WO2022058522A1 - Stabilization of thioketones on surfaces - Google Patents
Stabilization of thioketones on surfaces Download PDFInfo
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- WO2022058522A1 WO2022058522A1 PCT/EP2021/075651 EP2021075651W WO2022058522A1 WO 2022058522 A1 WO2022058522 A1 WO 2022058522A1 EP 2021075651 W EP2021075651 W EP 2021075651W WO 2022058522 A1 WO2022058522 A1 WO 2022058522A1
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- 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
Definitions
- the present invention relates to a method for stabilizing thioketones (thiones) on surfaces, in particular active substances which contain thione building blocks, in particular triazolinthiones, as functional groups, and the use of decenamide and tocopherols (vitamin E) for stabilizing thione compounds .
- thioketones thiones
- active substances which contain thione building blocks, in particular triazolinthiones, as functional groups
- vitamin E decenamide and tocopherols
- the present invention is aimed at stabilizing thiones on surfaces, in particular cotton or also leaf surfaces.
- the present invention is directed to a method for stabilizing thiones on surfaces, in particular leaf surfaces or cotton fabrics, using decenamide and/or tocopherols (vitamin E).
- the present invention is directed to a method for stabilizing thiones on surfaces, in particular cotton or else leaf surfaces, by applying a formulation containing decenamide and/or tocopherols (vitamin E).
- prothioconazole can be used in customary formulations for controlling fungi (WO-A 96/16 048).
- This active ingredient is 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-3H-l,2, 4-triazole-3-thione.
- Prothioconazole-containing formulations are generally liquid formulations and are available on the market, for example, as emulsion concentrates.
- formulations containing prothioconazole can contain a certain amount of 2-(l-chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4-triazole-l - yl)propan-2-ol included.
- PTZ prothioconazole
- the maximum permissible amount of Desthio in PTZ formulations depends on the amount of PTZ in the formulation in g/L.
- the maximum allowable amount of desthio is given in ppm, where the allowable amount of desthio in ppm is given as half the value of the PTZ loading in g/L.
- WO-A 2012/033590 discloses aqueous dispersions of prothioconazole which contain a sulfur-containing compound, such as L-cysteine, for stabilization.
- Stabilized PTZ-containing formulations are described in WO 2017/097882 and WO2018/228885, which can be regarded as the closest prior art. These describe emulsion concentrates and suspension concentrates with PTZ dissolved in a solvent. The formulation could be improved by adding compounds of formula (I) in which n is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15 or 18 and a reduction in the desthio content can be achieved.
- a disadvantage of these compounds is that very large amounts of up to 30% of the stabilizer are necessary to achieve a desired effect and thus represent a major intervention in the formulation.
- These are also novel additives, which in some cases first have to be approved for crop protection formulations. While the prior art describes the stabilization of thiones in spray liquors and concentrated storable formulations, the prior art gives no indication of how thiones can also be stabilized after they have been applied to surfaces, since the degradation products are also undesirable here.
- the object of the present invention was therefore to provide a method for stabilizing thiones on surfaces after they have been applied, in particular for stabilizing prothioconazole, in order to prevent degradation to 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-( to counteract lH-l,2,4-triazol-l-yl)propan-2-ol.
- antioxidants and free-radical scavengers such as decenamide and tocopherols (vitamin E), even in very small amounts, are extremely effective in preventing the degradation of thiones to desthio products on surfaces, especially prothioconazole, especially at high concentrations of active ingredient.
- the subject matter of the present invention is therefore the use of decenamide and tocopherols for stabilizing thiones on surfaces, in particular after these thiones have been applied as a fungicidal spray.
- the tocopherols are preferably selected from the group consisting of tocotrienols, tocopherols (e.g. (+)-delta-tocopherol, (+/-)-alpha-tocopherol), and mixtures of these compounds.
- a further object of the present invention is therefore the use of tocopherol- or decenamide-containing formulations for stabilizing the thiones on surfaces after application and drying.
- the formulations to be stabilized after application are agrochemical formulations.
- the active ingredient a) with a thione group is selected from the group consisting of prothioconazole and 4-((6-(2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3- (5-mercapio-IH,2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitrile, particularly preferably only prothioconazole.
- the active ingredient is preferably present in an amount of from 1% to 50% by weight, more preferably from 4% to 30% by weight, and particularly preferably from 5% to 28% by weight to the total weight of the formulation.
- the antioxidant b) is more preferably from the group that includes decenamide, unless otherwise specified for the purposes of the present invention, N,N-dimethyl-9-decenamide, and tocopherols and tocotrienols (preferably (+)-delta-tocopherol, (+/ -)-alpha-tocopherol, (+)-alpha-tocopherol as well as vitamin E and mixtures of tocopherols).
- Vitamin E is a collective term for fat-soluble substances with antioxidant effects, the most common forms being tocopherols and tocotrienols.
- the term vitamin E should include alpha-tocopherol (RRR-a-tocopherol or Da-T0), beta-tocopherol, gamma-tocopherol, delta-tocopherol, alpha-tocotrienol, beta-tocotrienol, gamma-tocotrienol, delta-tocotrienol, and derivatives thereof such as acetates.
- the antioxidants are preferably present in an amount of from 0.01% to 15.00% by weight, more preferably from 0.03% to 5.00% by weight, and most preferably 0 .2% by weight to 4% by weight based on the total weight of the formulation.
- water- or oil-based, water- or oil-soluble antioxidants are preferably used in the following amounts:
- the antioxidants are preferably at a level of from 0.01% to 10.00% by weight, more preferably from 0.03% to 5% by weight, even more preferably from 0.03% % by weight to 1.00% by weight, and more preferably 0.05% by weight to 0.5% by weight, based on the total weight of the formulation.
- the antioxidants are preferably in an amount of from 0.10% to 5.00% by weight, more preferably from 0.2% to 4.00% by weight, and particularly preferably 0. 2% by weight to 3% by weight based on the total weight of the formulation.
- the antioxidants are preferably at a level of from 0.50% to 15.00% by weight, more preferably from 1% to 10.00% by weight, and most preferably 3% by weight. % to 10% by weight based on the total weight of the formulation.
- Prothioconazole (with the chemical name 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-l,2-dihydro-3H-l,2,4-triazole-3-thione) (CAS number 178928-70-6) exists as a racemate. Suitable processes for its production are described in DE-A 195280. Prothioconazole can be in the thiono form of general formula (II) or in the tautomeric mercapto form of general formula (Ila) present. When the term prothioconazole is used below, the isomers shown here and other possible tautomers are always covered.
- the formulations according to the present invention can each contain further ingredients, such as: a) cl: nonionic dispersant/emulsifier, c2: ionic dispersant/emulsifier b) other agrochemical active ingredients different from a). c) solvents including OD carriers d) carriers (WGs, as well as aerosils for SC/TKWG) e) gl: organic thickener g2: inorganic thickener f) other additives and auxiliaries
- Formulation types are defined by the FAO and can be found at www.fao.org/ag/agp/agDD/pesticid. In the March 2016 issue, the usual formulation types are described on pages 66-231.
- the formulation according to the invention is one of the usual types of formulation described by the FAO. Examples include suspension concentrates (SC) and concentrates containing dye for seed treatment (FS), emulsion concentrates (EC), water-dispersible concentrates (WG), oil dispersions (OD), suspoemulsions (SE), aqueous emulsions (EW), microemulsions (ME) and liquid formulations (SL) mentioned here.
- SC suspension concentrates
- FS emulsion concentrates
- WG water-dispersible concentrates
- OD oil dispersions
- SE suspoemulsions
- EW aqueous emulsions
- ME microemulsions
- SL liquid formulations mentioned here.
- EC, SC, FS, SE, OD and WG formulation types are preferably EC, SC, FS, SE, OD and WG formulation types, very particularly preferably formulations in which at least one active ingredient is not present in dissolved form.
- these are FS, SC, SE, OD and WG formulations, very particularly preferably SC, FS and WG formulations.
- Suitable nonionic emulsifying and dispersing agents cl are customary surface-active substances present in formulations of agrochemically active compounds. Examples include ethoxylated nonylphenols, reaction products of linear or branched alcohols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, end-capped and uncapped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g.
- butoxypolyethylene-propylene glycols reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, furthermore fatty acid esters, fatty acid polyglycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyryl-phenol ethoxylate with an average of 16 ethylene oxide units per molecule, also ethoxylated and propoxylated Arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxylates and propoxylates.
- Tristryl-phenol alkoxylates and fatty acid polyglycol ether esters are particularly preferred. Tristyryl phenol ethoxylates, tristyryl phenol ethoxy propoxylates and castor oil polyglycol ether esters, each individually or in mixtures, are very particularly preferred. There may also be additives, such as surfactants or esters of fatty acids, which contribute to improving the biological effectiveness. Examples of suitable nonionic emulsifiers and dispersants cl) are Soprophor® 796/P, Targetamul® CO30, Targetamul® HOT, Targetamul® PSI 100 or Synperonic® T304.
- Suitable nonionic dispersants cl) can also be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymer of vinyl chloride and vinyl acetate, and partially hydrolyzed vinyl acetate, phenolic resins, modified cellulose Types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol) or modified cellulose. Polyvinylpyrrolidone grades are preferred, and low molecular weight grades such as Luviskol® K30 or Sokalan® K30 are particularly preferred.
- Suitable nonionic emulsifiers and dispersants cl) from the group of di- and tri-block copolymers of alkylene oxides are, for example, compounds which are based on ethylene and propylene oxide and have average molecular weights of between 200 and 10,000, preferably 1000 to 4000 g/mol, the mass fraction of the polyethoxylated block varying between 10 and 80%, such as Synperonic® PE series (Uniqema), Pluronic® PE series (BASF), VOP® 32 or Genapol® PF series (Clariant).
- the proportion of the nonionic emulsifiers and dispersants c1) in the suspension concentrates according to the invention is preferably 1 to 15% by weight, more preferably 2 to 10% by weight and particularly preferably 2.5 to 8% by weight.
- Suitable anionic emulsifiers and dispersants bl) such as emulsifiers, surfactants, wetting agents and dispersants are, for example, alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof such as the salts of alkyl sulfonic acids or alkyl phosphoric acids and alkylaryl sulfonic or alkylaryl phosphoric acids, Diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkyl phenols, sulfonates of alkoxylated aryl phenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecyl
- Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkyl phenols, of alcohols, of ethoxylated alcohols or of fatty acid esters.
- Examples of phosphates are phosphate esters.
- Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkyl phenol ethoxylates.
- Examples are calcium dodecyl benzene sulfonate such as Rhodocal® 70/B (Solvay), phenyl sulfonate CAI 00 (Clariant) or isopropylammonium dodecyl benzene sulfonate such as Atlox® 3300B (Croda).
- Rhodocal® 70/B Solvay
- phenyl sulfonate CAI 00 Clariant
- isopropylammonium dodecyl benzene sulfonate such as Atlox® 3300B (Croda).
- Typical representatives include phenylsulfonate CA (Ca-dodecylbenzenesulfonate), Soprophor® types (optionally esterified derivatives of tristyrylphenoi ethoxylates), Emmulsogen® 3510 (alkylated EO/PO copolymer), Emulsogen® EL 400 (ethoxylated castor oil), Tween® types (fatty-acylated sorbitan ethoxylates), Calsogen® AR 100 (Ca-dodecylbenzenesulfonate).
- CA Ca-dodecylbenzenesulfonate
- Soprophor® types optionally esterified derivatives of tristyrylphenoi ethoxylates
- Emmulsogen® 3510 alkylated EO/PO copolymer
- Emulsogen® EL 400 ethoxylated castor oil
- Tween® types fatty-acylated sorbitan
- Examples of further anionic emulsifiers and dispersants c2) from the group of naphthalene sulfonates are Galoryl® MT 800 (sodium dibutylnaphthalene sulfonic acid), Morwet® IP (sodium diisopropylnaphthalene sulfonate) and Nekal® BX (alkyl naphthalene sulfonate).
- anionic surfactants from the group of condensation products of naphthalene sulfonates with formaldehyde are Galoryl® DT 201 (naphthalene sulfonic acid hydroxy polymer with formaldehyde and methylphenol sodium salt), Galoryl® DT 250 (condensation product of phenol and naphthalene sulfonates), Reserve® C (condensation product of phenol and Naphthalene sulfonates) or Morwet® D-425, Tersperse® 2020.
- 1,2-dibutyl or diisobutyl-substituted naphthalene sulfonates such as products such as Galoryl® MT 800 (CFPI-Nufarm) and Nekal® BX (BASF ).
- Other typical surfactants are Soprophor® 3D33, Soprophor® 4D384, Soprophor® BSU, Soprophor® CY/8 (Solvay) and Hoe® S3474 and in the form of the Sapogenat® T products (Clariant), for example Sapogenat® T 100.
- the proportion of anionic emulsifiers and dispersants c2) in the technical concentrates according to the invention is preferably 2 to 35% by weight, more preferably 3 to 30% by weight, even more preferably 5 to 25% by weight, and particularly preferably 10 up to 20% by weight.
- the proportion of the anionic emulsifiers and dispersants c2) in the suspension concentrates according to the invention is preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight and particularly preferably 0.3 to 4% by weight. .
- agrochemical active ingredients d) for the purposes of the present invention are fungicidal, insecticidal or herbicidal active ingredients.
- the formulation according to the invention contains one or more other insecticidal or fungicidal active ingredients d), particularly preferably one or more fungicidal active ingredients d).
- the active ingredients used are preferably water-insoluble.
- Examples of preferred insecticidal components d) are imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole, spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flunicamid , indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, the compound from WO-A 2006/089633 as example Ila-4, the compound disclosed in WO-A 2008/06
- Preferred fungicidal components d) are, for example, bixafen, bixlozone, fenamidone, fenhexamid, fluopicolide, fluopyram, fluoxastrobin, isoflucypram, iprovalicarb, isotianil, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, ametoctradine, amisulbrom, azoxystrobin, benthiavalicarb-isopyr, benzovindiflupropyl , Boscalid, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole, Ethaboxam, Epoxiconazole, Famoxadone, Fluazinam, Fluquinconazole, Flusilazole, Flutianil, Flux
- prothioconazole examples include tebuconazole, spiroxamine, bixafen, fluoxastrobin, trifloxystrobin, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl -lH-pyrazole-4-carboxamide, (3S,6S,7R,8R)-8-Benzyl-3-[( ⁇ 3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl ⁇ carbonyl)amino]- 6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (lyserphenvalpyr) and fluopyram.
- the proportion of component d) in the formulations according to the invention is preferably 1% by weight to 40% by weight, more preferably 3% by weight to 35% by weight.
- the formulations can contain solvents e), for example in the case of EC, OD or SE formulations.
- solvents e for example in the case of EC, OD or SE formulations.
- Aromatic hydrocarbon mixtures preferably reduced naphalin
- Solvesso® such as Solvesso®
- Aromatic hydrocarbons such as white spirit, petroleum, alkyl benzenes and spindle oil, xylene, toluene or alkyl naphthalenes;
- Aliphatic/Cyclaliphatic hydrocarbons such as mineral oils, hexane, heptane, donean, nonane, decane, cyclopentane, cyclohexane, decalin or white oil;
- Chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene, or methylene chloride, chloroform or tetrachloromethane;
- ® alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol or benzyl alcohol;
- Ethers such as tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydropyran, 1,4-dioxanes, diethyl ether, methyl tert-butyl ether, dihexyl ether, dioctyl ether, didecyl ether, dibenzyl ether, dimethyl isosorbide, diphenyl ether, ethyl phenyl ether, phenyl benzyl ether or anisole;
- ® monoester/diester/glycerol ester such as ethyl acetate, butyl propionate, pentyl propionate, benzyl acetate, benzyl benzoate, butyl benzoate, Rhodiasolv® Polarclean, Rhodiasolv® RPDE, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate, ethyl 3-ethoxypropionate (UCAR® ester EEP, Dow Chemical Company), dimethyl succinate, diethyl succinate, dipropyl succinate, dimethyl adipate, diethyl adipate, dipropyl adipate, dimethyl glutarate, diethyl glutarate, dipropyl glutarate, bis(2-ethylhexyl) adipate, diisopropyl adipate, dimethyl-2-methylglutarate, dioctyl maleate,
- Lactones such as butyrolactone, alpha-methyl-gamma-butyrolactone, gamma-valerolactone or delta-valerolactone;
- Polyethylene/propylene oxides such as monoethylene glycol, monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monopentyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monophenyl ether, monoethylene glycol dimethyl ether, monoethylene glycol diethyl ether, monoethylene glycol dipropyl ether, monoethylene glycol dibutyl ether, monoethylene glycol dipentyl ether, monoethylene glycol dihexyl ether, monoethylene glycol diphenyl ether, and their longer ethylene glycol homologues; Monopropylene Glycol, Monopropylene Glycol Monomethyl Ether, Monopropylene Glycol Monoethyl Ether,
- monopropylene glycol diethyl ether monopropylene glycol dipropyl ether, monopropylene glycol dibutyl ether, monopropylene glycol dipentyl ether, monopropylene glycol dihexyl ether, monopropylene glycol diphenyl ether, and their longer propylene homologues; Monoethylene glycol monomethyl ether acetate, monoethylene glycol diacetates and their longer ethylene glycol homologues; monopropylene glycol monomethyl ether acetate,
- Simple and substituted amines such as diethylamine, triethylamine, diisopropylamine, diisopropylethylamine, monoethanolamine, diethanolamine, triethanolamine and higher alkoxylated amines, anilines or dimethylanilines;
- Amides/ureas such as N-formylmorpholine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylbenzamide, N,N-dimethyloctanamide, NN-dimethyldecanamide, N,N-dimethyl-dec-9-en-1 -amide, N,N-dimethyldodedecanamide, N,N-dimethyllactamide, N,N-decylmethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2 -pyrrolidone, N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-nonyl-2-pyrrolidone, N-decy
- Ketones such as acetone, diacetone alcohol, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone , methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, ethyl isopropyl ketone, ethyl isobutyl ketone, ethyl isopentyl ketone, propyl isopropyl ketone, propyl isobutyl ketone, propyl isopentyl ketone, 3,3-dimethyl-2-butanone, 2,4-dimethyl -3-pentanone, 4,4-dimethyl -2-pentanone, 2,6-dimethyl-4-heptanone, 2,
- Nitriles such as acetonitrile, propanenitrile, 2-methyl-propanenitrile, butanenitrile, 3-methyl-butanenitrile, pentanenitrile, 4-methyl-pentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, nonanenitrile, decanenitrile, benzonitrile, benzene-acetonitrile, pentane-dinitrile, 2-methylpentanedinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile or nonanedinitrile;
- ® acetals such as 1,1-dimethoxymethane; 1,1-dimethoxyethane; 1,1'-[methylenebis(oxy)]bis-ethane; 1,1-diethoxyethane; 1,1'-[methylenebis(oxy)]bispropane; 2,4,6,8-Tetraoxanonane, 1,1'-[Methylenebis(oxy)]bis-butane, 2-Methyl-1-[(2-methylpropoxy)methoxy]-propane, 2, 4, 6, 8, 10-
- Carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, didecyl carbonate, ethylene carbonate, 4-methyl-1,3-dioxolan-2-one, 4-(methoxymethyl)- 1,3-dioxolan-2-one, glycerol carbonate, butylene carbonate, 4,6-dimethyl-3-dioxan-2-one or dibenzyl carbonate;
- ® phosphates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-butoxyethyl) phosphate or triphenyl phosphate;
- Sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, 1,1-dioxide-tetrahydro-thiophene, 1,1-dioxide-tetrahydro-3-methyl-thiophene or 1,1-dioxide-tetrahydro-2,4-dimethyl-thiophene.
- the formulations according to the invention can optionally contain liquid fillers e), such as vegetable or mineral oils or esters of vegetable or mineral oils.
- suitable vegetable oils e) are all oils which can usually be used in agrochemicals and can be obtained from plants. Examples include sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, corn oil, cottonseed oil, walnut oil, coconut oil and soybean oil.
- esters examples include ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate. Rapeseed oil methyl ester and ethylhexyl palmitate are preferred.
