack by harmful fungi, insects, arachnids and nematodes, in particular against attack by harmful fungi. The formulations according to the invention can be administered undiluted or diluted with water. According to a preferred embodiment, the formulations are used undiluted. In a further preferred embodiment, the formulations are diluted prior to application with up to 50 parts of water, preferably with up to 10 parts of water and in particular with up to 3 parts of water per part of the formulations, all parts being parts by weight.

The dilution is usually accomplished by pouring the formulations of the invention into the water. For rapid mixing of the concentrate with water is usually agitation, such as stirring, used. However, agitation is usually not necessary. Although the temperature for the dilution process is an uncritical factor, dilutions are usually carried out at temperatures in the range of 0 ⁰ C to 50 ⁰ C, especially at 10 ⁰ C to 30 ⁰ C or at ambient temperature.

The water used for dilution is usually tap water. However, the water may already include water-soluble compounds used in crop protection, such as nutrients, fertilizers or pesticides.

The optionally diluted formulations of the invention are used or applied using methods and procedures known to those skilled in the art. In particular, their use for seed treatment may be carried out by conventional techniques of seed treatment, for example by seed dressing, seed coating (seed coating), seed soaking, seed film coating, multilayer Seed multilayer coating, seed encrusting, seed dripping, seed dusting and seed pelleting.

According to a first embodiment of the seed treatment, the seed, i. H. the replicable parts of the plant intended for sowing are treated with a formulation according to the invention or an aqueous dilution thereof. The term seed here includes seeds and propagatable plant parts of all kinds, including seeds, seeds, seed parts, saplings, fruits, tubers, cereal grains, cuttings or the like, in particular grains and seeds.

The treatment of the seed can be carried out, for example, by mixing, spraying or misting the seed with a crop protection formulation according to the invention or a spray mixture obtained therefrom by dilution with water before sowing and before the emergence of the plants. These measures can be used in special devices for the treatment of seeds, for example in seed drills be performed. However, the treatment is also possible in a simple manner by mixing an aqueous formulation according to the invention with the seed in a vessel, for example in a bucket or a tub, and then allowing the seed to dry.

Alternatively, one can treat the seeds during sowing with the crop protection formulation according to the invention.

In a further embodiment of the seed or soil treatment according to the invention, the formulation according to the invention will be given in furrows which already contain the seed. Alternatively, one can also first treat the furrow with the formulation of the invention and then introduce the seed into the furrow.

In a further embodiment of the invention, already grown plants are treated with the formulations, in particular by spraying. For this purpose, the formulations can be administered undiluted or in the form of an aqueous dilution to the plants.

In general, the way in which a formulation according to the invention is used should be determined by the particular use; In any case, the finest possible distribution of the plant protection active ingredients contained in the formulation should be ensured.

The amounts of formulation of the invention used for seed treatment should be selected so that the seed comes into contact with an effective amount of the plant protection active ingredients contained in the formulation. In general, for 100 kg of seed, the amount of a formulation according to the invention should be used which contains 0.1 g to 10 kg, especially 1 g to 5 kg and especially from 1 g to 2.5 kg of the plant active ingredient or a mixture of such active ingredients. For certain crops such as lettuce and onions, the amounts of active ingredient to be used may be larger.

Depending on the nature of the active ingredient used, the formulations according to the invention are suitable for treating the seed of any desired crop, for example corn plants, root plants, oil plants, vegetables, spices, ornamental plants and the like, for example for treating seed of the following plants: durum wheat and other wheat species Oats, rye, barley, maize, including forage maize and sweetcorn, soybeans, brassica, cotton, sunflower, bananas, rice, oilseed rape, beet, sugarbeet, fodder, eggplant, potatoes, grass, grass seed, tomato, leek, pumpkin, Cabbage, salads, peppers, cucumbers, melons, boh peas, garlic, onions, carrots, tobacco, grapes, petunia, geranium, pellargonium, pansy and the like.

