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EP2557917A1 - Uv absorber for reducing the e/z isomerization of pesticides - Google Patents

Uv absorber for reducing the e/z isomerization of pesticides

Info

Publication number
EP2557917A1
EP2557917A1 EP11714762A EP11714762A EP2557917A1 EP 2557917 A1 EP2557917 A1 EP 2557917A1 EP 11714762 A EP11714762 A EP 11714762A EP 11714762 A EP11714762 A EP 11714762A EP 2557917 A1 EP2557917 A1 EP 2557917A1
Authority
EP
European Patent Office
Prior art keywords
absorber
isomer
pesticide
double bond
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11714762A
Other languages
German (de)
French (fr)
Inventor
Michael Ishaque
Vijay Narayanan Swaminathan
Sylke Haremza
Claude Taranta
William Baxter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11714762A priority Critical patent/EP2557917A1/en
Publication of EP2557917A1 publication Critical patent/EP2557917A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34Nitriles

Definitions

  • UV absorber to reduce the E / Z isomerization of pesticides
  • the present invention is the use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond. Furthermore, it relates to a composition comprising an E and / or a Z isomer of a pesticide containing a double bond and a UV absorber. Combinations of preferred features with other preferred features are encompassed by the present invention.
  • Agrochemical active substances such as pesticides are exposed to sunlight, especially after application in the open field. This results in some agents to reduce their pesticides effectiveness.
  • Metaflumizone loses its efficacy upon exposure to light (Takagi et al., Veterinary Parasitology, 2007, 150, 177-181).
  • Metaflumizone can exist as an E and a Z isomer, with the E isomer having up to 10 times higher pesticidal activity than the Z isomer.
  • Light irradiation leads to isomerization of the originally applied E isomer to the Z isomer.
  • the object of the present invention was to suppress the E / Z isomerization of agrochemical active substances, such as metaflumizone. Another task was to find a cost-effective method for doing so.
  • the object has been achieved by the use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond.
  • E / Z isomerization is usually understood to mean the conversion of a double bond from the E isomer to the Z isomer or from the Z isomer to the E isomer.
  • E / Z isomerization usually occurs in unsymmetrically substituted double bonds, ie in double bonds, which may be present as E-isomer and as Z-isomer.
  • Pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners, pheromones and / or growth regulators.
  • Preferred pesticides are fungicides, insecticides and herbicides. Also, mixtures of pesticides of two or more of the above classes may be used.
  • Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flavinamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz,
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides , Dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones,
  • Suitable herbicides are herbicides of the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones , Nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates
  • Pesticides containing a double bond are usually those pesticides containing a CC double bond and / or a CN double bond. Usually the double bond is isolated from another multiple bond or conjugated to another multiple bond.
  • Preferred pesticides containing a double bond are abamectin, acetamiprid, acrinathrin, azoxystrobin, bifenthrin, butoxycarboxim, chlorfenvinfos, cyhalothrin, 1, 3 dichloropropene, dicrotophos, dimethomorph, diniconnazol, emamectin, empenthrin, fenpyroximate, flucycloxuron, flumethrin, flumorph, fluoxastrobin, hydroprene, Ki - noprene, kresoxim-methyl, lambda cyhalothrin, metaflumizone, metominostrobin, metoprene, mevinphos,
  • pesticides containing a double bond are abamectin, acetamiprid, azoxystrobin, bifenthrin, cyhalothrin, dimethomorph, diniconnazole, ememectin, flucycloxuron, fluoxastrobin, kresoxim-methyl, lambda cyhalothrin, metaflumizone, picoxystrobin, trifloxystrobin, triflumizole, and triticonazole.
  • pesticide containing a double bond is metaflumizone.
  • pesticides containing a double bond are suitable, wherein the E or the Z isomer of the pesticide has a higher activity than the respective other isomer.
  • the term "higher effectiveness" refers each on a specific biological activity in a particular target organism. These efficiencies of the E and Z isomers of the pesticide are mostly known from the literature. Higher efficacy is considered to be present if one of the isomers has an activity which is at least 1, 1-fold (preferably at least 2-fold, more preferably at least 4-fold) the activity of the other isomer.
  • the E or Z isomer of the pesticide containing a double bond is preferably at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of E- and Z-isomers of the pesticide. These values refer to the time when the UV absorber is mixed with the pesticide.
  • UV absorber refers to all chemical compounds that can absorb UV light.
  • the UV absorber can scatter UV light (such as inorganic UV absorbers) or absorb it. In most cases, the extinction coefficient of the UV absorber of UV light is greater than the extinction coefficient of the pesticide at the same wavelength.