- Possible mineral oils are Exxsol® D100 and white oils.
- Carrier materials f) for shared apartments are Carrier materials f) for shared apartments.
- Fillers and carrier materials f) in the formulations according to the invention are selected from the group containing minerals, carbonates, sulfates and phosphates of alkaline earth metals and earth metals such as calcium carbonate, polymeric carbohydrates, tectosilicates such as precipitated silicas with low absorbency and natural tectosilicates such as kaolin.
- suitable fillers f) are, for example, Agsorb® LVM®-GA (attapulgite), Harborlite® 300 (perlite), Collys® HV (modified starch), Omya® chalk (calcium carbonate), Kaolin® Tec 1 (kaolin, aluminum hydrosilicate) , Steamic® OOS (talc, magnesium silicate).
- Natural tectosilicates and types of calcium carbonate such as Omya® chalk (calcium carbonate), Kaolin Tec 1® (kaolin) and Harborlite® 300 (perlite) are preferred for c2) here, natural tectosilicates such as Kaolin®, Tec® 1 (kaolin, aluminum hydrosilicate) and Harborlite® 300 (perlite).
- Kaolin and calcium carbonate are very particularly preferably used for WG formulations.
- Other suitable carrier materials or fillers f) are selected from the group of highly absorbent carriers with an absorption capacity of at least 200 g dibutyl phthalate per 100 g carrier material.
- Preferred highly absorbent carriers f) are silicic acids such as, for example, Sipemat® types (synthetic precipitated silicic acid of high absorptivity) and pyrogenic silicic acid (Aerosil® types). Precipitated silica is preferred.
- the proportion of fillers f) in the TKs according to the invention is preferably 0.1 to 10% by weight, more preferably 0.3 to 8% by weight and very particularly preferably 1 to 7% by weight.
- Suitable thickeners g) are organic thickeners g1) and inorganic thickeners g2).
- Organic thickeners g1) are suitable as organically natural or biotechnologically modified or organically synthetic thickeners.
- Typical synthetic thickeners are Rheostrux® (Croda), Thixin® or Thixatrol® series (Elementis). These are typically based on acrylates.
- Typical organic thickeners are based on xanthan or cellulose (such as hydroxyethyl or carboxymethyl cellulose) or a combination thereof. Other typical representatives are based on lignin (such as lignin sulfonates, Borresperse®NA, REAX® 88 or Kraftsperse 25 S).
- Natural modified thickeners based on xanthan are preferably used. Typical representatives are, for example, Rhodopol® (Solvay) and Kelzan® (Kelco Corp.) and Satiaxane® (Cargill).
- the proportion of the organic thickeners g1) in the SCs B) according to the invention is less than or equal to 5% by weight, preferably from 0.01 to 1.0% by weight, particularly preferably from 0.01 to 0.6% by weight, in total more preferably 0.05 to 0.5% by weight and most preferably 0.1 to 0.3% by weight.
- Suitable inorganic thickeners g2) are modified natural silicates, such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone® (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel) or the Van Gel series (RT Vanderbilt).
- modified natural silicates such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone® (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel) or the Van Gel series (RT Vanderbilt).
- the proportion of inorganic thickeners g2) in the formulations according to the invention is up to 0 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.2 to 1.5% by weight, very particularly preferably 0. 3 to 1.5% by weight and most preferably 0.4 to 1.3% by weight.
- a mixture of thickeners g1) and g2) is preferably used.
- particular preference is given to using exclusively organic thickeners d1).
- Very particular preference is given to thickeners g1) based on xanthan gum (such as Rhodopol® G from Solvay).
- SC's or TC's or WG's according to the invention can optionally also contain as further components h):
- Suitable defoamers are surface-active compounds based on silicone or silane, such as the Tegopren® products (Goldschmidt), the SE® products (Wacker), and the Bevaloid® (Kemira), Rhodorsil® (Solvay) and Silcolapse® products (Blustar Silicones) SE® (Wacker), Rhodorsil® and Silcolapse® products are preferred, and products such as Silcolapse® 5020 are particularly preferred.
- Suitable antifreeze agents are those from the group of ureas, diols and polyols, such as ethylene glycol and propylene glycol, glycerol, preferably propylene glycol or glycerol.
- Suitable preservatives are, for example, products such as Acticide® MBS (Biozid, Thor Chemie), CIT, MIT or BIT such as Proxel® GXL (BIT), Acticide® SPX (MIT, CIT).
- Suitable adhesion promoters can be selected from the group of polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymer of vinyl chloride and vinyl acetate, sodium salt of the copolymer of propene sultanic acid and partially hydrolyzed vinyl acetate, sodium caseinate, Phenolic resins, modified cellulose types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol), modified cellulose
- Suitable antifoam agents can be selected from the group of esters of phosphoric acid with lower alcohols, Cg-Cio alcohols, silicone surfactants (suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), such as polydimethylsiloxane, and their absorbates on solid carrier material such as Rhodorsil® 432 (silicone surfactant), butyl phosphate, isobutyl phosphate, n-octanol, Wacker ASP 15 (polydimethylsiloxane, absorbed on a solid carrier), Antifoam Agent®SE (polydimethylsiloxane).
- liquid silicone surfactants such as Antischaum-ffen® SE (polydimethylsiloxane)
- solid antifoams such as Wacker ASP 15 (polydimethylsiloxane).
- additives h) optionally contained in the formulations according to the invention are penetration enhancers, wetting agents, spreading agents and/or retention aids. All substances which can usually be used in agrochemicals for this purpose are suitable.
- ® ethoxylated methyl-terminated branched alcohols e.g. Genapol® type XM with 2-20 EO units;
- ® ethoxylated coconut alcohols e.g. Genapol® C types
- 2-20 EO units e.g. Genapol® C types
- ® ethoxylated CI 2/ 15 alcohols e.g. Synperonic® A types
- Synperonic® A types with 2-20 EO units
- ® propoxy-ethoxylated alcohols branched or linear, eg Antarox® B/848, Atlas® G5000, Goalamul® HOT 5902; ® propoxy-ethoxylated methyl-terminated fatty acids, eg Leofat® OC0503M;
- organomodified polysiloxanes e.g., BreakThru® OE444, BreakThru® S240, Silwet® L77, Silwet® 408;
- Suitable defoamers h are all substances which can usually be used for this purpose in agrochemicals. Silicone oils, silicone oil preparations, magnesium stearate, phosphinic and phosphonic acids are preferred. Examples are Silcolapse® 482 from Bluestar Silicones, Silfoam® SCI 132 from Wacker [dimethylsiloxanes and silicones, CAS no. 63148-62-9], SAG 1538 or SAG 1572 from Momentive [dimethyl siloxanes and silicones, CAS no. 63148-62-9] or Fluowet® PL 80.
- Possible preservatives h are all substances that can usually be used in agrochemicals for this purpose.
- suitable preservatives are preparations containing 5-chloro-2-methyl-4-isothiazolin-3-one [CIT; CAS no. 26172-55-4], 2-methyl-4-isothiazolin-3-one [MIT, CAS no. 2682-20-4] or 1.2-benzisothiazol-3(2H)-one [BIT, CAS no. 2634-33-5]
- Examples include Preventol® D7 (Lanxess), Kathon® CG/ICP (Rohm & Haas), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).
- Possible dyes h are all substances which can usually be used for this purpose in agrochemicals. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, red pigments and Permanent Red FGR.
- Suitable inert fillers h are all substances which can usually be used for this purpose in agrochemicals and which do not function as thickeners.
- Inorganic particles such as carbonates, silicates and oxides, and also organic substances, such as urea-formaldehyde condensates, are preferred. Examples include kaolin, rutile, silicon dioxide (“highly dispersed silicic acid”), silica gel and natural and synthetic silicates, as well as talc.
- the present invention also relates to water-dispersible technical concentrates (TK's) based on the compositions described above, containing one or more anionic emulsifiers c2, one or more nonionic emulsifiers c1), at least one or more carrier materials f,
- TK's water-dispersible technical concentrates
- suspension concentrates containing one or more anionic emulsifiers c2, one or more nonionic emulsifiers cl, at least one or more thickeners g).
- the present invention also relates to EC's containing one or more nonionic emulsifiers cl, at least one other agrochemical active substance, this preferably being a fungicide.
- the present invention also relates to ODs containing one or more nonionic emulsifiers c1, one or more anionic emulsifiers c2, at least one solvent e) at least one thickener g)
- the respective area and/or object-related application rate of the crop protection agents of the most varied of formulation types for combating the harmful organisms mentioned varies greatly.
- the application media known to the person skilled in the art as customary for the respective area of use are used in the customary quantities for this purpose; such as from several hundred liters of water per hectare with standard spraying methods to a few liters of oil per hectare with 'ultra low volume' aircraft application to a few milliliters of a physiological solution with injection methods.
- concentrations of the crop protection agents according to the invention in the corresponding application media therefore vary within a wide range and depend on the respective Application dependent.
- concentrations are used which are known to the person skilled in the art as customary for the respective area of use. Concentrations of from 0.01% by weight to 99% by weight are preferred, particularly preferably from 0.1% by weight to 90% by weight.
- agrochemical formulations according to the invention can be applied, for example, in the preparation forms customary for liquid preparations, either as such or after prior dilution with water, ie, for example, as emulsions, suspensions or solutions.
- the application is carried out according to the usual methods, e.g. by spraying, pouring or injecting.
- the formulations according to the invention are useful for controlling a large number of pests and can be used not only for the treatment of plant cultures, but also for inanimate matter and in the home.
- Pests or “harmful organisms” are understood here to mean all types of pests that can be combated or kept under control with organic plant protection agents, i.e. plant protection products, in particular fungicides and mixtures of fungicides with other plant protection products.
- the term pest therefore includes organisms that damage plants, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants.
- control includes both curative treatment, i.e. treating infested plants with a formulation according to the invention, and protective treatment, i.e. treating plants to protect them from pest infestation.
- the present invention thus also relates to the use of formulations described herein for controlling pests, in particular plant pests; and a method for controlling noxious organisms, particularly plant-damaging organisms, comprising contacting the noxious organisms, their habitat, their hosts such as plants and seeds, and the soil, area and environment in which they grow or may grow , But also of materials, plants, seeds, soil, surfaces or rooms that are to be protected from attack or infestation by plant-damaging organisms, with an effective amount of the formulations according to the invention.
- a further aspect of the invention relates to the use of the formulations described herein for protecting plants, including seeds, in particular for protecting useful plants from infestation by harmful organisms, in particular harmful fungi.
- 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, in particular for controlling harmful fungi.
- the formulations of the invention can be used in crop protection, especially as foliar, dressing and soil fungicides, in a manner known per se for controlling phytopathogenic fungi.
- plants which can be treated with the formulations according to the invention cotton, flax, grapevines, fruit, vegetables such as Rosaceae sp. (For example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches and berries such as strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp.
- Rubiaceae sp. for example banana trees and plantations
- Rubiaceae sp. e.g. coffee
- Theaceae sp. Sterculiceae sp.
- Rutaceae sp. e.g. lemons, organs and grapefruit
- Solanaceae sp. e.g. tomatoes
- Liliaceae sp. Asteraceae sp.
- Umbelliferae sp. e.g. lettuce
- Umbelliferae sp. e.g. lettuce
- Umbelliferae sp. e.g. lettuce
- Umbelliferae sp. e.g.
- Cruciferae sp. Chenopodiaceae sp.
- Cucurbitaceae sp. e.g. cucumber
- Alliaceae sp. e.g. leeks, onions
- Papilionaceae sp. e.
- Gramineae sp. e.g. corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale
- Asteraceae sp. e.g. sunflower
- Brassicaceae sp. for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress
- Fabacae sp. e.g. beans, peanuts
- Papilionaceae sp. e.g. soybean
- Solanaceae sp. e.g. potatoes
- sugar beet e.g. sugar beet, fodder beet, chard, beetroot
- sugarcane poppy, olive, coconut, cocoa, tobacco and useful and ornamental plants in garden and forest; and in each case genetically modified species of these plants, and the seeds of these plants.
- the formulations according to the invention are preferably used for the treatment of wheat, barley, rye, soya, onions, corn and peanuts.
- the formulations of prothioconazole according to the invention can in principle be used to combat all harmful fungal diseases which can also be combated with the known formulations of prothioconazole.
- these are, for example, the following plant diseases:
- Alternaria species on vegetables, oilseed rape, sugar beets, soybeans, cereals, cotton, fruit and rice e.g. A. solani or A. alternata on potatoes and other plants
- Aphanomyces species on sugar beets and vegetables e.g. Ascochyta sp. on cotton and rice, bipalaris and turner species on maize, cereals, rice and turf (e.g. teres on barley, D. tritci-repentis on wheat), Blumeria graminis (powdery mildew) on cereals
- Botrytis cinerea grape mold
- Vegetables, flowers and vines Botryodiplodia sp.
- the formulations according to the invention can be applied undiluted or diluted with water.
- they are mixed with at least one part of water, preferably with 10 parts of water and particularly preferably with at least 100 parts of water, for example with 1 to 10,000, preferably 10 to 5,000 and very particularly preferably with 50 to 24,000 parts of water based on one part of the formulation diluted.
- the subject of the present invention is also an emulsion obtainable by mixing water with the liquid formulation according to the invention.
- the mixing ratio of water to emulsion concentrate can be in the range from 1000:1 to 1:1, preferably 400:1 to 10:1.
- the dilution is achieved by pouring the emulsion concentrates according to the invention to the water. Agitation, such as stirring. However, agitation is usually not necessary. Although temperature is not a critical factor in the dilution process, dilutions are usually carried out at temperatures in the range 0°C to 50°C, more preferably 10°C to 30°C, or at ambient temperature.
- the water used for dilution is usually tap water.
- the water can already contain water-soluble or finely dispersed compounds that are used in plant protection, such as nutrients, fertilizers or pesticides.
- oils, wetting agents, adjuvants, fertilizers or micronutrients and other pesticides can be added to the emulsion according to the invention as a premix or, if appropriate, only shortly before use (tank mix).
- pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
- These agents can be added to the formulations according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
- the user usually applies the formulation according to the invention from a pre-dosing device, a knapsack sprayer, a spray tank, a spray plane or an irrigation system; the formulation according to the invention is usually diluted to the desired application concentration with water, buffer and/or other auxiliary substances, as a result of which the ready-to-use spray liquid or Agrochemical composition of the invention.
- a pre-dosing device a knapsack sprayer, a spray tank, a spray plane or an irrigation system
- the formulation according to the invention is usually diluted to the desired application concentration with water, buffer and/or other auxiliary substances, as a result of which the ready-to-use spray liquid or Agrochemical composition of the invention.
- 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray mixture are applied per hectare of agricultural land.
- the required application rates of the pure active ingredients without formulation auxiliaries depend on the intensity of the pest infestation, the development phase of the plants, the climatic conditions at the place of use and the application method.
- the application rate is in the range from 0.001 to 3 kg, preferably from 0.005 to 2 kg, particularly preferably from 0.01 to 1 kg and very particularly preferably from 50 to 500 g of active ingredient per hectare, the active ingredient here being prothioconazole plus possible other active ingredients means.
- the generally diluted formulations of the invention are applied primarily by spraying, especially foliar spraying.
- the application can be carried out using spraying techniques known to those skilled in the art, for example using water as the carrier and amounts of spray mixture of about 50 to 1000 liters per hectare, for example from 100 to 00 liters per hectare.
- the new formulations containing prothioconazole have advantageous properties for the treatment of plants, in particular they are distinguished by good application properties, high stability and high fungicidal activity.
- the invention is explained in more detail by the examples without being restricted thereto.
- Rhodopol® 23 Xanthan Derivative Solvay
- 2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol is separated from the formulating ingredients on a reverse phase column using an isocratic eluent Cut.
- the quantitative evaluation is performed by comparing the peak areas with those of the reference object using an external standard.
- the samples are exposed to light and stored for 4 weeks.
- the actual PTZ concentration in the concentrated formulations is 125 g/L.
- Each of the three dilutions was sprayed onto 10 cotton squares mounted on cardboard, with only 6 cotton squares being sprayed as a control.
- the degradation of PTZ to Desthio is time-dependent for all formulations and all dilutions.
- the conversion rates on the cotton samples increase from 1 hour after spraying to 6 hours after spraying.
- the conversion rate is also dependent on the PTZ concentration, with lower concentrations exhibiting a higher conversion rate.
- the lowest PTZ degradation was observed in the 62.5 g/L PTZ solution, while the 0.2 g/L dilution showed the highest degradation.
- Vitamin E tocopherol
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Abstract
The present invention relates to a method for stabilizing thioketones (thiones) on surface, in particular of active substances containing thione structural elements, especially triazoline thiones, as functional groups, and to the use of decenamide and tocopherols (vitamin E) in order to stabilize thione compounds.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Stabilisierung von von Thioketonen (Thione) auf Oberflächen, insbesondere von Wirkstoffen, die Thion-Bausteine, insbesondere Triazolinthione, als Funktionsgruppen enthalten, sowie die Verwendung von Decenamid und Tocopherolen (Vitamin E) zur Stabilisierung von Thion-Verbindungen. The present invention relates to a method for stabilizing thioketones (thiones) on surfaces, in particular active substances which contain thione building blocks, in particular triazolinthiones, as functional groups, and the use of decenamide and tocopherols (vitamin E) for stabilizing thione compounds .
Im Besonderen ist die vorliegende Erfindung auf die Stabilisierung von Thionen auf Oberflächen, insbesondere Baumwolle oder auch Blattoberflächen gerichtet. In particular, the present invention is aimed at stabilizing thiones on surfaces, in particular cotton or also leaf surfaces.
Ferner ist die vorliegende Erfindung auf ein Verfahren zur Stabilisierung von Thionen auf Oberflächen, insbesondere Blattoberflächen oder Baumwollgeweben, durch Decenamid und/oder Tocopherolen (Vitamin E) gerichtet. Furthermore, the present invention is directed to a method for stabilizing thiones on surfaces, in particular leaf surfaces or cotton fabrics, using decenamide and/or tocopherols (vitamin E).
Darüberhinaus ist die vorliegende Erfindung auf ein Verfahren zur Stabilisierung von Thionen auf Oberflächen, insbesondere Baumwolle oder auch Blattoberflächen, durch Ausbringen einer Formulierung enthaltend Decenamid und/oder Tocopherolen (Vitamin E) gerichtet. In addition, the present invention is directed to a method for stabilizing thiones on surfaces, in particular cotton or else leaf surfaces, by applying a formulation containing decenamide and/or tocopherols (vitamin E).
Es ist bereits bekannt, dass beispielsweise Prothioconazol in üblichen Formulierungen zur Bekämpfung von Pilzen verwendet werden kann (WO-A 96/16 048). Bei diesem Wirkstoff handelt es sich um das 2- [2-(l-Chlor-cyclopropyl)-3-(2-chlor-phenyl)-2-hydroxy-propyl]-2,4-dihydro-3H-l,2,4-triazol-3-thion.It is already known that, for example, prothioconazole can be used in customary formulations for controlling fungi (WO-A 96/16 048). This active ingredient is 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-3H-l,2, 4-triazole-3-thione.
Prothioconazole-haltige Formulierungen sind im allgemeinen flüssige Formulierungen und werden beispielsweise als Emulsionskonzentrate auf dem Markt angeboten. Prothioconazole-containing formulations are generally liquid formulations and are available on the market, for example, as emulsion concentrates.
Es ist ferner bekannt, dass sich der Wirkstoff Prothioconazole unter bestimmten Bedingungen zu der Verbindung 2-( 1 -Chlorocyclopropyl)- 1 -(2-chlorophenyl)-3-( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol abbauen kann (PSM-Zulassungsbereicht, Tilmor, 2010.08.30, Lfd. Nr. 21, Bundesamt für Verbraucherschutz und Lebensmittelsicherheit). It is also known that the active ingredient prothioconazole converts under certain conditions to the compound 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propane -2-ol can degrade (PSM approval report, Tilmor, 08/30/2010, Serial No. 21, Federal Office for Consumer Protection and Food Safety).