The formulations according to the invention are also suitable for the treatment of the seed of useful plants which are resistant to herbicides, fungicides, insecticides or nematicides as a result of methods based on breeding, mutation and / or genetic engineering. For example, it is possible to use formulations for the treatment of seed of transgenic plants which are resistant to herbicides from the group consisting of the sulphonoureas (EP A 0 257 993, US Pat. No. 5,013,659), imidazolinones (cf., for example, US Pat. No. 6,222,100, WO 01 / 82685,

WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) , the glucosinates and related compounds (see, for example, EP-AO 242 236, EP-A-242 246) and the glyphosates and related compounds (cf., for example, WO 92/00377), or for the treatment of seed of plants which are resistant to herbicides selected from the group of the cyclohexadienone / aryloxyphenoxypropionic acid herbicides (US 5,162,602, US 5,290,696, US 5,498,544, US 5,428,001, US 6,069,298, US 6,268,550, US 6,146,867, US 6,222,099, US 6,414,222) or for treating seed of transgenic crops, such as cotton and corn, which have the ability to produce the toxins of Bacillus thuringiensis (Bt toxins), which confer resistance to certain pests (EP A 0 142 924, EP A 0 193 259).

Furthermore, the formulations of the invention can be used to treat the seeds of plants which have altered properties to existing plants and which can be produced, for example, by traditional breeding methods and / or mutations or by recombinant methods. Thus, the production of recombinant variants of crops which have the purpose of modifying the starch of these plants (eg WO 92/11376, WO 92/14827, WO 91/19806) or altering the fatty acid composition of the plants is described several times (WO 91/1997) / 13972).

The seed treated according to the invention is distinguished by advantageous properties compared with conventionally treated seed and is thus likewise the subject of the present application.

The following examples are intended to illustrate the invention.

I. Preparation of formulations (general rule)

The ingredients indicated in Table 1 were used. Table 1: Components a) to f) of the exemplary formulations listed in Table 2.

The solubility of the respective solvent in water at 20 ⁰ C is given in parentheses. Miscible means complete miscibility with water. All solvents of group d) have a solubility in water of less than 0.1 g / l at 20 ⁰ C.

The components a) to f) correspond to the components a) to f) of the formulations according to the invention.

Explanation of trade names:

Edenor ^® Tl 05: Fatty acids mixture with a high oleic acid content (Cognis)

Agnique ^® KE 3658: fatty acid dimethyl amides (Cognis); Agrisol PX401: 2-Phenoxyethanol (Akzo Nobel);

Solvesso ^® 150 ND: depleted predominantly C10 and Cn-alkylbenzenes having a boiling range from 175 to 209 ° C, naphthalene (ExxonMobil Chemical);

Solvesso ^® 200 ND: predominantly C10 and Cu alkylnaphthalenes with boiling range of

235 to 305 ^° C, naphthalene depleted (ExxonMobil Chemical); Lutensol ^® TO5: C13 Oxoalkoholpolyethoxylat with 5 ethylene oxide (EO) units, HLB

Value: 10.5 (BASF);

Lutensol ^® TO7: C13 Oxoalkoholpolyethoxylat with 7 EO units, HLB value: 12.0

(BASF); Lutensol ^® TO15: C13 Oxoalkoholpolyethoxylat with 15 EO units, HLB value: 15.5

(BASF);

Lutensol ^® XP50: 2-Propylheptanolpolyethoxylat with 5 EO Einheinten, HLB value: 1 1, 5

(BASF); Lutensol ^® XP140: 2-Propylheptanolpolyethoxylat with 14 EO-Einheinten, HLB value:

16.0 (BASF);

Soprophor ^® S 25: Tristyrylphenolpolyethoxylat with 25 EO units, HLB value: 14.5

(Rhodia);

S-MAZ ^® 20: sorbitan monofatty acid esters (mainly monododecanoate), HLB value: 8.0 (BASF);

T-MAZ ^® 20: polyethoxylated sorbitan monolaurate with about 20 EO units), HLB value: 16.7 (BASF);

Pluronic PE 6400: propylene oxide / ethylene oxide block polymer with about 40% EO content

(BASF); Lutensit® ^® A-BO: sodium ^ -Sulphonyl-dioctyl succinate (BASF);

Soprophor DSS ^® 15: ethoxylated Distyrylphenolsulphat with 15 EO units (Rhodia);

Soprophor ^® 4D 384: ethoxylated Tristyrylphenolammoniumsulfat with 16 EO units

(Rhodia).

