EP2348833A2 - Formulations phytoprotectrices aqueuses liquides - Google Patents

Formulations phytoprotectrices aqueuses liquides

Info

Publication number
EP2348833A2
EP2348833A2 EP09783906A EP09783906A EP2348833A2 EP 2348833 A2 EP2348833 A2 EP 2348833A2 EP 09783906 A EP09783906 A EP 09783906A EP 09783906 A EP09783906 A EP 09783906A EP 2348833 A2 EP2348833 A2 EP 2348833A2
Authority
EP
European Patent Office
Prior art keywords
crop protection
acid
solvent
formulation according
formulations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09783906A
Other languages
German (de)
English (en)
Inventor
Ulf Schlotterbeck
Claude Taranta
Ralf Lurtz
Jurith Montag
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09783906A priority Critical patent/EP2348833A2/fr
Publication of EP2348833A2 publication Critical patent/EP2348833A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • 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.
  • seed is treated prior to seeding with seed stains containing plant protection agents, usually fungicides and often other pesticides, in particular insecticides.
  • 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.
  • 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.
  • 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.
  • a low abrasion of the stain is advantageous because the concomitant reduced dust during pickling or seeding leads to improved Arbreitsterrorism 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.
  • 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.
  • an organic, water-immiscible solvent typically a hydrocarbon mixture and / or a fatty acid methyl ester.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • they should be distinguished by high stability and a homogeneous distribution of active ingredients.
  • Seeds treated with these formulations should have good flowability and low abrasion of the stain.
  • 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 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 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 at least one nonionic surfactant
  • f at least one anionic surfactant
  • g) contains water.
  • 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 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.
  • 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.
  • 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 can also be present as bicontinuous phases, ie the aqueous phase and the oil phase form mutually penetrating phases.
  • alkyl alkenyl
  • alkylene alkylene
  • aryl aryl
  • 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.
  • 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-d
  • 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.
  • 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.
  • DMSO dimethyl sulfoxide
  • 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.
  • hydroxylated alkanols examples include 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.
  • 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
  • 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-cycloheptaned
  • (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
  • (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.
  • N, N'-dimethyl- (C3-C4) -alkyleneurea 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 ⁇ -butyrolactone.
  • N-methyl- (C3-C5) -lactam an N-methylated derivative of a lactam having 3, 4 or 5 carbon atoms in the ring.
  • N-methyl- (C3-C5) -lactams are N-methylpyrrolidone and N-methylpiperidone.
  • 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 ⁇ -butyrolactone, dimethylsulfoxide, methoxypropyl acetate, 2-methyl-2,4-pentanediol, hexylene glycol (1 , 6-hexanediol), tetrahydrofurfuryl alcohol and n-propyl lactate.
  • solvent b) which is selected from dimethylsulfoxide, hydroxylated (C 4 -C 8) -alkane
  • the formulations according to the invention comprise as at least one solvent b) dimethyl sulfoxide.
  • 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, ⁇ -butyrolactone, N-methyl- (C3-C5) -lactams and Tn- (CrCs) -alkylphosphates, especially under ⁇ -butyrolactone, Methoxypropyl acetate, 2-methyl-2,4-pentanediol, hexylene glycol (1,6-hexanediol), tetrahydrofurfuryl alcohol and n-propyl lac
  • the formulation contains no or less than 0.1% by weight of DMSO, based on the total weight of the formulation.
  • 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 ⁇ -butyrolactone, dimethyl sulfoxide, methoxypropyl acetate, 2-methyl-2,4-pentanediol, hexylene glycol (1,6-hexanediol), tetrahydrofurfuryl alcohol and
  • 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 .-%.
  • 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.
  • 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.
  • 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.
  • (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
  • -Alkancarbonklarealkoxyalkylester 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, ethoxybut
  • (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, eth
  • (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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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) -Alkancarbonklarealkylestern, ( 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
  • 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 ,
  • 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.
  • 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.
  • Solvesso ® especially Solvesso ® 100, Solvesso ® 150, Solvesso 200, Solvesso ® 150 ND, Solves
  • Solvesso ® 150 and Solvesso ® 200 ND ND (Exxon Mobil Chemical) in which the potential carcinogen naphthalene was depleted are.
  • 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
  • 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.
  • An example of this is limonene.
  • (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.
  • alkanols esterified (Ci-C9) alkanecarboxylic acids wherein the total number of carbon atoms is 10 to 20.
  • alkanols esterified (Ci-C9) alkanecarboxylic acids wherein the total number of carbon atoms is 10 to 20.
  • alkanols esterified (Ci-C9) alkanecarboxylic acids wherein the total number of carbon atoms is 10 to 20.
  • alkanols esterified (Ci-C9) alkanecarboxylic acids wherein the total number of carbon atoms is 10 to 20.
  • alkanols esterified (Ci-C9) alkanecarboxylic acids wherein the total number of carbon atoms is 10 to 20.
  • alkanols esterified (Ci-C9) alkanecarboxylic acids wherein the total number of carbon atoms is 10 to 20.
  • (C9-C20) -Hydroxyalkancarbonklarealkylestern 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.
  • (Ci2-C28) -Cycloalkancarbonklarealkylestern or (Ci2-C28) -Cycloalkan dicarbonkladialkylestern 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,
  • 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.
  • (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.
  • (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, ⁇ -linolenic acid, ⁇ -linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid.
  • 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.
  • 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-
  • 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) -Hydroxyalkancarbonklarealkylestern, 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.
  • 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 ⁇ l Listerean- 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 Fettklaredimethy-, (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, C ⁇ -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.
  • 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.
  • 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).
  • 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.
  • 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:
  • 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,
  • 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 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.
  • 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.
  • ethoxylate refers to Oligoetherreste derived from ethylene oxide.
  • 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.
  • 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.
  • 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
  • component e) of the formulations comprises at least two nonionic surfactants having different HLB values.
  • 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
  • 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:
  • 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
  • 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.
  • 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.
  • 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.
  • Surfactants e.2) which are selected from propylene oxide-ethylene oxide block co-oligomers and oligoethylene oxide tristyrylphenyl ethers.
  • 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;
  • 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).