Daher können Prothioconazol (im Folgenden PTZ genannt)-haltige Formulierungen bereits bei der Herstellung eine gewisse Menge an 2-(l-Chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4-triazol-l- yl)propan-2-ol enthalten. Bei der Lagerung unter drastischen Bedingungen, wie erhöhten Temperaturen, Licht-Einstrahlung sowie intensiver Sauerstoffkontakt, kann ebenfalls ein Abbau von Prothioconazole zu 2-( 1 -Chlorocyclopropyl)- 1 -(2-chlorophenyl)-3-( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol stattfinden, wodurch sich der Anteil an Wirkstoff in den Formulierungen entsprechend verringert. Da es sich bei der Verbindung 2-( 1 -Chlorocyclopropyl)- 1 -(2-chlorophenyl)-3-( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol (im Folgenden Desthio genannt) um eine relevante Verunreinigung handelt, ist deren Gehalt in
Prothioconazol-haltigen Formulierungen regulatorisch limitiert. Gleiches gilt hier analog für andere Thion-haltige Verbindungen, wie z.B. 4-((6-(2-(2,4-difluorophenyl)- 1, I-difluoro-2-hydroxy-3-(5- mercapio-I H-l,2,4-triazol-l-yl)propyl)pyridin-3-yl)oxy)benzonitrile. Therefore, formulations containing prothioconazole (hereinafter referred to as PTZ) can contain a certain amount of 2-(l-chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4-triazole-l - yl)propan-2-ol included. When stored under drastic conditions, such as elevated temperatures, exposure to light and intensive contact with oxygen, prothioconazole can also degrade to 2-( 1 -chlorocyclopropyl)- 1 -(2-chlorophenyl)-3-( 1H- 1 ,2, 4-triazol-1-yl)propan-2-ol take place, which reduces the proportion of active ingredient in the formulations accordingly. Since the compound 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (hereinafter called desthio) is a relevant impurity, its content is in Prothioconazole-containing formulations limited by regulation. The same applies here analogously to other thione-containing compounds, such as 4-((6-(2-(2,4-difluorophenyl)-1,I-difluoro-2-hydroxy-3-(5-mercapio-I HI, 2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitriles.
Hierbei richtet sich die maximal zulässige Menge an Desthio in PTZ Formulierungen nach der Menge an PTZ in der Formulierung in g/L. Die maximal zulässige Menge an Desthio ergibt sich in ppm, wobei sich der Zulässige Anteil an Desthio in ppm als die Hälfte des Wertes der PTZ-Beladung in g/L ergibt. Der maximal zulässige Gehalt an Desthio in einer Formulierung mit 100 g/L PTZ ist somit 50 ppm (=0.005 wt.-%). The maximum permissible amount of Desthio in PTZ formulations depends on the amount of PTZ in the formulation in g/L. The maximum allowable amount of desthio is given in ppm, where the allowable amount of desthio in ppm is given as half the value of the PTZ loading in g/L. The maximum permissible Desthio content in a formulation with 100 g/L PTZ is therefore 50 ppm (=0.005 wt%).
In der WO-A 2012/033590 werden wässrige Dispersionen von Prothioconazole offenbart, die eine schwefelhaltige Verbindung, wie beispielsweise L-Cysteine, zur Stabilisierung enthalten. WO-A 2012/033590 discloses aqueous dispersions of prothioconazole which contain a sulfur-containing compound, such as L-cysteine, for stabilization.
In der WO 2017/097882 sowie der WO2018/228885 werden stabilisierte PTZ-haltige formulierungen beschrieben, die als nächstliegender Stand der Technik angesehen werden können. In diesen werden Emulsionskonzentrate sowie Suspensionskonzentrate mit in einem Lösemittel gelöstem PTZ beschrieben. Die Formulierung konnte durch durch Zugabe von Verbindungen der Formel (I)
in welcher n für 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15 oder 18 steht stabilisiert und eine Reduzierung des Gehalts an Desthio erreicht werden. Stabilized PTZ-containing formulations are described in WO 2017/097882 and WO2018/228885, which can be regarded as the closest prior art. These describe emulsion concentrates and suspension concentrates with PTZ dissolved in a solvent. The formulation could be improved by adding compounds of formula (I) in which n is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15 or 18 and a reduction in the desthio content can be achieved.
Verbindungen der Formel (I) sind aus der WO-A 2012/061094 bekannt und können über das Verfahren der Metathese hergestellt werden. Es handelt sich beispielsweise um Produkte der Firma Stepan ((N,N- Dimethyl 9-decenamid, CAS Nummer: 1356964-77-6, Hallcomid® 1025 bzw. Steposol® MET-10U).Compounds of the formula (I) are known from WO-A 2012/061094 and can be prepared via the metathesis process. These are, for example, products from the Stepan company ((N,N-dimethyl 9-decenamide, CAS number: 1356964-77-6, Hallcomid® 1025 or Steposol® MET-10U).
Nachteilig an diesen Verbindungen ist, dass sehr große Mengen von bis zu 30% des Stabilisierungsmittel notwendig sind, um einen gewünschten Effekt zu erzielen und somit einen großen Eingriff in die Formulierung darstellen. Auch handelt es sich um neuartige Zusatzstoffe, die in einigen Fällen erst für Pflanzenschutzformulierungen zugelassen werden müssen.
Während im Stand der Technik die Stabilisierung von Thionen in Spritzbrühen und konzentrierten lagerfähigen Formulierungen beschrieben wird, gibt der Stand der Technik keinen Hinweis darauf, wie sich Thione auch nach dem Ausbringen auf Oberflächen stabiliesieren lassen, da auch hier die Abbauprodukte unerwünscht sind. A disadvantage of these compounds is that very large amounts of up to 30% of the stabilizer are necessary to achieve a desired effect and thus represent a major intervention in the formulation. These are also novel additives, which in some cases first have to be approved for crop protection formulations. While the prior art describes the stabilization of thiones in spray liquors and concentrated storable formulations, the prior art gives no indication of how thiones can also be stabilized after they have been applied to surfaces, since the degradation products are also undesirable here.
Es bestand somit Bedarf an einem Verfahren zur Stabilisierung von PTZ-haltigen Formulierungen nach ihrer Ausbringung auf Oberflächen, wo sie z.B. Sauerstoffkontakt, hohen Temperaturen oder Lichteinfall ausgesetzt sind, die denn Abbau der Thione, insbesondere der Triazolinthione und besonders von PTZ zu den entsprechenden Desthioprodukten z.B. 2-(l-Chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4- triazol-l-yl)propan-2-ol (Verbindung III), wirksam beschleunigen. There was therefore a need for a method for stabilizing PTZ-containing formulations after they have been applied to surfaces where they are exposed, for example, to oxygen contact, high temperatures or exposure to light, for example the degradation of the thiones, in particular the triazoline thiones and especially PTZ to the corresponding desthio products 2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (Compound III), effectively accelerate.
Aufgabe der vorliegenden Erfindung bestand somit in der Bereitstellung eines Verfahrens zur Stabilisierung von Thionen auf Oberflächen nach ihrer Ausbringung, insbesondere der Stabilisieriung von Prothioconazole, um dem Abbau zu 2-(l-Chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4-triazol-l- yl)propan-2-ol entgegen zu wirken. The object of the present invention was therefore to provide a method for stabilizing thiones on surfaces after they have been applied, in particular for stabilizing prothioconazole, in order to prevent degradation to 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-( to counteract lH-l,2,4-triazol-l-yl)propan-2-ol.
Es hat sich ferner gezeigt, daß der Abbau von Thionen zu Desthioprodukten stark durch Licht, u.a. auch bestimmter Wellenlängen, getriggert wird. Überraschenderweise zeigen hier aber übliche UV-Blocker oder UV-Absorber nur eine unzureichende Wirkung. It has also been shown that the degradation of thiones to desthio products is strongly triggered by light, including certain wavelengths. Surprisingly, however, conventional UV blockers or UV absorbers show only an inadequate effect here.
Darüberhinaus stellte sich heraus, daß auch verschiedene handelsübliche Antioxidanzien keinen wirksamen Schutz vor Abbau der Thione boten, sondern vielmehr diesen sogar noch förderten. In addition, it turned out that various commercially available antioxidants did not offer any effective protection against degradation of the thiones, but rather even promoted it.
Überraschenderweise hat sich herausgestellt, daß bestimmte Antioxidanzien und Radikalfanger wie z.B. Decenamid und Tocopherole (Vitamin E) auch schon in sehr geringer Menge den Abbau von Thionen zu Desthioprodukten auf Oberflächen, insbesondere von Prothioconazol, ausgesprochen wirksam verhindern, insbesondere bei hoher Wirkstoffkonzentration. Surprisingly, it has been found that certain antioxidants and free-radical scavengers such as decenamide and tocopherols (vitamin E), even in very small amounts, are extremely effective in preventing the degradation of thiones to desthio products on surfaces, especially prothioconazole, especially at high concentrations of active ingredient.
Gegenstand der vorliegenden Erfindung ist daher die Verwendung von Decenamid und Tocopherolen zur Stabilisierung von Thionen auf Oberflächen, insbesondere nach der Ausbringung dieser Thione als fungizides Spritzmittel. Die Tocopherole sind dabei vorzugsweise ausgewählt aus der Gruppe bestehend aus Tocotrienole, Tocopherole (z.B. (+)-delta-Tocopherol, (+/-)-alpha-Tocopherol), sowie Mischungen dieser Verbindungen. The subject matter of the present invention is therefore the use of decenamide and tocopherols for stabilizing thiones on surfaces, in particular after these thiones have been applied as a fungicidal spray. The tocopherols are preferably selected from the group consisting of tocotrienols, tocopherols (e.g. (+)-delta-tocopherol, (+/-)-alpha-tocopherol), and mixtures of these compounds.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher die Verwendung Tocopherol- oder Decenamid enthaltender Formulierungen zur Stabilisierung der Thione auf Oberflächen nach Ausbringung und Trocknung. A further object of the present invention is therefore the use of tocopherol- or decenamide-containing formulations for stabilizing the thiones on surfaces after application and drying.
Vorzugsweise sind die zu nach der Ausbringung zu stabilisierenden Formulierungen agrochemische Formulierungen.
In einer weiteren bevorzugten Ausfuhrungsform ist der Wirkstoff a) mit einer Thiongruppe ausgewählt aus der Gruppe, die Prothioconazol und 4-((6-(2-(2,4-difluorophenyl)- 1, I-difluoro-2-hydroxy-3-(5- mercapio-I H-l,2,4-triazol-l-yl)propyl)pyridin-3-yl)oxy)benzonitrile, besonders bevorzugt nur Prothioconazol umfaßt. Preferably, the formulations to be stabilized after application are agrochemical formulations. In a further preferred embodiment, the active ingredient a) with a thione group is selected from the group consisting of prothioconazole and 4-((6-(2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3- (5-mercapio-IH,2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitrile, particularly preferably only prothioconazole.
Ferner liegt der Wirkstoff vorzugsweise in einer Menge von 1 Gew.-% bis 50 Gew.-%, weiter bevorzugt 4 Gew.-% bis 30 Gew.-%, und besonders bevorzugt 5 Gew.-% bis 28 Gew.-% bezogen auf das Gesamtgewicht der Formulierung vor. Furthermore, the active ingredient is preferably present in an amount of from 1% to 50% by weight, more preferably from 4% to 30% by weight, and particularly preferably from 5% to 28% by weight to the total weight of the formulation.
Das Antioxidanz b) ist weiter bevorzugt aus der Gruppe, die Decenamid, soweit nicht anders bezeichnet im Sinne der vorliegenden Erfindung N,N-Dimethyl-9-Decenamid, und Tocopherole und Tocotrienole (vorzugsweise (+)-delta-Tocopherol, (+/-)-alpha-Tocopherol, (+)-alpha-Tocopherol sowie Vitamin E und Mischungen von Tocopherolen) umfaßt. The antioxidant b) is more preferably from the group that includes decenamide, unless otherwise specified for the purposes of the present invention, N,N-dimethyl-9-decenamide, and tocopherols and tocotrienols (preferably (+)-delta-tocopherol, (+/ -)-alpha-tocopherol, (+)-alpha-tocopherol as well as vitamin E and mixtures of tocopherols).
Vitamin E ist ein Sammelbegriff für fettlösliche Substanzen mit antioxidativen Wirkungen, wobei die am häufigsten verkommenen Formen Tocopherole und Tocotrienole sind. Im folgenden soll der Begriff Vitamin E alpha-Tocopherol (RRR-a-Tocopherol oder D-a-T0), beta-Tocopherol, gamma-Tocopherol, delta-Tocopherol, alpha-Tocotrienol, beta-Tocotrienol, gamma-Tocotrienol, delta-Tocotrienol, sowie deren Derivate wie beispielsweise Acetate umfassen. Vitamin E is a collective term for fat-soluble substances with antioxidant effects, the most common forms being tocopherols and tocotrienols. In the following, the term vitamin E should include alpha-tocopherol (RRR-a-tocopherol or Da-T0), beta-tocopherol, gamma-tocopherol, delta-tocopherol, alpha-tocotrienol, beta-tocotrienol, gamma-tocotrienol, delta-tocotrienol, and derivatives thereof such as acetates.
Unabhängig vom Formulierungstypen hegen die Antioxiantien vorzugsweise in einer Menge von 0,01 Gew.-% bis 15,00 Gew.-%, weiter bevorzugt von 0,03 Gew.-% bis 5,00 Gew.-%, und besonders bevorzugt 0,2 Gew.-% bis 4 Gew.-% bezogen auf das Gesamtgewicht der Formulierung vor. Regardless of the type of formulation, the antioxidants are preferably present in an amount of from 0.01% to 15.00% by weight, more preferably from 0.03% to 5.00% by weight, and most preferably 0 .2% by weight to 4% by weight based on the total weight of the formulation.
In Abhängigkeit von der Formulierung, z.B. wasser- oder Öl-basiert, werden vorzugsweise wasser- oder öllösliche Antioxidantien vorzugsweise in den folgenden Mengen eingesetzt: Depending on the formulation, e.g. water- or oil-based, water- or oil-soluble antioxidants are preferably used in the following amounts:
SC-Formulierungen: SC formulations:
In SCs liegen die Antioxiantien vorzugsweise in einer Menge von 0,01 Gew.-%bis 10,00 Gew. -%„ weiter bevorzugt von 0,03 Gew.-% bis 5 Gew.-%, noch weiter bevorzugt von 0,03 Gew.-% bis 1,00 Gew.-%, und besonders bevorzugt 0,05 Gew.-% bis 0,5 Gew.-% bezogen auf das Gesamtgewicht der Formulierung vor. In SCs, the antioxidants are preferably at a level of from 0.01% to 10.00% by weight, more preferably from 0.03% to 5% by weight, even more preferably from 0.03% % by weight to 1.00% by weight, and more preferably 0.05% by weight to 0.5% by weight, based on the total weight of the formulation.
OD und EC- Formulierungen: OD and EC formulations:
In ODs liegen die Antioxiantien vorzugsweise in einer Menge von 0,10 Gew.-% bis 5,00 Gew.-%, weiter bevorzugt von 0,2 Gew.-% bis 4,00 Gew.-%, und besonders bevorzugt 0,2 Gew.-% bis 3 Gew.-% bezogen auf das Gesamtgewicht der Formulierung vor.
In ECs liegen die Antioxiantien vorzugsweise in einer Menge von 0,50 Gew.-% bis 15,00 Gew.-%, weiter bevorzugt von 1 Gew.-% bis 10,00 Gew.-%, und besonders bevorzugt 3 Gew.-% bis 10 Gew.-% bezogen auf das Gesamtgewicht der Formulierung vor. In ODs, the antioxidants are preferably in an amount of from 0.10% to 5.00% by weight, more preferably from 0.2% to 4.00% by weight, and particularly preferably 0. 2% by weight to 3% by weight based on the total weight of the formulation. In ECs, the antioxidants are preferably at a level of from 0.50% to 15.00% by weight, more preferably from 1% to 10.00% by weight, and most preferably 3% by weight. % to 10% by weight based on the total weight of the formulation.
Prothioconazole (mit dem chemischen Namen 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2- hydroxpropyl]-l,2-dihydro-3H-l,2,4-triazole-3-thione) (CAS-Nummer 178928-70-6), liegt als Racemat vor. Geeignete Verfahren zu dessen Herstellung werden in der DE-A 195280 beschrieben. Prothioconazole kann in der Thiono-Form der allgemeinen Formel (II)
oder in der tautomeren Mercapto-Form der allgemeinen Formel (Ila)
vorliegen. Mit der Verwendung des Begriffs Prothioconazole werden im Folgenden immer die hier dargestellten Isomere sowie weitere mögliche Tautomere abgedeckt. Prothioconazole (with the chemical name 2-[2-(l-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-l,2-dihydro-3H-l,2,4-triazole-3-thione) (CAS number 178928-70-6) exists as a racemate. Suitable processes for its production are described in DE-A 195280. Prothioconazole can be in the thiono form of general formula (II) or in the tautomeric mercapto form of general formula (Ila) present. When the term prothioconazole is used below, the isomers shown here and other possible tautomers are always covered.
2-( 1 -Chlorocyclopropyl)- 1 -(2-chlorophenyl)-3 -( 1H- 1 ,2,4-triazol- 1 -yl)propan-2-ol liegt ebenfalls als Racemat vor und hat die allgemeine Formel (III), wobei wiederum alle tautomeren Formen mit dieser Darstellung umfasst sein sollen.
2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol also exists as a racemate and has the general formula (III ), again all tautomeric forms are intended to be included within this representation.
Weiterhin können die Formulierungen gemäß der vorliegenden Erfindung, wie sie vorangehend beschrieben worden sind, jeweils noch weitere Inhaltsstoffe enthalten, wie: a) cl: nicht-ionischer Dispergator/Emulgator, c2: ionischer Dispergator/Emulgator b) andere von a) verschiedene agrochemische Wirkstoffe c) Lösemittel einsschlieplich OD Carrier d) Träger (WGs, sowie Aerosile fur SC/TKWG) e) gl: organischer Verdicker g2: anorganischer Verdicker f) weitere Zusatz- und Hilfsstoffe Furthermore, the formulations according to the present invention, as described above, can each contain further ingredients, such as: a) cl: nonionic dispersant/emulsifier, c2: ionic dispersant/emulsifier b) other agrochemical active ingredients different from a). c) solvents including OD carriers d) carriers (WGs, as well as aerosils for SC/TKWG) e) gl: organic thickener g2: inorganic thickener f) other additives and auxiliaries
Formuliertypen werden von der FAO festgelegt und finden sich auf www.fao.org/ag/agp/agDD/pesticid. In der März Ausgabe von 2016 finden sich die üblichen Formuliertypen auf den Seiten 66-231 beschrieben. Bei der erfindungsgemäßen Formulierung handelt es sich um übliche nach FAO beschriebene Formulierungstypen. Beispielhaft seien Suspensionskonzentrate (SC), sowie farbstoffhaltige Konzentrate für die Saatgutbehandlung (FS), Emulsionskonzentrate (EC), wasserdispergierbare Konzentrate (WG), Öldispersionen (OD), Suspoemulsionen (SE), wässrige Emulsionen (EW), Mikroemulsionen (ME) sowie Flüssigformulierungen (SL) hier genannt. Bevorzugt handelt es sich um EC, SC, FS, SE, OD sowie WG Formuliertypen, ganz besonders bevorzugt handelt sich um Formulierungen, wo mindestens ein Wirkstoff nicht gelöst vorhegt. Ganz besonders bevorzugt handelt es sich um FS, SC, SE, OD und WG Formulierungen, ganz besonders bevorzugt um SC, FS und WG Formulierungen. Formulation types are defined by the FAO and can be found at www.fao.org/ag/agp/agDD/pesticid. In the March 2016 issue, the usual formulation types are described on pages 66-231. The formulation according to the invention is one of the usual types of formulation described by the FAO. Examples include suspension concentrates (SC) and concentrates containing dye for seed treatment (FS), emulsion concentrates (EC), water-dispersible concentrates (WG), oil dispersions (OD), suspoemulsions (SE), aqueous emulsions (EW), microemulsions (ME) and liquid formulations (SL) mentioned here. These are preferably EC, SC, FS, SE, OD and WG formulation types, very particularly preferably formulations in which at least one active ingredient is not present in dissolved form. Very particularly preferably, these are FS, SC, SE, OD and WG formulations, very particularly preferably SC, FS and WG formulations.