Rhodiasolv ^® DIB: Mixture of diisobutyl glutarate, succinate and adipate (Rhodia). Table 2 lists formulations 1 to 23 according to the invention. Table 2 also shows the components and their amounts which were used to prepare the respective formulations. The preparation was carried out as described below, with all steps being carried out at room temperature (RT):

One or more components of component A were placed in a container and after addition of three or more components B, C and D was stirred until A was completely dissolved as possible. Subsequently, two or more components E and F were added with gentle stirring and stirring was continued until a very homogeneous solution was present. Thereafter, with stirring, the distilled water was added and stirred until a clear formulation was obtained.

II. Stability tests of the formulations according to the invention

The prepared formulations were allowed to stand overnight at RT and then visually inspected for their appearance. A homogeneous and clear liquid indicated a stable microemulsion, while a hazy or milky appearance would have indicated a significantly increased droplet size and possibly the conversion of the microemulsion into a common emulsion. The formulations were then each stored for 3 days at -10 ⁰ C and 54 ° C and then, as described above, checked by eye. From a clear, homogeneous appearance, it could be seen again whether the microemulsions are stable under these conditions. Streaking was interpreted as an indication that continued storage of the formulation under the given conditions could possibly lead to phase separation. The freezing of a formulation indicates a relatively high freezing point, which could be lowered, for example, by adding an antifreeze.

The results are summarized in Table 2.

Table 2: Preparation and Stability of the formulations

Table 2 (continued)

Table 2: Continuation

^* Acid Red 18

^** methylisothiazolinone / benzoisothiazolinone mixture: Acetide ^® MBS, Thor GmbH, Speyer

III. Studies of pickled seeds

The following formulations were used for comparative experiments: Formulation V3: Abavit UF (BASF); this is a conventional formulation for seed treatment, mainly the active ingredients carboxin and prochloraz and the organic solvent includes N-methylpryrrolidone. V3 was used undiluted below.

Formulation V4: Kinto Duo (BASF); this is a conventional aqueous suspension for seed treatment containing prochloraz and triticonazole. The formulations of Examples 24, 25 and 26 and the commercial formulation V4 were subsequently diluted with one part of water to a part of the formulation.

A) Seed dressing (general regulation)

Pickling was carried out with the formulations prepared according to the above instructions as pickling broths. A pickling device from SATEC was used, in which the seed is mixed according to the rotor-stator principle and the pickling broth is sprayed by means of a centrifuge plate. The speed of the rotor was set to 200 rpm, and the manometer of the compressed air connection adjusted the air flow of the device to 960 l / h. The batches used were the formulations prepared in accordance with the above instructions. The metering of a pickling broth in the desired amount was carried out with a peristaltic pump, the hose end being fixed just above the centrifuge plate. The application rates for the commercial pickling formulation V3 and the example formulations 19, 21 and 23 were in each case 2 ml / kg. Of the commercial mordant formulation V4 diluted with water in the ratio 1: 1 v / v and of the formulations diluted with water in the ratio 1: 1 v / v of Examples 24, 25 and 26, 4 ml / kg were used in each case. If necessary, the seed to be picked has been cleaned and conditioned in a climate cabinet for 24 hours at 20 ^° C. and 50% relative humidity in order to create more reproducible conditions. After filling with 2 kg of the seed, the spinning plate was switched on and the pickling started by switching on the pump. After 30 seconds, the dressing was stopped by draining the seeds.

B) Study of flowability

The time required for the pickled seed to drain from a jarred funnel was stopped and served as a measure of fluidity. For this purpose, the entire amount of seed (2 kg) was added to the funnel immediately after pickling, the outlet of which had a diameter of 2.8 cm and was vibrated with an amplitude of 1.5 mm. Using this method, wheat seeds treated with the formulations of Examples 19, 21, 23, 24, 25 and 26, respectively, were compared to seeds treated with the commercial mordant formulations V3 and V4. In all cases, seed was used according to the above procedure.

The results for the flow behavior thus obtained are summarized in Table 5. Table 5: Comparison of the flow behavior of pickled wheat seeds.