  • anionic surfactants the sodium, potassium,
  • 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,
  • 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 ,
  • 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.
  • 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. %.
  • 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.
  • 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 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.
  • 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.
  • the active ingredient compositions comprise at least one organic crop protection active ingredient.
  • 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;
  • 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.
  • 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.
  • 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;
  • 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: dim
  • Benzoic acid amides flumetover, fluopicolide (picobenzamide), zoxamide;
  • 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;
  • 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;
  • 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;
  • Pyrroles fludioxonil, fenpiclonil; • morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph;
  • Dicarboximides iprodione, procymidone, vinclozolin;
  • A.5. Carbamates and dithiocarbamates such as, for example, dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb,
  • 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.
  • 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;
  • Chloride channel activators abamectin, emamectin benzoate, milbemectin, lepimetin;
  • METI I compounds Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad, Flufenerim, Rotenone;
  • Anti-skinning compounds cyromazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide;
  • 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;
  • 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.
  • 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.
  • herbicidal active ingredients are mentioned in groups C.1 to C.15:
  • 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,
  • 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,
  • 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,
  • 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 -Alsu If onyl;
  • R 9 is a heterocyclic radical selected from the group of thiazol-2-yl, thiazole
  • R 11 is hydrogen, halogen or C 1 -C 6 -alkyl
  • R 12 is C 1 -C 6 -alkyl
  • R 13 is hydrogen or CrC ⁇ -alkyl.
  • C.6 EPSP synthase inhibitors such as glyphosate
  • C.7 glutamine synthase inhibitors such as glufosinate and bilanaphos
  • 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;
  • mitosis inhibitors such as, for example, benfluralin, butraline, dinitramine, ethalfluran-Nn, fluchloralin, isopropalin, methalpropaline, nitralin, oryzalin, pendimethalin, propiamine, profluralin, trifluralin, amiprofosmethyl, butamifos, dithi
  • 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,
  • 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;
  • auxin transport inhibitors such as naptalam and diflufenzopyr
  • 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.
  • growth regulators are 1-naphthylacetamide, 1-naphthylacetic acid, 2-Naphthyloxyessisgklare, 3-CPA, 4-CPA, Ancymidol, anthraquinone, BAP, Butifos; Tribufos, butralin, chlorofluorol, chlormequat, clofencet, cyclanilides, daminozides, dicamba, dikegulac sodium, dimethipine, chlorfenethol, et reviewingl, 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
  • the crop protection active ingredients are preferably selected from organic active substances which have a fungicidal, insecticidal, acaricidal and / or nematicidal action.
  • organic active substances which have a fungicidal, insecticidal, acaricidal and / or nematicidal action.
  • 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, metcon
  • 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, ze
  • crop protection active ingredients can be used alone or in combination with one another.
  • 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.
  • 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.
  • a 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.
  • 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.
  • azoxystrobin dimoxystrobin
  • enestroburin fluoxastro
  • 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 triflumizo
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the data in% by weight relate in each case to the total weight of the formulation according to the invention.
  • 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.
  • 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.
  • Suitable commercially available bactericidal products are Proxel ® (ICI), Acetide ® RS (Thor Chemie), Kathon ® (Rohm & Haas) and Acetide MBS (Thor Chemie).
  • the level of preservative will be from 0.1 to 10 grams per liter of the formulations.
  • 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,
  • 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,
  • 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.
  • the stabilizer is citric acid or ascorbic.
  • the amount of stabilizer will be in the range of 0.01 to 10 grams per liter of formulation.
  • thickeners ie compounds which impart to the formulation modified flow properties, ie, high viscosity at rest and low viscosity in motion
  • 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).
  • 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.
  • 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.
  • 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.
  • the ingredients may be added to a container and the resulting mixture homogenized, for example by stirring, until a homogeneous liquid has formed.
  • the temperature during mixing and the other mixing conditions are of secondary importance.
  • 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.
  • 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.
  • 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.
  • pest therefore includes plant-damaging organisms, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants.
  • 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:
  • a method for controlling harmful 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 - stricten 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.
  • 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.
  • the formulations are used undiluted.
  • 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.
  • agitation such as stirring, used.
  • agitation is usually not necessary.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the formulation according to the invention will be given in furrows which already contain the seed.
  • the formulations are treated with the formulations, in particular by spraying.
  • the formulations can be administered undiluted or in the form of an aqueous dilution to the plants.
  • a formulation according to the invention 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.
  • 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.
  • the amounts of active ingredient to be used may be larger.
  • 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.
  • 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
  • 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.
  • 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
  • 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.
  • 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.
  • Table 1 Components a) to f) of the exemplary formulations listed in Table 2.
  • the components a) to f) correspond to the components a) to f) of the formulations according to the invention.
  • 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
  • Lutensol ® TO5 C13 Oxoalkoholpolyethoxylat with 5 ethylene oxide (EO) units, HLB
  • Lutensol ® TO7 C13 Oxoalkoholpolyethoxylat with 7 EO units, HLB value: 12.0
  • Lutensol ® TO15 C13 Oxoalkoholpolyethoxylat with 15 EO units, HLB value: 15.5
  • Lutensol ® XP50 2-Propylheptanolpolyethoxylat with 5 EO Einheinten, HLB value: 1 1, 5
  • Lutensol ® XP140 2-Propylheptanolpolyethoxylat with 14 EO-Einheinten, HLB value:
  • Soprophor ® S 25 Tristyrylphenolpolyethoxylat with 25 EO units, HLB value: 14.5
  • 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
  • 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):
  • component A 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.
  • 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.
  • 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.
  • BASF Kinto Duo
  • 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.
  • 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.
  • 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.
  • 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.
  • Table 5 Comparison of the flow behavior of pickled wheat seeds.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pretreatment Of Seeds And Plants (AREA)