Weitere Gegenstände der vorliegenden Erfindung sind die Verwendung der erfindungsgemäßen Formulierungen zur Behandlung von Pflanzen sowie entsprechende Verfahren.
Nichtionische Emulgier-und Dispergiermittel cl) Further objects of the present invention are the use of the formulations according to the invention for the treatment of plants and corresponding methods. Nonionic emulsifiers and dispersants cl)
Als nichtionische Emulgier-und Dispergiermittel cl) wie Emulgatoren, Netzmittel, Tenside und Dispergatoren kommen übliche, in Formulierungen von agrochemischen Wirkstoffen vorhandene oberflächenative Substanzen in Frage. Beispielhaft genannt seien ethoxylierte Nonylphenole, Umsetzungsprodukte von linearen oder verzweigten Alkoholen mit Ethylenoxid und/oder Propylenoxid, Ethylenoxid-Propylenoxid-Blockcopolymere, Endgruppen-verschlossene und nicht Endgruppenverschlossene alkoxylierte lineare und verzweigte, gesättigte und ungesättigte Alkohole (z.B. Butoxypolyethylenpropylenglycole), Umsetzungsprodukte von Alkylphenolen mit Ethylenoxid und/oder Propylenoxid, Ethylenoxid- Propylenoxid-Blockcopolymere, Polyethylenglykole und Polypropylenglykole, weiterhin Fettsäureester, Fettsäurepolyglykoletherester, Alkylsulfonate, Alkylsulfate, Arylsulfate, ethoxylierte Arylalkylphenole, wie zum Beispiel Tristyryl-phenol-ethoxylat mit durchschnittlich 16 Ethylenoxid-Einheiten pro Molekül, weiterhin ethoxylierte und propoxylierte Arylalkylphenole sowie sulfatierte oder phosphatierte Arylalkylphenol-ethoxylate bzw. -ethoxy- und - propoxylate. Besonders bevorzugt sind Tristryl-phenol-alkoxylate und Fettsäurepolyglykoletherester. Ganz besonders bevorzugt sind Tristyryl-phenol-ethoxylate, Tristyryl-phenol-ethoxy-propoxylate und Ricinusölpolyglykoletherestem, jeweils einzeln oder in Mischungen. Hinzu kommen gegebenenfalls Additive, wie Tenside oder Ester von Fettsäuren, die zur Verbesserung der biologischen Wirksamkeit beitragen. Geeignete nichtionische Emulgier-und Dispergiermittel cl) sind beispielsweise Soprophor® 796/P, Lucramul® CO30, Lucramul® HOT, Lucramul® PSI 100 oder Synperonic® T304. Suitable nonionic emulsifying and dispersing agents cl), such as emulsifiers, wetting agents, surfactants and dispersants, are customary surface-active substances present in formulations of agrochemically active compounds. Examples include ethoxylated nonylphenols, reaction products of linear or branched alcohols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, end-capped and uncapped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxypolyethylene-propylene glycols), reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, furthermore fatty acid esters, fatty acid polyglycol ether esters, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyryl-phenol ethoxylate with an average of 16 ethylene oxide units per molecule, also ethoxylated and propoxylated Arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxylates and propoxylates. Tristryl-phenol alkoxylates and fatty acid polyglycol ether esters are particularly preferred. Tristyryl phenol ethoxylates, tristyryl phenol ethoxy propoxylates and castor oil polyglycol ether esters, each individually or in mixtures, are very particularly preferred. There may also be additives, such as surfactants or esters of fatty acids, which contribute to improving the biological effectiveness. Examples of suitable nonionic emulsifiers and dispersants cl) are Soprophor® 796/P, Lucramul® CO30, Lucramul® HOT, Lucramul® PSI 100 or Synperonic® T304.
Geeignete nicht-ionische Dispergatoren cl) können ebenfalls ausgewählt werden aus der Gruppe enthaltend Polyvinylpyrrolidon (PVP), Polyvinylalkohol, Co-Polymer aus PVP und Dimethylaminoethylmethacrylat, butyliertes PVP, Co-Polymer aus Vinylchlorid und Vinylacetat, und partiell hydrolysiertem Vinylacetat, Phenolharze, modifizierte Cellulose Typen wie beispielsweise Luviskol® (Polyvinylpyrrolidon), Mowiol® (Polyvinylalkohol) oder modifizierte Cellulose. Bevorzugt sind Polyvinylpyrrolidon-Typen, besonders bevorzugt sind Typen von niedrigem Molekulargewicht wie Luviskol® K30 oder Sokalan® K30. Suitable nonionic dispersants cl) can also be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymer of vinyl chloride and vinyl acetate, and partially hydrolyzed vinyl acetate, phenolic resins, modified cellulose Types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol) or modified cellulose. Polyvinylpyrrolidone grades are preferred, and low molecular weight grades such as Luviskol® K30 or Sokalan® K30 are particularly preferred.
Als weitere nicht-ionische Emulgier-und Dispergiermittel cl) aus der Gruppe der Di- und Tri-block- copolymere aus Alkylenoxiden kommen z.B. Verbindungen in Frage, die auf Basis von Ethylen- und Propylenoxid aufgebaut sind, mit mittleren Molmassen zwischen 200 und 10000, bevorzugt 1000 bis 4000 g/mol, wobei der Massenanteil des polyethoxylierte Blocks zwischen 10 und 80% variiert, wie z.B. Synperonic® PE-Reihe (Uniqema), Pluronic® PE-Reihe (BASF), VOP® 32- oder Genapol® PF-Reihe (Clariant). Other suitable nonionic emulsifiers and dispersants cl) from the group of di- and tri-block copolymers of alkylene oxides are, for example, compounds which are based on ethylene and propylene oxide and have average molecular weights of between 200 and 10,000, preferably 1000 to 4000 g/mol, the mass fraction of the polyethoxylated block varying between 10 and 80%, such as Synperonic® PE series (Uniqema), Pluronic® PE series (BASF), VOP® 32 or Genapol® PF series (Clariant).
Der Anteil der nicht-ionischen Emulgier-und Dispergiermittel cl) in den erfindungsgemäßen Suspensionskonzentraten beträgt bevorzugt 1 bis 15 Gew.-%, weiter bevorzugt 2 bis 10 Gew.-%, und besonders bevorzugt 2,5 bis 8 Gew.-%.
Anionische Emulgier-und Dispergiermittel c2) The proportion of the nonionic emulsifiers and dispersants c1) in the suspension concentrates according to the invention is preferably 1 to 15% by weight, more preferably 2 to 10% by weight and particularly preferably 2.5 to 8% by weight. Anionic emulsifiers and dispersants c2)
Geeignete anionische Emulgier-und Dispergiermittel bl) wie Emulgatoren, Tenside, Netzmittel und Dispergatoren sind beispielweise Alkali-, Erdalkali- oder Ammoniumsalze von Sulfonaten, Sulfaten, Phosphaten, Carboxylaten und deren Mischungen wie z.B. die Salze der Alkylsulphonsäuren oder Alkylphosphorsäuren sowie Alkylarylsulphon- oder Alkylarylphosphorsäuren, Diphenylsulfonate, alpha- Olefmsulfonate, Ligninsulfonate, Sulfonate von Fettsäuren und Ölen, Sulfonate von ethoxylierten Alkylphenolen, Sulfonate von alkoxylierten Arylphenolen, Sulfonate von kondensierten Naphthalinen, Sulfonate von Dodecyl- und Tridecylbenzolen, Sulfonate von Naphthalinen und Alkylnaphthalinen, Sulfosuccinate oder Sulfosuccinamate. Beispiele für Sulfate sind Sulfate von Fettsäuren und Ölen, von ethoxylierten Alkylphenolen, von Alkoholen, von ethoxylierten Alkoholen oder von Fettsäureestem. Beispiele für Phosphate sind Phosphatester. Beispiele für Carboxylate sind Alkylcarboxylate sowie carboxylierte Alkohol- oder Alkylphenolethoxylate. Ebenfalls geeignet ist die Gruppe der anionischen Emulgatoren der Alkalimetall-, Erdalkalimetall- und Ammoniumsalze der Polystyrolsulfonsäuren, Salze der Polyvinylsulphonsäuren, Salze der Alkylnaphthalinsulphonsäuren, Salze von Alkylnaphthalinsulphonsäure-Formaldehyd Kondensationsprodukte, Salze von Kondensationsprodukte der Naphthalinsulphonsäure, Phenolsulphonsäure und Formaldehyd. Beispiele sind Kalziumdodecylbenzensulfonat wie Rhodocal® 70/B (Solvay), Phenylsulfonat CAI 00 (Clariant) oder Isopropylammoniumdodecylbenzenesulfonate wie Atlox® 3300B (Croda). Suitable anionic emulsifiers and dispersants bl) such as emulsifiers, surfactants, wetting agents and dispersants are, for example, alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof such as the salts of alkyl sulfonic acids or alkyl phosphoric acids and alkylaryl sulfonic or alkylaryl phosphoric acids, Diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkyl phenols, sulfonates of alkoxylated aryl phenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecyl benzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkyl phenols, of alcohols, of ethoxylated alcohols or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkyl phenol ethoxylates. Also suitable is the group of anionic emulsifiers of the alkali metal, alkaline earth metal and ammonium salts of polystyrene sulfonic acids, salts of polyvinyl sulfonic acids, salts of alkyl naphthalene sulfonic acids, salts of alkyl naphthalene sulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalene sulfonic acid, phenol sulfonic acid and formaldehyde. Examples are calcium dodecyl benzene sulfonate such as Rhodocal® 70/B (Solvay), phenyl sulfonate CAI 00 (Clariant) or isopropylammonium dodecyl benzene sulfonate such as Atlox® 3300B (Croda).
Weitere typische Vertreter sind unter anderem Phenylsulfonat CA (Ca-Dodecylbenzolsulfonat), Soprophor®-Typen (gegebenenfalls veresterte Derivate von Tristyrylphenoi-Ethoxylaten), Emmulsogen® 3510 (alkyliertes EO/PO Copolymerisat), Emulsogen® EL 400 (ethoxyliertes Ricinusöl), Tween®-Typen (fettacylierte Sorbitan-Ethoxylate), Calsogen® AR 100 (Ca-Dodecylbenzolsulfonat). Bevorzugt sind Kombinationen aus Salzen alkylierter aromatischer Sulfonsäuren, wie Phenylsulfonat Ca und/oder Calsogen® AR 100, mit alkylierten Copolymerisaten aus Ethylen- und Propylenoxid, wie Emulsogen® 3510. Besonders bevorzugt sind Kombinationen aus Salzen der Dodecylbenzolsulfonsäure, wie Calsogen® AR 1 00 mit alkyliertem Copolymerisat aus Ethylen- und Propylenoxid, wie Emulsogen® 3510.Other typical representatives include phenylsulfonate CA (Ca-dodecylbenzenesulfonate), Soprophor® types (optionally esterified derivatives of tristyrylphenoi ethoxylates), Emmulsogen® 3510 (alkylated EO/PO copolymer), Emulsogen® EL 400 (ethoxylated castor oil), Tween® types (fatty-acylated sorbitan ethoxylates), Calsogen® AR 100 (Ca-dodecylbenzenesulfonate). Combinations of salts of alkylated aromatic sulfonic acids, such as phenylsulfonate Ca and/or Calsogen® AR 100, with alkylated copolymers of ethylene and propylene oxide, such as Emulsogen® 3510, are preferred. Combinations of salts of dodecylbenzenesulfonic acid, such as Calsogen® AR 100 with alkylated copolymer of ethylene and propylene oxide, such as Emulsogen® 3510.
Beispiele für weitere anionische Emulgier-und Dispergiermittel c2) aus der Gruppe der Naphthalinsulfonate sind Galoryl® MT 800 (Natrium-Dibutylnaphthalinsulfonsäure), Morwet® IP (Natriumdiisopropylnaphthalinsulfonat) und Nekal® BX (Alkylnaphthalinsulfonat). Beispiele für anionische Tenside aus der Gruppe der Kondensationsprodukte von Naphthalinsulfonaten mit Formaldehyd sind Galoryl® DT 201 (Naphthalinsulfonsäure Hydroxypolymer mit Formaldeyd und Methylphenol Natriumsalz), Galoryl® DT 250 (Kondensationsprodukt aus Phenol- und Naphthalinsulfonaten), Reserve® C (Kondensationsprodukt aus Phenol- und Naphthalinsulfonaten) oder Morwet® D-425, Tersperse® 2020. Bevorzugt sind 1,2 mit Di-Butyl- oder Di-Isobutyl-substituierte Naphthalinsulfonate, wie z.B. Produkte wie Galoryl® MT 800 (CFPI-Nufarm) und Nekal® BX (BASF). Weitere typische Tenside sind Soprophor® 3D33, Soprophor® 4D384, Soprophor® BSU, Soprophor®
CY/8 (Solvay) und Hoe® S3474 und in Form der Sapogenat® T-Produkte (Clariant), beispielsweise Sapogenat® T 100. Examples of further anionic emulsifiers and dispersants c2) from the group of naphthalene sulfonates are Galoryl® MT 800 (sodium dibutylnaphthalene sulfonic acid), Morwet® IP (sodium diisopropylnaphthalene sulfonate) and Nekal® BX (alkyl naphthalene sulfonate). Examples of anionic surfactants from the group of condensation products of naphthalene sulfonates with formaldehyde are Galoryl® DT 201 (naphthalene sulfonic acid hydroxy polymer with formaldehyde and methylphenol sodium salt), Galoryl® DT 250 (condensation product of phenol and naphthalene sulfonates), Reserve® C (condensation product of phenol and Naphthalene sulfonates) or Morwet® D-425, Tersperse® 2020. Preferred are 1,2-dibutyl or diisobutyl-substituted naphthalene sulfonates, such as products such as Galoryl® MT 800 (CFPI-Nufarm) and Nekal® BX (BASF ). Other typical surfactants are Soprophor® 3D33, Soprophor® 4D384, Soprophor® BSU, Soprophor® CY/8 (Solvay) and Hoe® S3474 and in the form of the Sapogenat® T products (Clariant), for example Sapogenat® T 100.
Der Anteil der anionischen Emulgier-und Dispergiermittel c2) in den erfindungsgemäßen Technischen Konzentraten beträgt bevorzugt 2 bis 35 Gew.-%, weiter bevorzugt 3 bis 30 Gew.-%, noch weiter bevorzugt 5 bis 25 Gew.-%, und besonders bevorzugt 10 bis 20 Gew.%. The proportion of anionic emulsifiers and dispersants c2) in the technical concentrates according to the invention is preferably 2 to 35% by weight, more preferably 3 to 30% by weight, even more preferably 5 to 25% by weight, and particularly preferably 10 up to 20% by weight.
Der Anteil der anionischen Emulgier-und Dispergiermittel c2) in den erfmdungsgemäßen Suspensionskonzentraten beträgt bevorzugt 0,1 bis 10 Gew.-%, weiter bevorzugt 0,2 bis 7 Gew.-%, und besonders bevorzugt 0,3 bis 4 Gew.-%. The proportion of the anionic emulsifiers and dispersants c2) in the suspension concentrates according to the invention is preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight and particularly preferably 0.3 to 4% by weight. .
Agrochemische weitere von PTZ verschiedene Wirkstoffe d): Agrochemical other active ingredients other than PTZ d):
Weitere agrochemische Wirkstoffe d) im Sinne der vorliegenden Erfindung sind fungizide, insektizide oder herbizide Wirkstoffe. In einer alternativen Ausfuhrungsform enthält die erfmdungsgemäße Formulierung ein oder mehrere weitere insektizide oder fungizide Wirkstoffe d), besonders bevorzugt ein oder mehrere fungizide Wirkstoffe d). Bevorzugt sind die eingesetzten Wirkstoffe wasserunlöslich. Further agrochemical active ingredients d) for the purposes of the present invention are fungicidal, insecticidal or herbicidal active ingredients. In an alternative embodiment, the formulation according to the invention contains one or more other insecticidal or fungicidal active ingredients d), particularly preferably one or more fungicidal active ingredients d). The active ingredients used are preferably water-insoluble.
Eine Übersicht typischer Pflanzenschutzwirkstoffe findet sich im Pesticide manual. An overview of typical crop protection agents can be found in the Pesticide manual.
Bevorzugte insektizide Komponenten d) sind beispielsweise Imidacloprid, Nitenpyram, Acetamiprid, Thiacloprid, Thiamethoxam, Clothianidin, Cyantraniliprole, Chlorantraniliprole, Flubendiamide, Tetraniliprole, Cyclaniliprole, Spirodiclofen, Spiromesifen, Spirotetramat, Abamectin, Acrinathrin, Chlorfenapyr, Emamectin, Ethiprole, Fipronil, Flonicamid, Flupyradifurone, Indoxacarb, Metaflumizone, Methoxyfenozid, Milbemycin, Pyridaben, Pyridalyl, Silafluofen, Spinosad, Sulfoxaflor, Triflumuron, die Verbindung aus WO-A 2006/089633 als Beispiel I-l-a-4, die Verbindung offenbart in WO-A 2008/067911 als Beispiel I-l-a-4, die Verbindung offenbart in WO 2013/092350 als Beispiel Ib-14, die Verbindung offenbart in WO 2010/51926 als Beispiel Ik-84. Examples of preferred insecticidal components d) are imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole, spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flunicamid , indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, the compound from WO-A 2006/089633 as example Ila-4, the compound disclosed in WO-A 2008/067911 as example Ila- 4, the compound disclosed in WO 2013/092350 as example Ib-14, the compound disclosed in WO 2010/51926 as example Ik-84.
Bevorzugte fungizide Komponenten d) sind beispielsweise Bixafen, Bixlozone, Fenamidone, Fenhexamid, Fluopicolide, Fluopyram, Fluoxastrobin, Isoflucypram, Iprovalicarb, Isotianil, Isopyrazam, Pencycuron, Penflufen, Propineb, Tebuconazole, Trifloxystrobin, Ametoctradin, Amisulbrom, Azoxystrobin, Benthiavalicarb-isopropyl, Benzovindiflupyr, Boscalid, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole, Ethaboxam, Epoxiconazole, Famoxadone, Fluazinam, Fluquinconazole, Flusilazole, Flutianil, Fluxapyroxad, Isopyrazam, Kresoxim- methyl, Lyserphenvalpyr, Mancozeb, Mandipropamid, Metconazol, Pyriofenone, Folpet, Metaminostrobin, Oxathiapiprolin, Penthiopyrad, Picoxystrobin, Probenazole, Proquinazid, Pydiflumetofen, Pyraclostrobin, Sedaxane, Spiroxamin, Tebufloquin, Tetraconazole, Valiphenalate, Zoxamide, Ziram, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl- lH-pyrazole-4-carboxamide, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-
fluoro- 1 -methyl- lH-pyrazole-4-carboxamide, 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3- [2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro- l,2-oxazol-5-yl}-3-chlorophenylmethane-sulfonate, (3S,6S,7R,8R)-8-Benzyl-3-[({3-Preferred fungicidal components d) are, for example, bixafen, bixlozone, fenamidone, fenhexamid, fluopicolide, fluopyram, fluoxastrobin, isoflucypram, iprovalicarb, isotianil, isopyrazam, pencycuron, penflufen, propineb, tebuconazole, trifloxystrobin, ametoctradine, amisulbrom, azoxystrobin, benthiavalicarb-isopyr, benzovindiflupropyl , Boscalid, Carbendazim, Chlorothanonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Difenoconazole, Ethaboxam, Epoxiconazole, Famoxadone, Fluazinam, Fluquinconazole, Flusilazole, Flutianil, Fluxapyroxad, Isopyrazam, Kresoxim- methyl, Lyserphenvalpyr, Mancozeb, Mandipropamid, Metconazole, Fol , Metaminostrobin, Oxathiapiproline, Penthiopyrad, Picoxystrobin, Probenazole, Proquinazid, Pydiflumetofen, Pyraclostrobin, Sedaxane, Spiroxamine, Tebufloquine, Tetraconazole, Valiphenalate, Zoxamide, Ziram, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-( difluoromethyl)-5-fluoro-l-methyl- lH-pyrazole-4-carboxamide, N-(5-chloro-2-isopropylbenzyl)- N-cyclopropyl-3-(difluoromethyl)-5- fluoro- 1 -methyl- lH-pyrazole-4-carboxamide, 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidine-4- yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(l-{[3,5- bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}- 3-chlorophenylmethane-sulfonate, (3S,6S,7R,8R)-8-benzyl-3-[({3-
[(isobutyryloxy)methoxy] -4-methoxypyridin-2-yl} carbonyl)amino] -6-methyl-4,9-dioxo- 1 ,5 -dioxonan-7- yl 2-methylpropanoat (Lyserphenvalpyr). [(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (lyserphenvalpyr).