C) investigation of dust evolution

The investigations were carried out in the same pickling device one day after the pickling described above. Stained seed was stored in the meantime in a climatic cabinet for 24 hours at 20 ⁰ C and 50% humidity. The speed of the rotor and the air flow of the device were set as described above and the device was run for 10 minutes for conditioning. By means of a suction filter, a previously balanced filter (Fisherbrand glass fiber filter 38 mm, Product No. FB59403) was placed in the lid of the pickling device. A vacuum pump sucked in part of the compressed air passed through the device, including any dust that may have formed. Then, with the pump and rotor running, the device was charged with 1 kg of seed and the pump stopped after 30 seconds. The filter was weighed to determine the dust residue in grams per 100 kilograms of seed.

Using this method, wheat kernels pickled with the formulations of Examples 19, 21, 23, 24, 25 and 26, respectively, were compared with those treated with the commercial pickles V3 and V6. The results for the dust development thus obtained are summarized in Table 6.

Table 6: Comparison of the dust development of pickled wheat seeds.

Claims

claims:

1. A liquid aqueous crop protection formulation comprising: a) at least one organic crop protection active ingredient with a water solubility of less than 5 g / l at 20 ⁰ C; b) at least one organic solvent having a water solubility of more than 100 g / l at 20 ⁰ C; c) at least one organic solvent having a water solubility of 2 to 100 g / l at 20 ° C; d) at least one organic solvent having a water solubility of less than 2 g / l at 20 ⁰ C; e) at least one nonionic surfactant; f) at least one anionic surfactant; and g) water.

2. Phytosanitary formulation according to claim 1, wherein the at least one solvent b) is selected from hydroxylated (C ₄ -Cs) - alkanecarboxylic acid esters, aliphatic (C ₂ -C 8) -di- and triols, (Cs-Cs) - Alkancarbonsäurealkoxyalkylestern, dimethyl sulfoxide, tetrahydrofurfuryl alcohol , (C ₃ -C ₄ ) -alkylene carbonates, N, N'-dimethyl- (C ₃ -C ₄ ) -alkyleneureas, (C ₃ -C ₅ ) -

Lactones, N-methyl (C ₃ -C 5) lactams and tri (C ₁ -C ₃ ) alkyl phosphates.

The crop protection formulation of claim 2, wherein the at least one solvent comprises b) dimethyl sulfoxide.

The crop protection formulation of claim 3, wherein the at least one solvent b) comprises at least one second solvent other than dimethyl sulfoxide b).

5. Phytosanitary formulation according to one of the preceding claims, wherein the at least one solvent c) is selected from (C5-C9) -alkanecarboxylic acid alkyl esters, (C9-C12) -alkanecarboxylic acid alkyl esters, (Cs-C ^ dialkyldicarboxylic acid esters, (Cs-C ^ Ketones, (C5-C9) -arylalkyl alcohols, (C5-C9) -aryloxyalkyl alcohols, (C5-C9) -cycloalkyl alcohols, (C5-Cg) -alkanediolalkanoates,

(C5-C9) alkanetriolalkanoates and

6. Phytosanitary formulation according to one of the preceding claims, wherein the at least one solvent d) is selected from aliphatic, aromatic and cycloaliphatic hydrocarbons having boiling points of 100 to 310 ⁰ C, (C ₈ -C ₂ ⁰ ) -alkylphenols, (C ₈ -C ₂ ⁰ ) -alkanols, (C 10 -C 20) -alkanecarboxylic acid alkyl esters, (C 9 -C 20) -hydroxyalkanecarboxylic acid alkyl esters , (C 12 -C 28) -cycloalkanecarboxylic acid alkyl esters, (C 12 -C 28) -cycloalkanedicarboxylic acid dialkyl esters,

(Cio-Ci5) -Dialkyldicarbonsäureestern, (C25-C35) -Alkantriolalkanoaten, N- (C6-Ci8) alkyl (C3-C5) -lactams, (C8-C26) fatty acids, their dialkylamides and their alkyl esters.