Abstract

L'invention concerne une nouvelle formulation phytoprotectrice aqueuse liquide contenant a) au moins un agent phytoprotecteur organique ayant une hydrosolubilité inférieure à 5 g/l à 20 °C; b) au moins un solvant organique ayant une hydrosolubilité supérieure à 100 g/l à 20 °C; c) au moins un solvant organique ayant une hydrosolubilité de 2 à 100 g/l à 20 °C; d) au moins un solvant organique ayant une hydrosolubilité inférieure à 2 g/l à 20 °C; e) au moins un tensioactif non-ionique; f) au moins un tensioactif anionique; et g) de l'eau. L'invention concerne également l'utilisation de la formulation phytoprotectrice pour le traitement de plantes et de semences, des procédés correspondants et des semences traitées.
EP09783906A 2008-10-10 2009-10-09 Formulations phytoprotectrices aqueuses liquides Withdrawn EP2348833A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09783906A EP2348833A2 (fr) 2008-10-10 2009-10-09 Formulations phytoprotectrices aqueuses liquides

Applications Claiming Priority (3)

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EP08166374 2008-10-10
PCT/EP2009/063196 WO2010040834A2 (fr) 2008-10-10 2009-10-09 Formulations phytoprotectrices aqueuses liquides
EP09783906A EP2348833A2 (fr) 2008-10-10 2009-10-09 Formulations phytoprotectrices aqueuses liquides

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EP (1) EP2348833A2 (fr)
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AR (1) AR075284A1 (fr)
AU (1) AU2009301114B2 (fr)
BR (1) BRPI0919701A2 (fr)
EA (1) EA021204B1 (fr)
TW (1) TW201018400A (fr)
UA (1) UA106732C2 (fr)
UY (1) UY32169A (fr)
WO (1) WO2010040834A2 (fr)

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AR075284A1 (es) 2011-03-23
BRPI0919701A2 (pt) 2015-08-18
AU2009301114B2 (en) 2015-03-19
UA106732C2 (uk) 2014-10-10
WO2010040834A3 (fr) 2010-12-09
CN102176821A (zh) 2011-09-07
WO2010040834A2 (fr) 2010-04-15
EA201100596A1 (ru) 2011-12-30
US20110195839A1 (en) 2011-08-11
TW201018400A (en) 2010-05-16
EA021204B1 (ru) 2015-04-30
US8716182B2 (en) 2014-05-06
AU2009301114A1 (en) 2010-04-15
UY32169A (es) 2010-04-30

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