Besonders bevorzugte fungizide Mischungspartner d) des Prothioconazols sind beispielsweise: Tebuconazol, Spiroxamin, Bixafen, Fluoxastrobin, Trifloxystrobin, N-(5-chloro-2-isopropylbenzyl)-N- cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (3S,6S,7R,8R)-8- Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo- l,5-dioxonan-7-yl 2-methylpropanoat (Lyserphenvalpyr) sowie Fluopyram. Examples of particularly preferred fungicidal mixing partners d) of prothioconazole are: tebuconazole, spiroxamine, bixafen, fluoxastrobin, trifloxystrobin, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl -lH-pyrazole-4-carboxamide, (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]- 6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2-methylpropanoate (lyserphenvalpyr) and fluopyram.
Ganz besonders bevorzugt sind die Mischungen von a) (Prothioconazole) mit ein oder mehreren Verbindungen ausgewählt aus der Gruppe der Verbindungen d): a) + d) Tebuconazole; a) + d) Trifloxystrobin; a) + d) Fluoxastrobin; a) + d) Bixafen; a) + d) Bixlozone a) + d) Isoflucypram; a) + d) Fluopyram; a) + d) Spiroxamine; a) + d) Fluoxastrobin + Trifloxystrobin; a) +d) Trifloxystrobin+Spiroxamin; a) + d) Bixafen + Tebuconazole; a) + d) Bixafen + Fluoxastrobin; a) + d) Bixafen + Trifloxystrobin; a) + d) Bixafen + Spiroxamin; a) + d) Bixafen + Fluopyram; a) + d) Tebuconazole + Spiroxamin; a) + d) Tebuconazole + Fluopyram; a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide + Tebuconazole
a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide + Flupyram a) +d) Bixafen + (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2- yl}carbonyl)amino]-6-methyl-4,9-dioxo-l,5-dioxonan-7-yl 2-methylpropanoatThe mixtures of a) (prothioconazole) with one or more compounds selected from the group of compounds d): a) + d) tebuconazole; a) + d) trifloxystrobin; a) + d) fluoxastrobin; a) + d) bixafen; a) + d) bixlozone a) + d) isoflucypram; a) + d) fluopyram; a) + d) spiroxamines; a) + d) fluoxastrobin + trifloxystrobin; a) +d) trifloxystrobin + spiroxamine; a) + d) bixafen + tebuconazole; a) + d) bixafen + fluoxastrobin; a) + d) bixafen + trifloxystrobin; a) + d) bixafen + spiroxamine; a) + d) bixafen + fluopyram; a) + d) tebuconazole + spiroxamine; a) + d) tebuconazole + fluopyram; a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide a) +d) N-( 5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide + tebuconazole a) +d) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide + flupyram a) +d) bixafen + (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9- dioxo-1,5-dioxonan-7-yl 2-methylpropanoate
(Lyserphenvalpyr) (Lyserphenvalpyr)
Der Anteil der Komponente d) in den erfindungsgemäßen Formulierungen beträgt vorzugsweise 1 Gew.- % bis 40 Gew.-%, weiter bevorzugt 3 Gew.-% bis 35 Gew.-%. The proportion of component d) in the formulations according to the invention is preferably 1% by weight to 40% by weight, more preferably 3% by weight to 35% by weight.
Lösemittel e): solvent e):
Die Formulierungen können Lösemittel e) enthalten, etwa im Falle von EC, OD oder SE Formulierungen. ® Aromatische Kohlenwasserstoffgemische (bevorzugt Naphalin reduziert) wie z.B. Solvesso®;The formulations can contain solvents e), for example in the case of EC, OD or SE formulations. ® Aromatic hydrocarbon mixtures (preferably reduced naphalin) such as Solvesso®;
® Aromatische Kohlenwasserstoffe wie z.B. Testbenzin, Petroleum, Alkylbenzole und Spindelöl, Xylol, Toluol oder Alkylnaphthaline; ® Aromatic hydrocarbons such as white spirit, petroleum, alkyl benzenes and spindle oil, xylene, toluene or alkyl naphthalenes;
® Aliphatische/Cyclaliphatische Kohlenwasserstoffe wie z.B. Mineralöle, Hexan, Heptan, Getan, Nonan, Decan, Cylcopentan, Cyclohexan, Decalin oder Weiß-Öl; ® Aliphatic/Cyclaliphatic hydrocarbons such as mineral oils, hexane, heptane, donean, nonane, decane, cyclopentane, cyclohexane, decalin or white oil;
® Chlorierte aromatische oder aliphatische Kohlenwasserstoffe wie z.B. Chlorbenzol, Chlorethylen, oder Methylenchlorid, Chloroform oder Tetrachloromethane; ® Chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene, or methylene chloride, chloroform or tetrachloromethane;
® Alkohole wie z.B. Methanol, Ethanol, iso-Propanol, Butanol, Ethylenglykol, Propylenglykol oder Benzylalkohol; ® alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol or benzyl alcohol;
® Ether wie z.B. Tetrahydrofuran, Tetrahydrofurfurylalkohol, Tetrahydropyran, 1,4-Dioxane, Diethylether, Methyl-tert-butylether, Dihexylether, Dioctylether, Didecylether, Dibenzylether, Dimethylisosorbid, Diphenylether, Ethylphenylether, Phenylbenzylether oder Anisol; ® Ethers such as tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydropyran, 1,4-dioxanes, diethyl ether, methyl tert-butyl ether, dihexyl ether, dioctyl ether, didecyl ether, dibenzyl ether, dimethyl isosorbide, diphenyl ether, ethyl phenyl ether, phenyl benzyl ether or anisole;
® Monoester/Diester/Glycerin-Ester wie z.B. Ethylacetat, Butylpropionat, PentylPropionat, Benzylacetat, Benzylbenzoat, Butylbenzoat, Rhodiasolv® Polarclean, Rhodiasolv® RPDE, Methyllactat, Ethyllactat, Propyllactat, Butyllactat, 2-Ethylhexyllactat, Ethyl-3-Ethoxypropionat (UCAR® Ester EEP, Dow Chemical Company), Dimethylsuccinat, Diethyl-succinat, Dipropylsuccinat, Dimethyladipat, Diethyladipat, Dipropyladipat, Dimethyl-glutarat, Diethylglutarat, Dipropylglutarat, Bis(2-ethylhexyl)adipat, Diisopropyladipat, Dimethyl-2- methylglutarat, Dioctylmaleat, Glycerin-monoacetat, Glycerin- diacetat, Glycerin-triacetat, Pflanzenöle wie z.B. Rapsöl, Sonnenblumenöl, Sojabohnenöl, Rizinusöl oder Maisöl; ® monoester/diester/glycerol ester such as ethyl acetate, butyl propionate, pentyl propionate, benzyl acetate, benzyl benzoate, butyl benzoate, Rhodiasolv® Polarclean, Rhodiasolv® RPDE, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate, ethyl 3-ethoxypropionate (UCAR® ester EEP, Dow Chemical Company), dimethyl succinate, diethyl succinate, dipropyl succinate, dimethyl adipate, diethyl adipate, dipropyl adipate, dimethyl glutarate, diethyl glutarate, dipropyl glutarate, bis(2-ethylhexyl) adipate, diisopropyl adipate, dimethyl-2-methylglutarate, dioctyl maleate, glycerol monoacetate, glycerol diacetate, glycerol triacetate, vegetable oils such as rapeseed oil, sunflower oil, soybean oil, castor oil or corn oil;
® Lactone wie z.B. Butyrolacton, alpha-Methyl-gamma-Butyrolacton, gamma-Valerolacton oder delta-Valerolacton; ® Lactones such as butyrolactone, alpha-methyl-gamma-butyrolactone, gamma-valerolactone or delta-valerolactone;
® Polyethylen/Propylenoxide wie z.B. Monoethylenglycol, Monoethylenglycol-monomethylether, Monoethylenglycol-monoethylether, Monoethylenglycol-monopropylether, Monoethylenglycol- monobutylether, Monoethylenglycol-monopentylether, Monoethylenglycol-monohexylether, Monoethylenglycol-monophenylether, Monoethylenglycol-dimethylether, Monoethylenglycol-
diethylether, Monoethylenglycol-dipropylether, Monoethylenglycol-dibutylether, Monoethylenglycol-dipentylether, Monoethylenglycol-dihexylether, Monoethylenglycol- diphenylether, sowie deren längere Ethylenglycol Homologen; Monopropylenglycol, Monopropylenglycol-monomethylether, Monopropylenglycol-monoethylether,® Polyethylene/propylene oxides such as monoethylene glycol, monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monobutyl ether, monoethylene glycol monopentyl ether, monoethylene glycol monohexyl ether, monoethylene glycol monophenyl ether, monoethylene glycol dimethyl ether, monoethylene glycol diethyl ether, monoethylene glycol dipropyl ether, monoethylene glycol dibutyl ether, monoethylene glycol dipentyl ether, monoethylene glycol dihexyl ether, monoethylene glycol diphenyl ether, and their longer ethylene glycol homologues; Monopropylene Glycol, Monopropylene Glycol Monomethyl Ether, Monopropylene Glycol Monoethyl Ether,
Monopropylenglycol-monopropylether, Monopropylenglycol-monobutylether,monopropylene glycol monopropyl ether, monopropylene glycol monobutyl ether,
Monopropylenglycol-monopentylether, Monopropylenglycol-monohexylether,monopropylene glycol monopentyl ether, monopropylene glycol monohexyl ether,
Monopropyleneglycol-monophenylether, Monopropylenglycol-dimethylether,monopropylene glycol monophenyl ether, monopropylene glycol dimethyl ether,
Monopropylenglycol-diethylether, Monopropylenglycol-dipropylether, Monopropylenglycol- dibutylether, Monopropylenglycol-dipentylether, Monopropylenglycol-dihexylether, Monopropylenglycol-diphenylether, sowie deren längeren Propylen Homologen; Monoethylenglycol-monomethyletheracetat, Monoethylenglycol-diacetate, sowie deren längere Ethylenglycol Homologen; Monopropylenglycol-monomethyletheracetat,monopropylene glycol diethyl ether, monopropylene glycol dipropyl ether, monopropylene glycol dibutyl ether, monopropylene glycol dipentyl ether, monopropylene glycol dihexyl ether, monopropylene glycol diphenyl ether, and their longer propylene homologues; Monoethylene glycol monomethyl ether acetate, monoethylene glycol diacetates and their longer ethylene glycol homologues; monopropylene glycol monomethyl ether acetate,
Monopropylenglycoldiacetat, sowie deren längere Polypropylenglycol Homologen; monopropylene glycol diacetate and their longer polypropylene glycol homologues;
Einfache und substituierte Amine wie z.B. Diethylamine, Triethylamine, Diisopropylamine, Diisopropylethylamine, Monoethanolamine, Diethanolamine, Triethanolamine und höher alkoxylierte Amine, Aniline oder Dimethylaniline; Simple and substituted amines such as diethylamine, triethylamine, diisopropylamine, diisopropylethylamine, monoethanolamine, diethanolamine, triethanolamine and higher alkoxylated amines, anilines or dimethylanilines;
Amide/Hamstoffe wie z.B. N-Formylmorpholin, N,N-Dimethylformamid, N,N-Dimethylacetamid, N,N-Dimethylbenzamid, N,N-Dimethyloctanamid, N-N-Dimethyldecanamid, N,N-Dimethyl-dec- 9-en-l-amid, N,N-Dimethyldodedecanamid, N,N-Dimethyllactamid, N,N-Decylmethylformamid, N-Methyl-2-pyrrolidon, N-Ethyl-2-pyrrolidon, N-Propyl-2-pyrrolidon, N-Butyl-2-pyrrolidon, N- Pentyl-2-pyrrolidon, N-Hexyl-2-pyrrolidon, N-Heptyl-2-pyrrolidon, N-Octyl-2-pyrrolidon, N- Nonyl-2-pyrrolidon, N-Decyl-2-pyrrolidon, N-Undecenyl-2-pyrrolidon, N-Dodecyl-2-pyrrolidon, N-Methyl-2-Piperidon, N-Methyl-caprolactam, N-Octyl-caprolactam, Tetramethylhamstoff, Tetraethylhamstoff, l,3-Dimethyl-2-imidazolidinon, l,3,4-Trimethyl-2-imidazolidinon, 1,3- Dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidinon, l-Heptyl-3 -methyl -2-Imidazolidinon, 1-Heptyl- l,3-dihydro-3-methyl-2H-Imidazol-2-on; Amides/ureas such as N-formylmorpholine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylbenzamide, N,N-dimethyloctanamide, NN-dimethyldecanamide, N,N-dimethyl-dec-9-en-1 -amide, N,N-dimethyldodedecanamide, N,N-dimethyllactamide, N,N-decylmethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2 -pyrrolidone, N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-nonyl-2-pyrrolidone, N-decyl-2-pyrrolidone , N-undecenyl-2-pyrrolidone, N-dodecyl-2-pyrrolidone, N-methyl-2-piperidone, N-methyl-caprolactam, N-octyl-caprolactam, tetramethylurea, tetraethylurea, l,3-dimethyl-2-imidazolidinone , l,3,4-Trimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidinone, l-heptyl-3 -methyl -2-imidazolidinone, 1- heptyl-1,3-dihydro-3-methyl-2H-imidazol-2-one;
Ketone wie z.B. Aceton, Diaceton-alkohol, Methylethylketon, 2 -Pentanon, 3 -Pentanon, 2- Hexanon, 3 -Hexanon, 2 -Heptanon, 3 -Heptanon, 4-Heptanon, 2 -Octanon, 3 -Octanon, 4-Octanon, Methylisopropylketon, Methyl-isobutylketone, Methyl-isopentylketon, Ethyl-isopropylketon, Ethyl-isobutylketon, Ethyl-isopentylketon, Propyl isopropyl keton, Propyl-isobutylketon, Propyl- isopentylketon, 3,3-Dimethyl-2-Butanon, 2, 4-Dimethyl-3 -Pentanon, 4, 4-Dimethyl -2 -Pentanon, 2,6-Dimethyl-4-Heptanon, 2,2,4,4-Tetramethyl-3-Pentanon, Cyclopentanon, Cyclohexanon. Cycloheptanon, Cyclooctanon, 2,4,6-Cycloheptatrien-l-on, Acetophenon, Propiophenon, l-(4- Methylphenyl)-Ethanon, l-(4-Ethylphenyl)-Ethanon, 2-Methyl-l -phenyl- 1-Propanon, l-(3- Ethylphenyl)-Ethanon, 4-phenyl-2-Butanon, 1 -Phenyl -2 -propanon, 1 -Phenyl -2 -butanon, 2-Phenyl- 3-butanon, Butyrophenon oder Valerophenon.
• Nitrile wie z.B. Acetonitril, Propannitril, 2-Methyl-Propannitril, Butannitrile, 3 -Methyl -Butannitril, Pentannitril, 4-Methyl-Pentannitril, Hexannitril, Heptannitril, Octannitril, Nonannitril, Decannitril, Benzonnitril, Benzen-acetonitril, Pentan-dinitril, 2-Methyl-pentan-dinitril, Hexan-dinitril, Heptan- dinitril, Octan-dinitril oder Nonan-dinitril; Ketones such as acetone, diacetone alcohol, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone , methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, ethyl isopropyl ketone, ethyl isobutyl ketone, ethyl isopentyl ketone, propyl isopropyl ketone, propyl isobutyl ketone, propyl isopentyl ketone, 3,3-dimethyl-2-butanone, 2,4-dimethyl -3-pentanone, 4,4-dimethyl -2-pentanone, 2,6-dimethyl-4-heptanone, 2,2,4,4-tetramethyl-3-pentanone, cyclopentanone, cyclohexanone. Cycloheptanone, Cyclooctanone, 2,4,6-cycloheptatrien-l-one, acetophenone, propiophenone, l-(4-methylphenyl)-ethanone, l-(4-ethylphenyl)-ethanone, 2-methyl-l -phenyl- 1- propanone, 1-(3-ethylphenyl)-ethanone, 4-phenyl-2-butanone, 1-phenyl-2-propanone, 1-phenyl-2-butanone, 2-phenyl-3-butanone, butyrophenone or valerophenone. • Nitriles such as acetonitrile, propanenitrile, 2-methyl-propanenitrile, butanenitrile, 3-methyl-butanenitrile, pentanenitrile, 4-methyl-pentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, nonanenitrile, decanenitrile, benzonitrile, benzene-acetonitrile, pentane-dinitrile, 2-methylpentanedinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile or nonanedinitrile;
® Acetale wie z.B. 1,1-Dimethoxymethan; 1,1-Dimethoxyethan; l,l'-[Methylenbis(oxy)]bis-ethan; 1,1-Diethoxyethan; l,l'-[Methylenbis(oxy)]bis-propan; 2,4,6,8-Tetraoxanonan, 1,1'- [Methylenebis(oxy)]bis-butan, 2-Methyl-l-[(2-methylpropoxy)methoxy] -propan, 2, 4, 6, 8, 10-® acetals such as 1,1-dimethoxymethane; 1,1-dimethoxyethane; 1,1'-[methylenebis(oxy)]bis-ethane; 1,1-diethoxyethane; 1,1'-[methylenebis(oxy)]bispropane; 2,4,6,8-Tetraoxanonane, 1,1'-[Methylenebis(oxy)]bis-butane, 2-Methyl-1-[(2-methylpropoxy)methoxy]-propane, 2, 4, 6, 8, 10-
Pentaoxaundecan, 2,5,7, 10-Tetraoxaundecan, 1,3-Dioxolan, 1,3-Dioxan oder 4-Methyl-l,3- Dioxan;Orthoester wie z.B. 1,1,1-Trimethoxymethan, 1,1,1-Trimethoxyethan, 1,1,1- Trimethoxypropan, 2-Methoxy- 1,3 -dioxolan, 2-Methoxy-2 -methyl- 1, 3 -dioxolan, 2-Methoxy-2- methyl- 1,3 -dioxolan, 2-Ethoxy-l,3-dioxolan, 2-Ethoxy-2 -methyl- 1,3 -dioxolan, 2-Ethyl-2- methoxy- 1,3 -dioxolan, 2-Methoxy-l,3-dioxan, 2-Methoxy-2 -methyl- 1, 3 -dioxan oder 2-Ethoxy- 1,3-dioxan; pentaoxaundecane, 2,5,7,10-tetraoxaundecane, 1,3-dioxolane, 1,3-dioxane or 4-methyl-1,3-dioxane; orthoesters such as 1,1,1-trimethoxymethane, 1,1,1 -trimethoxyethane, 1,1,1-trimethoxypropane, 2-methoxy-1,3-dioxolane, 2-methoxy-2-methyl-1,3-dioxolane, 2-methoxy-2-methyl-1,3-dioxolane, 2 -Ethoxy-1,3-dioxolane, 2-ethoxy-2-methyl-1,3-dioxolane, 2-ethyl-2-methoxy-1,3-dioxolane, 2-methoxy-1,3-dioxane, 2-methoxy -2-methyl-1,3-dioxane or 2-ethoxy-1,3-dioxane;
® Carbonate wie z.B. Dimethylcarbonat, Methylethylcarbonat, Diethylcarbonat, Dipropylcarbonat, Diisopropylcarbonat, Dibutylcarbonat, Dipentylcarbonat, Dihexylcarbonat, Diheptylcarbonat, Dioctylcarbonat, Dinonylcarbonat, Didecylcarbonat, Ethylencarbonat, 4-Methyl-l,3-Dioxolan-2- on, 4-(Methoxymethyl)-l,3-Dioxolan-2-on, Glycericarbonat, ButylencCarbonat, 4,6-Dimethyl-3- Dioxan-2-onoder Dibenzylcarbonat; ® Carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, didecyl carbonate, ethylene carbonate, 4-methyl-1,3-dioxolan-2-one, 4-(methoxymethyl)- 1,3-dioxolan-2-one, glycerol carbonate, butylene carbonate, 4,6-dimethyl-3-dioxan-2-one or dibenzyl carbonate;
® Phosphate wie z.B. Trimethylphosphat, Triethylphosphat, Tripropylphosphat, Tributylphosphat, Triisobutylphosphat, Tripentylphosphat, Trihexylphosphat, Tris(2-ethylhexyl)phosphat, Tris(2- butoxyethyl) phosphat oder Triphenylphosphat; ® phosphates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-butoxyethyl) phosphate or triphenyl phosphate;
® Sulfoxide wie z.B. Dimethylsulfoxid, Diethylsulfoxid, 1,1-Dioxidtetrahydro-thiophen, 1,1-Dioxid- tetrahydro-3 -methyl -thiophen oder 1, l-Dioxid-tetrahydro-2,4-dimethyl-thiophen. ® Sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, 1,1-dioxide-tetrahydro-thiophene, 1,1-dioxide-tetrahydro-3-methyl-thiophene or 1,1-dioxide-tetrahydro-2,4-dimethyl-thiophene.