7. Plant protection formulation according to one of the preceding claims, wherein the at least one nonionic surfactant e) is selected from monofatty acid esters of polyhydroxylated compounds and compounds which have at least one oligo- (C 2 -C 4) -alkylene ether group.

8. Phytosanitary formulation according to claim 7, wherein the at least one nonionic surfactant e) is selected from sorbitan monofatty acid esters, homo- or co-oligomers of (C 2 -C 4) -alkylene oxides, oligo- (C 2 -C 4) -alkylene oxide (C 8 -C 22) -alkyl ethers, Oligo- (C 2 -C 4) -alkylene oxide (C 1 -C 16) -alkylbenzene ethers, oligo- (C 2 -C 4) -alkylene oxide mono-, -di- or -tristyrylphenyl ethers and oligo- (C 2 -C 4) -alkylene oxide mono- or -distyryl- phenyl ether-formaldehyde condensates.

A crop protection formulation according to any one of the preceding claims, wherein component e) comprises at least two nonionic surfactants having different HLB values.

The crop protection formulation of claim 9, wherein component e) comprises at least one nonionic surfactant having an HLB value of at most 13 and at least one nonionic surfactant having an HLB value above 13.

A crop protection formulation according to claim 10, wherein the nonionic surfactant having an HLB value of at most 13 is selected from oligo- (C ₂ -C ₄ ) alkylene (C ₈ -C ₂ 2) alkyl ethers.

12. Plant protection formulation according to claim 10 or 11, wherein the nonionic surfactant having an HLB value of more than 13 is selected from propylene oxide-ethylene oxide block co-oligomers, oligo- (C2-C3) -alkylene oxide (C8-C22 ) - alkyl ethers, oligo- (C2-C3) alkylene oxide mono-, di- and tristyrylphenyl ethers.

13. Plant protection formulation according to one of the preceding claims, comprising: a) from 0.1 to 40 wt .-% of at least one organic crop protection agent having a water solubility of less than 5 g / l at 20 ⁰ C; b) from 10 to 40 wt .-% of at least one solvent having a water solubility of about 100 g / l at 20 ⁰ C; c) from 10 to 40% by weight of at least one solvent having a water solubility of from 2 to 100 g / l at 20 ° C; d) from 5 to 45 wt .-% of at least one solvent having a water solubility of less than 2 g / l at 20 ⁰ C; e) from 2 to 25% by weight of at least one nonionic surfactant; f) from 1 to 25% by weight of at least one anionic surfactant; and g) water ad 100% by weight.

14. A crop protection formulation according to any preceding claim, wherein the at least one crop protection agent a) has a melting point of at most 120 ° C.

A crop protection formulation according to any one of the preceding claims, wherein the at least one crop protection agent a) is a fungicide.

16. Plant protection formulation according to claim 15, wherein the fungicide is selected from the groups of the azoles, strobilurins and N-biphenylamides of heteroaromatic carboxylic acids.

17. Phytosanitary formulation according to claim 16, wherein the fungicide is selected from prochloraz, boscalid, pyraclostrobin, triticonazole, pyrimethanil, fluquinconazole, 4-difluoromethyl-2-methylthiazole-5-carboxylic acid (4'-bromobiphenyl-2-yl) amide, 4-difluoromethyl-2-methylthiazole-5-carboxylic acid (4'-trifluoromethylbiphenyl-2-yl) -amide, 4-difluoromethyl-2-methylthiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl) 2-yl) amide, 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluorobiphenyl-2-yl) -amide and 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid - (3 ', 4', 5'-trifluorobiphenyl-2-yl) -amide.

18. Plant protection formulation according to one of the preceding claims, additionally containing at least one organic colorant.

19. Use of an aqueous crop protection formulation according to one of the preceding claims for the treatment of plants or seeds.

A method of treating seed, comprising contacting seed with an effective amount of an aqueous crop protection formulation according to any one of claims 1 to 18.

21. A method according to claim 20, wherein the contacting is by means of spraying.

22. Seed obtainable by a method according to any one of claims 20 or 21.

23. A method for controlling plant-damaging organisms, comprising contacting the plant-damaging organisms, the plants, the soil or the environment in which the plants grow, with an effective amount of the formulations according to any one of claims 1 to 18.