Des Weiteren können die erfindungsgemäßen Formulierungen gegebenenfalls flüssige Füllstoffe e) wie beispielsweise Pflanzen- oder Mineralöle oder Ester von Pflanzen- oder Mineralölen enthalten. Geeignete Pflanzenöle e) sind alle Öle, die üblicherweise in Agrochemikalien eingesetzt werden können und sich aus Pflanzen gewinnen lassen. Als Beispiele seien Sonnenblumenöl, Rapsöl, Olivenöl, Ricinusöl, Kolzaöl, Maisöl, Baumwollsamenöl, Wallnussöl, Kokosnussöl und Sojaöl genannt. Mögliche Ester sind beispielsweise Ethylhexylpalmitat, Ethylhexyloleat, Ethylhexylmyristat, Ethylhexylcaprylat, Isopropylmyristat, Isopropylpalmitat, Methyloleat, Methylpaimitat, Ethyloleat. Bevorzugt sind Rapsöl- Methylester und Ethylhexylpalmitat. Mögliche Mineralöle sind Exxsol® D100 und Weißöle. Furthermore, the formulations according to the invention can optionally contain liquid fillers e), such as vegetable or mineral oils or esters of vegetable or mineral oils. Suitable vegetable oils e) are all oils which can usually be used in agrochemicals and can be obtained from plants. Examples include sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, corn oil, cottonseed oil, walnut oil, coconut oil and soybean oil. Examples of possible esters are ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate. Rapeseed oil methyl ester and ethylhexyl palmitate are preferred. Possible mineral oils are Exxsol® D100 and white oils.
Tabelle 1: Beispielhafte Handelsnamen und CAS-Nummern bevorzugter Verbindungen e)
Table 1: Exemplary trade names and CAS numbers of preferred compounds e)
Trägermaterialien f) für WGs. Carrier materials f) for shared apartments.
Füllstoffe und Trägermaterialien f) in den erfmdungsgemäßen Formulierungen sind ausgewählt aus der Gruppe enthaltend Mineralien, Carbonate, Sulfate und Phosphate von Erdalkali- und Erdmetallen, wie Calciumcarbonat, polymere Kohlenhydrate, Gerüstsilikate, wie Fällungskieselsäuren mit geringer Saugfähigkeit und natürliche Gerüstsilikate, wie Kaolin. Typische Vertreter geeigneter Füllstoffe f) sind beispielsweise Agsorb® LVM®-GA (Attapulgit), Harborlite® 300 (Perlit), Collys® HV (modifizierte Stärke), Omya®-Kreide (Calciumcarbonat), Kaolin® Tec 1 (Kaolin, Aluminiumhydrosilicat), Steamic® OOS (Talk, Magnesiumsilicat). Bevorzugt für c2) sind hier natürliche Gerüstsilikate und Calciumcarbonat-Typen wie Omya®-Kreide (Calciumcarbonat), Kaolin Tec 1® (Kaolin) und Harborlite® 300 (Perlit), besonders bevorzugt natürliche Gerüstsilikate wie Kaolin®, Tec® 1 (Kaolin, Aluminiumhydrosilicat) und Harborlite® 300 (Perlit). Ganz besonders bevorzugt werden für WG Formulierungen Kaolin und Calciumcarbonat verwendet. Weitere geeignete Trägermaterialien bzw. Füllstoffe f) sind ausgewählt aus der Gruppe der der hochsaugfahigen Träger mit einer Aufnahmefähigkeit von wenigstens 200 g Dibutylphthalat pro 100 g Trägermaterial. Bevorzugte hochsaugfahige Träger f) sind Kieselsäuren wie beispeilsweise Sipemat®-Typen (synthetische Fällungskieselsäure von hoher Saugfähigkeit) sowie pyrogene Kieselsäure (Aerosil® Typen). Bevorzugt ist Fällungskieselsäure. Der
Anteil der Füllstoffe f) in den erfmdungsgemäßen TK‘s beträgt vorzugsweise 0,1 bis 10 Gew.-% , weiter bevorzugt 0,3 bis 8 Gew.-% und ganz besonders bevorzugt 1 bis 7 Gew.-%. Fillers and carrier materials f) in the formulations according to the invention are selected from the group containing minerals, carbonates, sulfates and phosphates of alkaline earth metals and earth metals such as calcium carbonate, polymeric carbohydrates, tectosilicates such as precipitated silicas with low absorbency and natural tectosilicates such as kaolin. Typical representatives of suitable fillers f) are, for example, Agsorb® LVM®-GA (attapulgite), Harborlite® 300 (perlite), Collys® HV (modified starch), Omya® chalk (calcium carbonate), Kaolin® Tec 1 (kaolin, aluminum hydrosilicate) , Steamic® OOS (talc, magnesium silicate). Natural tectosilicates and types of calcium carbonate such as Omya® chalk (calcium carbonate), Kaolin Tec 1® (kaolin) and Harborlite® 300 (perlite) are preferred for c2) here, natural tectosilicates such as Kaolin®, Tec® 1 (kaolin, aluminum hydrosilicate) and Harborlite® 300 (perlite). Kaolin and calcium carbonate are very particularly preferably used for WG formulations. Other suitable carrier materials or fillers f) are selected from the group of highly absorbent carriers with an absorption capacity of at least 200 g dibutyl phthalate per 100 g carrier material. Preferred highly absorbent carriers f) are silicic acids such as, for example, Sipemat® types (synthetic precipitated silicic acid of high absorptivity) and pyrogenic silicic acid (Aerosil® types). Precipitated silica is preferred. the The proportion of fillers f) in the TKs according to the invention is preferably 0.1 to 10% by weight, more preferably 0.3 to 8% by weight and very particularly preferably 1 to 7% by weight.
Verdicker g) thickener g)
Als Verdicker g) kommen organische Verdicker gl) sowie anorganische Verdicker g2) in Frage. Suitable thickeners g) are organic thickeners g1) and inorganic thickeners g2).
Organische Verdicker gl) kommen als organisch natürliche bzw. biotechnologisch modifizierte oder organisch synthetische Verdicker in Frage. Typische synthetische Verdicker sind Rheostrux® (Croda), Thixin®- oder Thixatrol®-Reihe (Elementis). Diese sind typischerweise auf Basis von Acrylaten. Typische organische Verdicker sind auf Basis von Xanthan oder Cellulose (wie etwa Hydroxyethyl oder Carboxymethylcellulose) oder einer Kombination davon. Weitere typische Vertreter sind auf Basis von Lignin (wie Ligninsulfonate, Borresperse®NA, REAX® 88 oder Kraftsperse 25 S). Bevorzugt werden natürliche modifizierte Verdicker auf Basis von Xanthan verwendet. Typische Vertreter sind beispielsweise Rhodopol® (Solvay) und Kelzan® (Kelco Corp.) sowie Satiaxane® (Cargill). Organic thickeners g1) are suitable as organically natural or biotechnologically modified or organically synthetic thickeners. Typical synthetic thickeners are Rheostrux® (Croda), Thixin® or Thixatrol® series (Elementis). These are typically based on acrylates. Typical organic thickeners are based on xanthan or cellulose (such as hydroxyethyl or carboxymethyl cellulose) or a combination thereof. Other typical representatives are based on lignin (such as lignin sulfonates, Borresperse®NA, REAX® 88 or Kraftsperse 25 S). Natural modified thickeners based on xanthan are preferably used. Typical representatives are, for example, Rhodopol® (Solvay) and Kelzan® (Kelco Corp.) and Satiaxane® (Cargill).
Der Anteil der organischen Verdicker gl) in den erfmdungsgemäßen SC’s B) beträgt kleiner gleich 5 Gew.-%, bevorzugt 0,01 bis 1,0 Gew.-%, besonders bevorzugt 0,01 bis 0,6 Gew.-%, ganz besonders bevorzugt 0,05 bis 0,5 Gew.-% und ganz besonders bevorzugt 0,1 bis 0,3 Gew.-%. The proportion of the organic thickeners g1) in the SCs B) according to the invention is less than or equal to 5% by weight, preferably from 0.01 to 1.0% by weight, particularly preferably from 0.01 to 0.6% by weight, in total more preferably 0.05 to 0.5% by weight and most preferably 0.1 to 0.3% by weight.
Als anorganische Verdicker g2) geeignet sind beispielsweise modifizierte natürliche Silikate, wie chemisch modifizierte Bentonite, Hectorite, Attapulgite, Montmorillonite, Smektite oder andere Silikatmineralien, wie Bentone® (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) oder Hectorite® (Akzo Nobel) oder der Van Gel-Reihe (R.T. Vanderbilt). Examples of suitable inorganic thickeners g2) are modified natural silicates, such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone® (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel) or the Van Gel series (RT Vanderbilt).
Der Anteil anorganischer Verdicker g2) in den erfmdungsgemäßen Formulierungen beträgt bis 0 bis 5 Gew.-%, bevorzugt 0,1 bis 3 Gew.-%, besonders bevorzugt 0,2 bis 1,5 Gew.-%, ganz besonders bevorzugt 0,3 bis 1,5 Gew.-% und ganz besonders bevorzugt 0,4 bis 1,3 Gew.-%.. The proportion of inorganic thickeners g2) in the formulations according to the invention is up to 0 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.2 to 1.5% by weight, very particularly preferably 0. 3 to 1.5% by weight and most preferably 0.4 to 1.3% by weight.
Bevorzugt wird eine Mischung aus Verdicker gl) und g2) eingesetzt. Besonders bevorzugt werden im Falle von SCs ausschließlich organische Verdicker dl) eingesetzt. Ganz besonders bevorzugt sind solche Verdicker gl) auf Basis von Xanthan (wie Rhodopol® G von Solvay). A mixture of thickeners g1) and g2) is preferably used. In the case of SCs, particular preference is given to using exclusively organic thickeners d1). Very particular preference is given to thickeners g1) based on xanthan gum (such as Rhodopol® G from Solvay).
Weitere Komponenten h) Other components h)
Darüber hinaus können die erfmdungsgemäßen SC ’s oder TK’s oder WG’s als weitere Komponenten h) gegebenenfalls noch enthalten: In addition, the SC's or TC's or WG's according to the invention can optionally also contain as further components h):
Netzmittel, pH-Wert-Einstellungsmittel, Entschäumer, Biozide, Desintergrationsmittel, Haftvermittler, Frostschutzmittel, Konservierungsmittel, Farbstoffe oder Dünger, sowie von Komponente c) verschiedene Tenside.
Geeignete Entschäumer sind oberflächenaktive Verbindungen auf Silikon- bzw. Silanbasis wie die Tegopren®-Produkte (Goldschmidt), die SE®-Produkte (Wacker), sowie die Bevaloid®- (Kemira), Rhodorsil®- (Solvay) und Silcolapse®-Produkte (Blustar Silicones) bevorzugt sind SE®- (Wacker), Rhodorsil®-und Silcolapse®-Produkte, besonders bevorzugt sind z.B. Produkte wie Silcolapse® 5020.Wetting agents, pH adjusters, defoamers, biocides, disintegration agents, adhesion promoters, antifreeze agents, preservatives, dyes or fertilizers, and surfactants different from component c). Suitable defoamers are surface-active compounds based on silicone or silane, such as the Tegopren® products (Goldschmidt), the SE® products (Wacker), and the Bevaloid® (Kemira), Rhodorsil® (Solvay) and Silcolapse® products (Blustar Silicones) SE® (Wacker), Rhodorsil® and Silcolapse® products are preferred, and products such as Silcolapse® 5020 are particularly preferred.
Geeignete Frostschutzmittel sind solche aus der Gruppe der Harnstoffe, Diole und Polyole, wie Ethylenglycol und Propylenglycol, Glycerin bevorzugt Propylenglycol oder Glycerin. Suitable antifreeze agents are those from the group of ureas, diols and polyols, such as ethylene glycol and propylene glycol, glycerol, preferably propylene glycol or glycerol.
Geeignete Konservierungsmittel sind z.B. Produkte wie Acticide® MBS (Biozid, Thor Chemie), CIT, MIT oder BIT wie etwa Proxel® GXL (BIT), Acticide® SPX (MIT, CIT). Suitable preservatives are, for example, products such as Acticide® MBS (Biozid, Thor Chemie), CIT, MIT or BIT such as Proxel® GXL (BIT), Acticide® SPX (MIT, CIT).
Geeignete Haftvermittler können ausgewählt werden aus der Gruppe Polyvinylpyrrolidon (PVP), Polyvinylalkohol, Co-Polymer aus PVP und Dimethylaminoethylmethacrylat, butyliertes PVP, Co- Polymer aus Vinylchlorid und Vinylacetat, Na-Salz des Co-Polymers aus Propensultansäure und partiell hydrolysiertem Vinylacetat, Natriumcaseinat, Phenolharze, modifizierte CelluloseTypen wie beispielsweise Luviskol® (Polyvinylpyrrolidon), Mowiol® (Polyvinylalkohol), modifizierte CelluloseSuitable adhesion promoters can be selected from the group of polyvinylpyrrolidone (PVP), polyvinyl alcohol, copolymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, copolymer of vinyl chloride and vinyl acetate, sodium salt of the copolymer of propene sultanic acid and partially hydrolyzed vinyl acetate, sodium caseinate, Phenolic resins, modified cellulose types such as Luviskol® (polyvinylpyrrolidone), Mowiol® (polyvinyl alcohol), modified cellulose
Geeignete Antischaum -Mittel können ausgewählt werden aus der Gruppe der Ester der Phosphorsäure mit niederen Alkoholen, Cg-Cio Alkohole, Silicontenside (Suspoemulsionen von hydrophobisierten Kieselsäurepartikeln in wässrigen Emulsionskonzentraten auf der Basis flüssiger Silicontenside), wie Polydimethylsiloxan, sowie deren Absorbate an festes Trägermaterial wie beispielsweise Rhodorsil® 432 (Silicontensid), Butylphosphat, iso-Butylphosphat, n-Octanol, Wacker ASP 15 (Polydimethylsiloxan, an festem Träger absorbiert), Antischaum-Mittel®SE (Polydimethylsiloxan). Bevorzugt sind Suspoemulsionen von hydrophobisierten Kieselsäurepartikeln in wässrigen Emulsionskonzentraten auf der Basis flüssiger Silicontenside, wie Antischaum-Mittel® SE (Polydimethylsiloxan), und feste Antischaum-Mittel, wie Wacker ASP 15 (Polydimethylsiloxan). Suitable antifoam agents can be selected from the group of esters of phosphoric acid with lower alcohols, Cg-Cio alcohols, silicone surfactants (suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), such as polydimethylsiloxane, and their absorbates on solid carrier material such as Rhodorsil® 432 (silicone surfactant), butyl phosphate, isobutyl phosphate, n-octanol, Wacker ASP 15 (polydimethylsiloxane, absorbed on a solid carrier), Antifoam Agent®SE (polydimethylsiloxane). Preference is given to suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants, such as Antischaum-mittel® SE (polydimethylsiloxane), and solid antifoams, such as Wacker ASP 15 (polydimethylsiloxane).
Weitere, gegebenenfalls in den erfmdungsgemäßen Formulierungen enthaltene Zusätze h) sind Penetrationsförderer, Netzmittel, Spreitmittel und/oder Retentionsmittel. Geeignet sind alle Substanzen, die üblicherweise in Agrochemikalien zu diesem Zweck eingesetzt werden können. Other additives h) optionally contained in the formulations according to the invention are penetration enhancers, wetting agents, spreading agents and/or retention aids. All substances which can usually be used in agrochemicals for this purpose are suitable.
Als Zusätze h) geeignet sind beispielsweise Examples of suitable additives h) are:
• ethoxylierte verzweigte Alkohole (z.B. Genapol® Typ X) mit 2-20 EO-Einheiten; • ethoxylated branched alcohols (e.g. Genapol® type X) with 2-20 EO units;
® ethoxylierte verzweigte Alkohole mit endständigem Methyl (z.B. Genapol® Typ XM) mit 2-20 EO-Einheiten; ® ethoxylated methyl-terminated branched alcohols (e.g. Genapol® type XM) with 2-20 EO units;
® ethoxylierte Kokosnussalkohole (z.B. Genapol® C-Typen) mit 2-20 EO-Einheiten; ® ethoxylated coconut alcohols (e.g. Genapol® C types) with 2-20 EO units;
® ethoxylierte CI 2/ 15 -Alkohole (z.B. Synperonic® A-Typen) mit 2-20 EO-Einheiten; ® ethoxylated CI 2/ 15 alcohols (e.g. Synperonic® A types) with 2-20 EO units;
® propoxy-ethoxylierte Alkohole, verzweigt oder linear, z.B. Antarox® B/848, Atlas® G5000, Lucramul® HOT 5902;
® propoxy-ethoxylierte Fetsäuren mit endständigem Methyl, z.B. Leofat® OC0503M; ® propoxy-ethoxylated alcohols, branched or linear, eg Antarox® B/848, Atlas® G5000, Lucramul® HOT 5902; ® propoxy-ethoxylated methyl-terminated fatty acids, eg Leofat® OC0503M;
® organomodifizierte Polysiloxane, z.B. BreakThru® OE444, BreakThru® S240, Silwet® L77, Silwet® 408; ® organomodified polysiloxanes, e.g., BreakThru® OE444, BreakThru® S240, Silwet® L77, Silwet® 408;
® Mono- und Diester von Sulfosuccinat-Na-Salzen mit verzweigten oder linearen Alkoholen mit 1- 10 Kohlenstoffatomen; ® mono- and diesters of sodium sulfosuccinate salts with branched or linear alcohols having 1-10 carbon atoms;
® ethoxylierte Diacetylendiole (z.B. Surfynol®). ® ethoxylated diacetylene diols (e.g. Surfynol®).
Tabelle 2: Beispielhafte Handelsnamen und CAS-Nummern bevorzugter Verbindungen h)
Als Entschäumer h sind alle Substanzen geeignet, die üblicherweise in Agrochemikalien zu diesem Zweck eingesetzt werden können. Bevorzugt sind Siliconöle, Siliconölzubereitungen Magnesiumstearat, Phosphin- und Phosphonsäuren. Beispiele sind Silcolapse® 482 von Bluestar Silicones, Silfoam® SCI 132 von Wacker [Dimethylsiloxane und -silicone, CAS-Nr. 63148-62-9], SAG 1538 oder SAG 1572 von Momentive [Dimethylsiloxane und -silicone, CAS-Nr. 63148-62-9] oder Fluowet® PL 80. Table 2: Exemplary trade names and CAS numbers of preferred compounds h) Suitable defoamers h are all substances which can usually be used for this purpose in agrochemicals. Silicone oils, silicone oil preparations, magnesium stearate, phosphinic and phosphonic acids are preferred. Examples are Silcolapse® 482 from Bluestar Silicones, Silfoam® SCI 132 from Wacker [dimethylsiloxanes and silicones, CAS no. 63148-62-9], SAG 1538 or SAG 1572 from Momentive [dimethyl siloxanes and silicones, CAS no. 63148-62-9] or Fluowet® PL 80.
Mögliche Konservierungsmittel h sind alle Substanzen, die üblicherweise in Agrochemikalien zu diesem Zweck eingesetzt werden können. Als Konservierungsmittel eignen sich beispielsweise Zubereitungen mit 5-Chlor-2-methyl-4-isothiazolin-3-on [CIT; CAS-Nr. 26172-55-4], 2-Methyl-4-isothiazolin-3-on [MIT, CAS-Nr. 2682-20-4] oder 1.2-Benzisothiazol-3(2H)-on [BIT, CAS-Nr. 2634-33-5], Als Beispiele seien Preventol® D7 (Lanxess), Kathon® CG/ICP (Rohm & Haas), Acticide® SPX (Thor GmbH) und Proxel® GXL (Arch Chemicals) genannt. Possible preservatives h are all substances that can usually be used in agrochemicals for this purpose. Examples of suitable preservatives are preparations containing 5-chloro-2-methyl-4-isothiazolin-3-one [CIT; CAS no. 26172-55-4], 2-methyl-4-isothiazolin-3-one [MIT, CAS no. 2682-20-4] or 1.2-benzisothiazol-3(2H)-one [BIT, CAS no. 2634-33-5], Examples include Preventol® D7 (Lanxess), Kathon® CG/ICP (Rohm & Haas), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).
Als Antioxidantien h sind alle Substanzen geeignet, die üblicherweise in Agrochemikalien zu diesem Zweck eingesetzt werden können. Bevorzugt ist Butylhydroxytoluol [3.5-Di-tert.-butyl-4-hydroxytoluol, CAS-Nr. 128-37-0] und Zitronensäure. All substances which can usually be used in agrochemicals for this purpose are suitable as antioxidants h. Butylhydroxytoluene [3,5-di-tert-butyl-4-hydroxytoluene, CAS no. 128-37-0] and citric acid.
Mögliche Farbstoffe h sind alle Substanzen, die üblicherweise in Agrochemikalien zu diesem Zweck eingesetzt werden können. Als Beispiele seien Titandioxid, Ruß, Zinkoxid, blaue Pigmente, rote Pigmente und Permanent Red FGR genannt. Possible dyes h are all substances which can usually be used for this purpose in agrochemicals. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, red pigments and Permanent Red FGR.
Als inerte Füllstoffe h) sind alle Substanzen geeignet, die üblicherweise in Agrochemikalien zu diesem Zweck eingesetzt werden können und die nicht als Verdicker fungieren. Bevorzugt sind anorganische Partikel, wie Carbonate, Silicate und Oxide, und auch organische Substanzen, wie Hamstoff- Formaldehyd-Kondensate. Als Beispiele seien Kaolin, Rutil, Siliciumdioxid („hochdisperse Kieselsäure“), Kieselgel sowie natürliche und synthetische Silicate, zudem Talk genannt. Suitable inert fillers h) are all substances which can usually be used for this purpose in agrochemicals and which do not function as thickeners. Inorganic particles, such as carbonates, silicates and oxides, and also organic substances, such as urea-formaldehyde condensates, are preferred. Examples include kaolin, rutile, silicon dioxide (“highly dispersed silicic acid”), silica gel and natural and synthetic silicates, as well as talc.
Weiterhin Gegenstand der vorliegenden Erfindung sind wasserdispergierbare Technische Konzentrate (TK‘s) basierend auf den oben beschriebenen Zusammensetzungen enthaltend, ein oder mehrere anionische Emulgatoren c2, ein oder mehrere nichtionische Emulgatoren cl), mindestens ein oder mehrere Trägermaterialien f, The present invention also relates to water-dispersible technical concentrates (TK's) based on the compositions described above, containing one or more anionic emulsifiers c2, one or more nonionic emulsifiers c1), at least one or more carrier materials f,
Ebenfalls Gegenstand der vorliegenden Erfindung sind Suspensionskonzentrate (SC ’s) enthaltend
ein oder mehrere anionische Emulgatoren c2, ein oder mehrere nichtionische Emulgatoren cl, mindestens ein oder mehrere Verdicker g). Also subject of the present invention are suspension concentrates (SC's) containing one or more anionic emulsifiers c2, one or more nonionic emulsifiers cl, at least one or more thickeners g).
Ebenfalls Gegenstand der vorliegenden Erfindung sind EC’s enthaltend ein oder mehrere nichtionische Emulgatoren cl, mindestens ein Lösemittel e) Also subject of the present invention are EC's containing one or more nonionic emulsifiers cl, at least one solvent e)
Ebenfalls Gegenstand der vorliegenden Erfindung sind EC’s enthaltend ein oder mehrere nichtionische Emulgatoren cl, mindestens ein weiterer agrochemischer Wirkstoff, wobei dieser bevorzugt ein Fungizid ist. The present invention also relates to EC's containing one or more nonionic emulsifiers cl, at least one other agrochemical active substance, this preferably being a fungicide.
Ebenfalls Gegenstand der vorliegenden Erfindung sind OD’s enthaltend ein oder mehrere nichtionische Emulgatoren cl, ein oder mehrere anionische Emulgatoren c2 mindestens ein Lösemittel e) mindestens einen Verdicker g)
The present invention also relates to ODs containing one or more nonionic emulsifiers c1, one or more anionic emulsifiers c2, at least one solvent e) at least one thickener g)
Als Applikationsformen können alle, dem Fachmann als gebräuchlich bekannten Verfahren verwendet werden; beispielsweise genannt seien: Spritzen, Tauchen, Nebeln sowie eine Reihe spezieller Verfahren zur direkten unter- oder oberirdischen Behandlung von gesamten Pflanzen oder Teilen (Saatgut, Wurzel, Stolonen, Stängel, Stamm, Blatt), wie beispielsweise Stamminjektion bei Bäumen oder Stängelbandagen bei perennierenden Pflanzen, und eine Reihe spezieller indirekter Applikationsverfahren. All methods known to those skilled in the art as customary can be used as application forms; Examples include: spraying, dipping, misting and a number of special methods for direct underground or above-ground treatment of entire plants or parts (seeds, roots, stolons, stalks, stems, leaves), such as trunk injections for trees or stalk bandages for perennial plants , and a number of special indirect application methods.
Die jeweilige flächen- und/oder objektbezogene Aufwandmenge der Pflanzenschutzmittel unterschiedlichster Formulierungstypen zur Bekämpfung der genannten Schadorganismen variiert sehr stark. Im Allgemeinen werden hierfür die, dem Fachmann als gebräuchlich für das jeweilige Einsatzgebiet bekannten Applikationsmedien in den gebräuchlichen Mengen eingesetzt; wie beispielsweise von mehreren hundert Liter Wasser pro Hektar bei Standard- Spritzverfahren über wenige Liter Öl pro Hektar bei der 'Ultra Low Volume'-Flugzeugapplikation bis hin zu wenigen Millilitern einer physiologischen Lösungen bei Injektionsverfahren. Die Konzentrationen der erfindungsgemäßen Pflanzenschutzmittel in den entsprechenden Applikationsmedien variieren daher in einem weiten Bereich und sind vom jeweiligen
Einsatzgebiet abhängig. Im Allgemeinen werden Konzentrationen verwendet, die dem Fachmann als gebräuchlich für das jeweilige Einsatzgebiet bekannt sind. Bevorzugt sind Konzentrationen von 0,01 Gew.% bis 99 Gew.%, besonders bevorzugt von 0,1 Gew.% bis 90 Gew.%. The respective area and/or object-related application rate of the crop protection agents of the most varied of formulation types for combating the harmful organisms mentioned varies greatly. In general, the application media known to the person skilled in the art as customary for the respective area of use are used in the customary quantities for this purpose; such as from several hundred liters of water per hectare with standard spraying methods to a few liters of oil per hectare with 'ultra low volume' aircraft application to a few milliliters of a physiological solution with injection methods. The concentrations of the crop protection agents according to the invention in the corresponding application media therefore vary within a wide range and depend on the respective Application dependent. In general, concentrations are used which are known to the person skilled in the art as customary for the respective area of use. Concentrations of from 0.01% by weight to 99% by weight are preferred, particularly preferably from 0.1% by weight to 90% by weight.
Die erfmdungsgemäßen agrochemischen Formulierungen können z.B. in den für Flüssigpräparate üblichen Zubereitungsformen entweder als solche oder nach vorherigem Verdünnen mit Wasser ausgebracht werden, also z.B. als Emulsionen, Suspensionen oder Lösungen. Die Anwendung erfolgt dabei nach üblichen Methoden, also z.B. durch Verspritzen, Gießen oder Injizieren. The agrochemical formulations according to the invention can be applied, for example, in the preparation forms customary for liquid preparations, either as such or after prior dilution with water, ie, for example, as emulsions, suspensions or solutions. The application is carried out according to the usual methods, e.g. by spraying, pouring or injecting.
In Abhängigkeit von der Art des neben Prothioconazole möglicherweise zusätzlich vorliegenden Wirkstoffs sind die erfmdungsgemäßen Formulierungen zur Bekämpfung einer großen Zahl von Schädlingen nützlich und können sowohl zur Behandlung von Pflanzenkulturen, aber auch von unbelebter Materie und im Haushalt eingesetzt werden. Depending on the type of active ingredient that may be present in addition to prothioconazole, the formulations according to the invention are useful for controlling a large number of pests and can be used not only for the treatment of plant cultures, but also for inanimate matter and in the home.
Unter "Schädlingen" oder "schädlichen Organismen" werden hier alle Arten von Schädlingen verstanden, die mit organischen Pflanzenschutzwirkstoffen, d.h. Pflanzenschutzmitteln, insbesondere Fungiziden und Mischungen von Fungiziden mit anderen Pflanzenschutzmitteln, bekämpft bzw. unter Kontrolle behalten werden können. Der Begriff Schädling umfasst daher pflanzenschädigende Organismen, insbesondere Schadpilze und deren Sporen, aber auch schädliche Insekten, Arachniden, Nematoden und Schadpflanzen. Der Begriff "Kontrolle" umfasst sowohl die kurative Behandlung, d.h. die Behandlung von befallenen Pflanzen mit einer erfmdungsgemäßen Formulierung, als auch die protektive Behandlung, d.h. die Behandlung von Pflanzen zum Schutz vor einem Schädlingsbefall. "Pests" or "harmful organisms" are understood here to mean all types of pests that can be combated or kept under control with organic plant protection agents, i.e. plant protection products, in particular fungicides and mixtures of fungicides with other plant protection products. The term pest therefore includes organisms that damage plants, in particular harmful fungi and their spores, but also harmful insects, arachnids, nematodes and harmful plants. The term "control" includes both curative treatment, i.e. treating infested plants with a formulation according to the invention, and protective treatment, i.e. treating plants to protect them from pest infestation.
Die vorliegende Erfindung betrifft somit auch die Verwendung von hierin beschriebenen Formulierungen zur Bekämpfung von Schädlingen, insbesondere Pflanzenschädlingen; und ein Verfahren zur Bekämpfung von schädlichen Organismen, insbesondere von pflanzenschädigenden Organismen, umfassend das in Kontakt Bringen der schädlichen Organismen, ihres Habitats, ihrer Wirte, wie Pflanzen und Saatgut, sowie des Erdreichs, des Gebiets und der Umgebung in denen sie wachsen oder wachsen könnten, aber auch von Materialien, Pflanzen, Saatgut, Erdreich, Oberflächen oder Räumen, die vor dem Angriff oder dem Befall durch pflanzenschädigende Organismen geschützt werden sollen, mit einer wirksamen Menge der erfmdungsgemäßen Formulierungen. The present invention thus also relates to the use of formulations described herein for controlling pests, in particular plant pests; and a method for controlling noxious organisms, particularly plant-damaging organisms, comprising contacting the noxious organisms, their habitat, their hosts such as plants and seeds, and the soil, area and environment in which they grow or may grow , But also of materials, plants, seeds, soil, surfaces or rooms that are to be protected from attack or infestation by plant-damaging organisms, with an effective amount of the formulations according to the invention.
Ein weiterer Gesichtspunkt der Erfindung betrifft die Verwendung der hierin beschriebenen Formulierungen zum Schutz von Pflanzen einschließlich Saatgut, insbesondere um Nutzpflanzen vor dem Befall durch schädliche Organismen, insbesondere Schadpilzen, zu schützen. Die vorliegende Erfindung betrifft somit auch die Verwendung der Formulierungen zur Bekämpfung pflanzenschädlicher Organismen wie beispielsweise Schadpilzen, Insekten, Arachniden, Nematoden und Schadpflanzen, insbesondere zur Bekämpfung von Schadpilzen.
Die Formulierungen der Erfindung können im Pflanzenschutz vor allem als Blatt-, Beiz- und Bodenfungizide in an sich bekannter Weise zur Bekämpfung von pflanzenpathogenen Pilzen eingesetzt werden. A further aspect of the invention relates to the use of the formulations described herein for protecting plants, including seeds, in particular for protecting useful plants from infestation by harmful organisms, in particular harmful fungi. 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, in particular for controlling harmful fungi. The formulations of the invention can be used in crop protection, especially as foliar, dressing and soil fungicides, in a manner known per se for controlling phytopathogenic fungi.
Als Pflanzen, welche mit den erfindungsgemäßen Formulierungen behandelt werden können, seien folgende erwähnt: Baumwolle, Flachs, Weinrebe, Obst, Gemüse, wie Rosaceae sp. (beispielsweise Kernfrüchte wie Apfel und Birne, aber auch Steinfrüchte wie Aprikosen, Kirschen, Mandeln und Pfirsiche und Beerenfrüchte wie Erdbeeren), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (beispielsweise Bananenbäume und -plantagen), Rubiaceae sp. (beispielsweise Kaffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (beispielsweise Zitronen, Organen und Grapefruit); Solanaceae sp. (beispielsweise Tomaten), Liliaceae sp., Asteraceae sp. (beispielsweise Salat), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (beispielsweise Gurke), Alliaceae sp. (beispielsweise Lauch, Zwiebel), Papilionaceae sp. (beispielsweise Erbsen); Hauptnutzpflanzen, wie Gramineae sp. (beispielsweise Mais, Rasen, Getreide wie Weizen, Roggen, Reis, Gerste, Hafer, Hirse und Triticale), Asteraceae sp. (beispielsweise Sonnenblume), Brassicaceae sp. (beispielsweise Weißkohl, Rotkohl, Brokkoli, Blumenkohl, Rosenkohl, Pak Choi, Kohlrabi, Radieschen sowie Raps, Senf, Meerrettich und Kresse), Fabacae sp. (beispielsweise Bohne, Erdnüsse), Papilionaceae sp. (beispielsweise Sojabohne), Solanaceae sp. (beispielsweise Kartoffeln), Chenopodiaceae sp. (beispielsweise Zuckerrübe, Futterrübe, Mangold, Rote Rübe); Zuckerrohr, Mohn, Olive, Kokosnuss, Kakao, Tabak und Nutzpflanzen und Zierpflanzen in Garten und Wald; sowie jeweils genetisch modifizierte Arten dieser Pflanzen, sowie die Samen dieser Pflanzen. The following may be mentioned as plants which can be treated with the formulations according to the invention: cotton, flax, grapevines, fruit, vegetables such as Rosaceae sp. (For example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches and berries such as strawberries), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g. lemons, organs and grapefruit); Solanaceae sp. (e.g. tomatoes), Liliaceae sp., Asteraceae sp. (e.g. lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g. cucumber), Alliaceae sp. (e.g. leeks, onions), Papilionaceae sp. (e.g. peas); Major crops such as Gramineae sp. (e.g. corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (e.g. sunflower), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress), Fabacae sp. (e.g. beans, peanuts), Papilionaceae sp. (e.g. soybean), Solanaceae sp. (e.g. potatoes), Chenopodiaceae sp. (e.g. sugar beet, fodder beet, chard, beetroot); sugarcane, poppy, olive, coconut, cocoa, tobacco and useful and ornamental plants in garden and forest; and in each case genetically modified species of these plants, and the seeds of these plants.
Bevorzugt werden die erfindungsgemäßen Formulierungen zur Behandlung von Weizen, Gerste, Roggen, Soja, Zwiebeln, Mais und Erdnüssen eingesetzt. The formulations according to the invention are preferably used for the treatment of wheat, barley, rye, soya, onions, corn and peanuts.
Insbesondere lassen sich mit den erfindungsmäßigen Formulierungen des Prothioconazols grundsätzlich alle Schadpilzerkrankungen bekämpfen, die auch mit den bekannten Formulierungen des Prothioconazols bekämpft werden können. Abhängig von dem jeweiligen, gegebenenfalls vorliegenden Mischungspartner handelt es sich beispielsweise um die folgenden Pflanzenerkrankungen: In particular, the formulations of prothioconazole according to the invention can in principle be used to combat all harmful fungal diseases which can also be combated with the known formulations of prothioconazole. Depending on the respective mixing partner, if any, these are, for example, the following plant diseases:
Alternaria Arten an Gemüse, Raps, Zuckerrüben, Soja, Getreide, Baumwolle, Obst und Reis (z.B. A. solani oder A. alternata an Kartoffel und anderen Pflanzen), Aphanomyces Arten an Zuckerrüben und Gemüse, Ascochyta sp. an Baumwolle und Reis, Bipalaris- und Drechslern Arten an Mais, Getreide, Reis und Rasen (z.B. teres an Gerste, D. tritci-repentis an Weizen), Blumeria graminis (Echter Mehltau) an Getreide, Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Blumen und Weinreben, Botryodiplodia sp. an Baumwolle, Bremia lactucae an Salat, Cerospora Arten an Mais, Sojabohnen, Reis und Zuckerrüben (z.B. C. beticula an Zuckerrüben), Cochliobolus Arten an Mais, Getreide, Reis (z.B. Cochliobolus sativus an Getreide, Cochliobolus miyabeanus an Reis), Corynespora sp. an Sojabohnen,
Baumwolle und anderen Pflanzen, Colletotrichum Arten an Sojabohnen, Baumwolle und anderen Pflanzen (z.B. C. acutatum an verschiedenen Pflanzen), Curvularia sp. an Getreide und Reis, Diplodia sp. an Getreide und Reis, Exserohilum Arten an Mais, Erysiphe cichoracearum und Sphaerotheca fuliginea an Gurkengewächsen, Fusarium und Verticillium Arten (z.B. V. dahliae) an verschiedenen Pflanzen (z.B. F. graminearum an Weizen), Gaeumanomyces graminis an Getreide, Gibberella Arten an Getreide und Reis (z.B. Gibberella fujikuroi an Reis), Grainstaining complex an Reis, Helminthosporium Arten (z.B. H. graminicola) an Mais und Reis, Macrophomina sp. an Soja und Baumwolle, Michrodochium sp. (z.B. M. nivale an Getreide), Mycosphaerella Arten an Getreide, Bananen und Erdnüssen (M. graminicola an Weizen, M. fijiesis an Banane), Phaeoisaripsis sp. an Sojabohnen, Phakopsara sp. (z.B. P. pachyrhizi und P. meibomiae an Sojabohnen), Phoma sp. an Soja, Phomopsis Arten an Sojabohnen, Sonnenblumen und Weinreben (P. viticola an Weinreben, P. helianthii an Sonnenblumen), Phytophthora infestans an Kartoffeln und Tomaten, Plasmopara viticola an Weinreben, Penecilium sp. an Soja und Baumwolle, Podosphaera leucotricha an Apfel, Pseudocercosporella herpotrichoides an Getreide, Pseudoperonospora Arten an Hopfen und Gurkengewächsen (z.B. P. cubenis an Gurke), Puccinia Arten an Getreide, Mais und Spargel (P. triticina und P. striformis an Weizen, P. asparagi an Spargel), Pyrenophora Arten an Getreide, Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae an Reis, Pyricularia grisea an Rasen und Getreide, Pythium spp. an Rasen, Reis, Mais, Baumwolle, Raps, Sonnenblumen, Zuckerrüben, Gemüse und anderen Pflanzen, Rhizoctonia-Ax n (z.B. R. solani) an Baumwolle, Reis, Kartoffeln, Rasen, Mais, Raps, Kartoffeln, Zuckerrüben, Gemüse und anderen Pflanzen, Rynchosporium sp. (z.B. R. secalis) an Reis und Getreide, Sclerotinia Arten (z.B. S. sclerotiorum) an Raps, Sonnenblumen und anderen Pflanzen, Septoria tritici und Stagonospora nodorum an Weizen, Erysiphe (syn. Uncinulanecator) an Weinrebe, Setospaeria Arten an Mais und Rasen, Sphacelotheca reilinia an Mais, Thievaliopsis Arten an Sojabohnen und Baumwolle, Tilletia Arten an Getreide, Ustilago Arten an Getreide, Mais und Zuckerrübe, und Venturia Arten (Schorf) an Apfel und Birne (z.B. V. inaequalis an Apfel). Alternaria species on vegetables, oilseed rape, sugar beets, soybeans, cereals, cotton, fruit and rice (e.g. A. solani or A. alternata on potatoes and other plants), Aphanomyces species on sugar beets and vegetables, Ascochyta sp. on cotton and rice, bipalaris and turner species on maize, cereals, rice and turf (e.g. teres on barley, D. tritci-repentis on wheat), Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, Vegetables, flowers and vines, Botryodiplodia sp. on cotton, Bremia lactucae on lettuce, Cerospora species on maize, soybeans, rice and sugar beets (e.g. C. beticula on sugar beets), Cochliobolus species on maize, cereals, rice (e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice), Corynespora sp . on soybeans, cotton and other plants, Colletotrichum species on soybeans, cotton and other plants (e.g. C. acutatum on various plants), Curvularia sp. on cereals and rice, Diplodia sp. on cereals and rice, Exserohilum species on maize, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber plants, Fusarium and Verticillium species (e.g. V. dahliae) on various plants (e.g. F. graminearum on wheat), Gaeumanomyces graminis on cereals, Gibberella species on cereals and rice (e.g. Gibberella fujikuroi on rice), grainstaining complex on rice, Helminthosporium species (e.g. H. graminicola) on corn and rice, Macrophomina sp. on soya and cotton, Michrodochium sp. (eg M. nivale on cereals), Mycosphaerella species on cereals, bananas and peanuts (M. graminicola on wheat, M. fijiesis on banana), Phaeoisaripsis sp. on soybeans, Phakopsara sp. (eg P. pachyrhizi and P. meibomiae on soybeans), Phoma sp. on soybeans, Phomopsis species on soybeans, sunflowers and vines (P. viticola on vines, P. helianthii on sunflowers), Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Penecilium sp. on soya and cotton, Podosphaera leucotricha on apple, Pseudocercosporella herpotrichoides on cereals, Pseudoperonospora species on hops and cucumbers (e.g. P. cubenis on cucumber), Puccinia species on cereals, corn and asparagus (P. triticina and P. striformis on wheat, P .asparagi on asparagus), Pyrenophora spp. on cereals, Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice, Pyricularia grisea on turf and cereals, Pythium spp. on turf, rice, corn, cotton, rape, sunflower, sugar beet, vegetables and other plants, Rhizoctonia axes (e.g. R. solani) on cotton, rice, potato, turf, corn, rape, potato, sugar beet, vegetables and others plants, Rynchosporium sp. (e.g. R. secalis) on rice and cereals, Sclerotinia species (e.g. S. sclerotiorum) on oilseed rape, sunflowers and other plants, Septoria tritici and Stagonospora nodorum on wheat, Erysiphe (syn. Uncinulanecator) on grapevines, Setospaeria species on maize and turf , Sphacelotheca reilinia on corn, Thievaliopsis spp. on soybeans and cotton, Tilletia spp. on corn, Ustilago spp. on corn, corn and sugar beet, and Venturia spp. (scab) on apple and pear (eg V. inaequalis on apple).
Die erfmdungsgemäßen Formulierungen können unverdünnt oder mit Wasser verdünnt appliziert werden. In der Regel werden sie mit wenigstens einem Teil Wasser, bevorzugt mit 10 Teilen Wasser und besonders bevorzugt mit wenigstens 100 Teilen Wasser, beispielsweise mit 1 bis 10.000, vorzugsweise 10 bis 5.000 und ganz besonders bevorzugt mit 50 bis 24000 Teilen Wasser bezüglich eines Teiles der Formulierung verdünnt. The formulations according to the invention can be applied undiluted or diluted with water. As a rule, they are mixed with at least one part of water, preferably with 10 parts of water and particularly preferably with at least 100 parts of water, for example with 1 to 10,000, preferably 10 to 5,000 and very particularly preferably with 50 to 24,000 parts of water based on one part of the formulation diluted.
Ebenfalls Gegenstand der vorliegenden Erfindung ist eine Emulsion erhältlich durch Mischen von Wasser mit der erfmdungsgemäßen flüssigen Formulierung. Das Mischungsverhältnis von Wasser zu Emulsionskonzentrat kann im Bereich von 1000 zu 1 bis 1 zu 1, bevorzugt 400 zu 1 bis 10 zu 1 betragen.The subject of the present invention is also an emulsion obtainable by mixing water with the liquid formulation according to the invention. The mixing ratio of water to emulsion concentrate can be in the range from 1000:1 to 1:1, preferably 400:1 to 10:1.
Die Verdünnung wird erreicht, indem die erfmdungsgemäßen Emulsionskonzentrate zu dem Wasser gegossen werden. Zur raschen Vermischung des Konzentrats mit Wasser wird üblicherweise Agitation,
wie beispielsweise Rühren, eingesetzt. Allerdings ist eine Agitation in der Regel nicht notwendig. Obwohl die Temperatur für den Verdünnungsvorgang ein unkritischer Faktor ist, werden Verdünnungen üblicherweise bei Temperaturen im Bereich von 0°C bis 50°C, insbesondere bei 10°C bis 30°C oder bei Umgebungstemperatur durchgeführt. The dilution is achieved by pouring the emulsion concentrates according to the invention to the water. Agitation, such as stirring. However, agitation is usually not necessary. Although temperature is not a critical factor in the dilution process, dilutions are usually carried out at temperatures in the range 0°C to 50°C, more preferably 10°C to 30°C, or at ambient temperature.
Das zum Verdünnen eingesetzte Wasser ist in der Regel Leitungswasser. Das Wasser kann aber bereits wasserlösliche oder feindispergierte Verbindungen beinhalten, die im Pflanzenschutz verwendet werden, wie etwa Nährstoffe, Düngemittel oder Pestizide. The water used for dilution is usually tap water. However, the water can already contain water-soluble or finely dispersed compounds that are used in plant protection, such as nutrients, fertilizers or pesticides.
Zu der erfindungsgemäßen Emulsion können als Vormischung oder gegebenenfalls erst kurz vor der Verwendung (Tank-Mix) verschiedene Arten von Ölen, Netzmitteln, Adjuvantien, Düngemitteln oder Mikronährstoffen sowie weitere Pestizide (z.B. Herbizide, Insektizide, Fungizide, Wachstumsregulatoren, Safener) hinzugefügt werden. Diese Mittel können den erfindungsgemäßen Formulierungen im Gewichtsverhältnis 1: 100 bis 100: 1, bevorzugt 1: 10 bis 10: 1, zugemischt werden. Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the emulsion according to the invention as a premix or, if appropriate, only shortly before use (tank mix). These agents can be added to the formulations according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
Der Verwender appliziert die erfindungsgemäße Formulierung üblicherweise aus einem Vordosierungsgerät, einer Rückenspritze, einem Spritztank, einem Spritzflugzeug oder einem Bewässerungssystem, üblicherweise wird die erfmdungsgemäße Formulierung mit Wasser, Puffer und/oder weiteren Hilfsstoffen auf die gewünschte Ausbringungskonzentration verdünnt, wodurch man die gebrauchsfertige Spritzflüssigkeit bzw. agrochemische Zusammensetzung der Erfindung erhält. Üblicherweise werden pro Hektar landwirtschaftlicher Nutzfläche 20 bis 2000 Liter, bevorzugt 50 bis 400 Liter, der gebrauchsfertigen Spritzbrühe ausgebracht. The user usually applies the formulation according to the invention from a pre-dosing device, a knapsack sprayer, a spray tank, a spray plane or an irrigation system; the formulation according to the invention is usually diluted to the desired application concentration with water, buffer and/or other auxiliary substances, as a result of which the ready-to-use spray liquid or Agrochemical composition of the invention. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray mixture are applied per hectare of agricultural land.
Die erforderlichen Aufwandmengen der reinen Wirkstoffe ohne Formulierungshilfsstoffe hängen von der Intensität des Schädlingsbefalls, von der Entwicklungsphase der Pflanzen, von den klimatischen Bedingungen des Einsatzortes und dem Applikationsverfahren ab. Im Allgemeinen liegt die Aufwandmenge im Bereich von 0,001 bis 3 kg, bevorzugt von 0,005 bis 2 kg, besonders bevorzugt von 0,01 bis 1 kg und ganz besonders bevorzugt von 50 bis 500 g Wirkstoff pro Hektar, wobei Wirkstoff hier Prothioconazole zuzüglich möglicher weiterer Wirkstoffe bedeutet. The required application rates of the pure active ingredients without formulation auxiliaries depend on the intensity of the pest infestation, the development phase of the plants, the climatic conditions at the place of use and the application method. In general, the application rate is in the range from 0.001 to 3 kg, preferably from 0.005 to 2 kg, particularly preferably from 0.01 to 1 kg and very particularly preferably from 50 to 500 g of active ingredient per hectare, the active ingredient here being prothioconazole plus possible other active ingredients means.
Die in der Regel verdünnten Formulierungen der Erfindung werden hauptsächlich durch Besprühen, insbesondere Besprühen der Blätter, appliziert. Die Applikation kann mit dem Fachmann bekannten Sprühtechniken, beispielsweise unter Verwendung von Wasser als Träger und Spritzbrühenmengen von etwa 50 bis 1 000 Litern pro Hektar, beispielsweise von 100 bis 00 Litern pro Hektar, durchgeführt werden. The generally diluted formulations of the invention are applied primarily by spraying, especially foliar spraying. The application can be carried out using spraying techniques known to those skilled in the art, for example using water as the carrier and amounts of spray mixture of about 50 to 1000 liters per hectare, for example from 100 to 00 liters per hectare.
Die neuen Prothioconazole -haltigen Formulierungen verfügen über vorteilhafte Eigenschaften für die Behandlung von Pflanzen, insbesondere zeichnen sie sich durch gute Anwendungseigenschaften, hohe Stabilität und hohe fungizide Aktivität aus.
Die Erfindung wird durch die Beispiele näher erläutert ohne sie darauf zu beschränken.
The new formulations containing prothioconazole have advantageous properties for the treatment of plants, in particular they are distinguished by good application properties, high stability and high fungicidal activity. The invention is explained in more detail by the examples without being restricted thereto.
Beispiele examples
Verwendete Einsatzstoffe: Materials used:
Die in den nachfolgenden Beispielen verwendeten Begriffe haben folgende Bedeutung: The terms used in the following examples have the following meanings:
Prothioconazol PTZ (Bayer AG) Prothioconazole PTZ (Bayer AG)
Atlox Metasperse 500 Croda, Acrylat-basiertes Co-Polymer Atlox Metasperse 500 Croda, acrylate based co-polymer
Vitamin E Sigma-Aldrich, alpha-Tocopherol Vitamin E Sigma-Aldrich, alpha-tocopherol
Pluronic PE 10500 Propylenoxid-Ethylenoxid-(PO-EO)-Blockpolymer (BASF) Pluronic PE 10500 propylene oxide ethylene oxide (PO-EO) block polymer (BASF)
Rhodopol® 23 Xanthan Derivat (Solvay) Rhodopol® 23 Xanthan Derivative (Solvay)
Silcolapse® 426 Silikon-Entschäumer (Solvay) Silcolapse® 426 Silicone Defoamer (Solvay)
Proxel® GXL Konservierungsmittel (Biozid, Proxel) Proxel® GXL Preservative (Biocide, Proxel)
Lucramul® CO30 Nichtionischer Emulgator, Rizinusöl ethoxyliert , Levaco Chemicals, DELucramul® CO30 Nonionic Emulsifier, Castor Oil Ethoxylated, Levaco Chemicals, DE
SAG 1572 Wässrige Emulsion von Polydimethylsiloxan Momentive® SAG 1572 Aqueous emulsion of polydimethylsiloxane Momentive®
Genagen® 4296 Di-Methyl-Decanamid (DAA), Clariant Genagen® 4296 dimethyl decanamide (DAA), Clariant
Hallcomid® 1025 N,N-Dimethyl 9-decenamid, CAS Nummer: 1356964-77-6 Hallcomid® 1025 N,N-dimethyl 9-decenamide, CAS number: 1356964-77-6
Allgemeine Herstellung eines wässrigen Suspensionskonzentrats (SC): General Preparation of an Aqueous Suspension Concentrate (SC):
Es wird zunächst Wasser bei Raumtemperatur vorgelegt. Unter Rühren werden die Wirkstoffe sowie die weiteren Komponenten hinzugegeben (ohne besondere Reihenfolge). Es erfolgt eine Vorzerkleinerung mit einer Kolloidmühle, gefolgt von einer Nassvermahlung beispielsweise mittels einer Perlmühle. Abschließend wird der organische Verdicker zugegeben. Water at room temperature is initially introduced. The active ingredients and the other components are added while stirring (in no particular order). Pre-comminution takes place using a colloid mill, followed by wet grinding, for example using a bead mill. Finally, the organic thickener is added.
Allgemeine Herstellung eines Emulsionskonzentrates (EC) General Preparation of an Emulsion Concentrate (EC)
Das organische Lösemittel wird vorgelegt. Unter Rühren werden anschließend alle Komponenten hinzugegeben (ohne besondere Reihenfolge). Es wird solange gerührt, bis eine klare Lösung entsteht. The organic solvent is presented. All components are then added while stirring (in no particular order). It is stirred until a clear solution is formed.
-2-01
Die Baumwollproben wurden mit Acetonitril (enthaltend 20mg/L Cysteinhydrochlorid) extrahiert und vor der Analyse tiefgefroren. -2-01 The cotton samples were extracted with acetonitrile (containing 20 mg/L cysteine hydrochloride) and deep-frozen prior to analysis.
2-(l-Chlorocyclopropyl)-l-(2-chlorophenyl)-3-(lH-l,2,4-triazol-l-yl)propan-2-ol wird von den Formulierbestandteilen auf einer Umkehrphasensäule unter Verwendung eines isokratischen Laufmittels getrennt. Nach der MS/MS Detektion, wird die quantitative Auswertung durch Vergleich der Peakflächen mit denen des Referenzgegenstandes, unter Verwendung eines externen Standards durchgeführt. 2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol is separated from the formulating ingredients on a reverse phase column using an isocratic eluent Cut. After the MS/MS detection, the quantitative evaluation is performed by comparing the peak areas with those of the reference object using an external standard.
Hochdruckflüssigkeitschromatograph : HP 1090 High Pressure Liquid Chromatograph : HP 1090
Probeninjektion : HP 1090 Autoinjector Sample injection : HP 1090 Autoinjector
Massenspektrometer : Quattro I, Fisons Mass spectrometer : Quattro I, Fisons
Integration und Auswertung MassLynx von Micromass Integration and evaluation MassLynx from Micromass
Die Proben werden jeweils, soweit nicht anders angegeben, Licht ausgesetzt und 4 Wochen gelagert. Unless otherwise stated, the samples are exposed to light and stored for 4 weeks.
Es wurden drei Verdünnungen jeder Formulierung enthaltend 62,5 g/L, 2 g/L und 0,2 g/L PTZ hergestellt.Three dilutions of each formulation containing 62.5 g/L, 2 g/L and 0.2 g/L PTZ were prepared.
Die tatsächliche PTZ-Konzentration in den konzentrierten Formulierungen ist 125 g/L. The actual PTZ concentration in the concentrated formulations is 125 g/L.
Jede der drei Verdünnungen wurde auf 10 auf Karton aufgespannte Baumwollquadrate gesprüht, wobei als Kontrolle lediglich 6 Baumwollquadrate besprüht wurden. Each of the three dilutions was sprayed onto 10 cotton squares mounted on cardboard, with only 6 cotton squares being sprayed as a control.
Nach dem Besprühen wurden die Kartons mit den Baumwollquadraten unter einer Tageslichtlampe plaziert. Je 5 der Baumwollquadrate wurden 1h und 6h nach dem Besprühen analysiert, wobei die
Baumwollproben nach oben beschriebener Methode analysiert wurden. Die Analyte (PTZ und Desthio) wurden via HPLC-MS bestimmt. After spraying, the cartons of cotton squares were placed under a daylight lamp. 5 each of the cotton squares were analyzed 1 hour and 6 hours after spraying, with the Cotton samples were analyzed using the method described above. The analytes (PTZ and Desthio) were determined via HPLC-MS.
Das Ergebnis der Auswertung ist in Figur 1 dargestellt (Prosare = Bsp. 1 Vergleich). The result of the evaluation is shown in FIG. 1 (Prosare=example 1 comparison).
Wie das Ergebnis zeigt, ist bei allen Formulierungen und allen Verdünnungen der Abbau von PTZ zu Desthio zeitabhängig. Die Umwandlungsraten auf den Baumwollproben steigen von 1h nach dem Besprühen zu 6h nach dem Besprühen an. Die Umwandlungsrate ist ebenso abhängig von der PTZ- Konzentration, wobei geringere Konzentrationen eine höhere Umwandlungsrate aufweisen. Der geringste PTZ-Abbau wurde in der Lösung mit 62,5 g/L PTZ festgestellt, während die 0,2 g/L Verdünnung den höchsten Abbau zeigte. As the result shows, the degradation of PTZ to Desthio is time-dependent for all formulations and all dilutions. The conversion rates on the cotton samples increase from 1 hour after spraying to 6 hours after spraying. The conversion rate is also dependent on the PTZ concentration, with lower concentrations exhibiting a higher conversion rate. The lowest PTZ degradation was observed in the 62.5 g/L PTZ solution, while the 0.2 g/L dilution showed the highest degradation.
Einen besonders gute Stabilisierung von PTZ auf den Oberflächen zeigte Vitamin E (Tocopherol).
Vitamin E (tocopherol) showed a particularly good stabilization of PTZ on the surfaces.
Claims
1. Verwendung von Decenamid und/oder Tocopherolen zur Stabilisierung von Thionen auf Oberflächen. 1. Use of decenamide and/or tocopherols to stabilize thiones on surfaces.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, Tocopherol verwendet wird. 2. Use according to claim 1, characterized in that tocopherol is used.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Thion Prothioconazole ist. 3. Use according to claim 1 or 2, characterized in that the thione is prothioconazole.
4. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß Thione aus agrochemischen Formulierungen auf Oberflächen stabilisiert werden. 4. Use according to any one of the preceding claims, characterized in that thiones from agrochemical formulations are stabilized on surfaces.
5. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Oberfläche eine Blattoberfläche ist. 5. Use according to any one of the preceding claims, characterized in that the surface is a leaf surface.
6. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Oberfläche ein Baumwollgewebe ist.
6. Use according to any one of the preceding claims, characterized in that the surface is a cotton fabric.
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2021
- 2021-09-17 EP EP21778415.6A patent/EP4213627A1/en active Pending
- 2021-09-17 CA CA3195732A patent/CA3195732A1/en active Pending
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