  • the UV absorbers may be oil-soluble or water-soluble. They may also be present in polymers, for example as copolymerized.
  • the UV absorbers may be UV-A absorbers, UV-B absorbers, broadband absorbers (i.e., UV-A and UV-B), or optical brighteners.
  • the UV absorber can be used in pure form, as a technical mixture, or as a mixture of different UV absorbers. Preference is given to UV absorbers having a solubility in water at 20 ° C. of at least 0.01 g / L, preferably at least 0.1 g / L, and particularly preferably at least 1 g / L.
  • the UV absorber is water-soluble.
  • the composition contains a further UV absorber, wherein the further UV absorber is oil-soluble.
  • at least one UV absorber is water-soluble and at least one UV absorber is oil-soluble.
  • water-soluble UV absorbers are suitable having a solubility in water at 20 ° C. of at least 5.0 g / l, preferably at least 10.0 g / l, more preferably at least 50 g / l, and especially at least 100 g / l.
  • the further oil-soluble UV absorber usually has a solubility in water at 20 ° C. of below 5.0 g / l, preferably below 1.0 g / l, more preferably below 0.5 g / l, and especially below 0.1 g / l.
  • Inorganic UV absorbers are likewise suitable oil-soluble UV absorbers in the context of this application.
  • Suitable UV absorbers are, for example: A) Benzotriazoles, such as 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Tinuvin® 900, BASF SE), [3- [3- ( 2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1 -oxopropyl] -w- [3- [3- (2-benzotriazol-2-yl) -5- (1, 1-dimethyl-ethyl) -4-hydroxyphenyl] -1-oxopropoxy] poly (oxy-1,2-ethanediyl) (Tinuvin® 1 130, BASF SE), 6-tert-butyl-2- (5-chloro-1-one) 2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® 326, BASF SE), 2,4
  • cyanoacrylates such as 2-cyano-3-phenylcinnamate ethyl ester (Uvinul ® 3035, BASF SE), 2-cyano-3,3-diphenylacrylate 2'-ethylhexyl ester or 2-ethylhexyl-2-cyano-3-phenylcinnamate ( Octocrylene, Uvinul ® 539 T, Uvinul 3039, BASF SE);
  • PABA Para-aminobenzoic acid
  • esters such as ethyl-PABA, ethoxylated PABA, ethyl-dihydroxypropyl-PABA, glycerol-PABA, 2-ethylhexyl
  • esters of salicylic acid such as 2-ethylhexyl salicylate, 4-lsopropylbenzyl salicylate, homomenthyl salicylate, TEA salicylate (Neo Heliopan TS ®, Haarmann and Reimer), Dipropyleneglycol salicylate;
  • esters of cinnamic acids such as 2-ethylhexyl 4-methoxycinnamate (Uvinul® MC 80), octyl-p-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, conoxates, diisopropyl methyl cinnamate, etocrylene (Uvinul® N 35, BASF SE );
  • benzophenone such as 2-hydroxy-4-methoxybenzophenone (Uvinul® M 40, BASF SE), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2- Hexyl (4-diethylamino-2-hydroxybenzoyl) benzoate (Uvinul® A Plus, BASF SE), 4-n-octyloxy-2-hydroxybenzophenone (Uvinul® 3008, BASF SE), 2-hydroxybenzophenone derivatives such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy, 2'-hydroxy-4 , 4'-dimethoxy-2-hydroxybenzophenones, Sulfonkladerivative of benzophenones, such as 2-hydroxy-4-methoxybenzo-phenone-5-sulfonic acid (Uvinul® M 40, BASF
  • sulfonic acid Derivative of 3-Benzylidenecamphor, such as 4- (2-oxo-3-bornyl-idenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bionylidenes) - sulfonic acid and its salts;
  • esters of benzalmalonic acid such as 2-ethylhexyl 4-methoxybenzmalonate
  • triazine derivatives such as dioctylbutamidotriazone (Uvasorb® HEB, Sigma), 2,4,6-trinanilino-p- (carbo-2'-ethylhexyl-1'-oxy) -1, 3,5-triazine (Uvinul T 150, BASF SE), 2- [4 - [(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl ) -1, 3,5-triazine (Tinuvin® 405, BASF SE), anisotriazine (Tinosorb® S, BASF
  • propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;
  • N) aminohydroxy-substituted derivatives of benzophenones such as N, N-diethylaminohydroxybenzoyl-n-hexylbenzoate;
  • O) derivatives of stilbene for example salts of distyrylbiphenyl disulphonate, such as disodium dististylbiphenyl disulphonate (Uvitex® NFW, BASF SE), 2,2 '- [1,2-ethenediylbis [(3-sulfo-4,1-phenylene) imono [6- (diethylamino) -1, 3,5-triazine-4,2-diyl] imino]] bis-1,4-benzenedisulfonic acid hexasodium salt (Tinopal® SFP, BASF
  • inorganic UV absorbers for example those based on ZnO (like Z Cote ® products, BASF SE), Ti0 2 (such as T-Lite TM productions, BASF SE) or Ce0 2, as well as the UV absorber as described in WO 2009 / 153231, page 2, line 24 to page 6, line 18 described.
  • Preferred UV absorbers are those of the group F) (derivatives of benzophenone) and the group O) (derivatives of stilbene), particularly preferably 2-hydroxybenzophenone derivatives, sulfonic acid derivatives of benzophenones and salts of distyrylbiphenyl disulfonate, in particular 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, disodium distyrylbiphenyl disulfonate and 2-hydroxy-4-octoxybenzophenone.
  • UV absorbers are used. Preference is given to using a UV absorber from group A) to N) and a UV absorber from group O).
  • UV absorbers are used which contain a sulfonic acid group or a polyalkylene oxide group. Preference is given to UV absorbers which contain a sulfonic acid group. UV absorbers containing a sulfonic acid group are well known.
  • Examples are 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul ® MS 40, BASF SE) and its salts (for example, alkali salt such as sodium), 2,2'-dihydroxy-4,4'-dimethoxybenzophenon- 5 , 5'-sulfonic acid and its salts (eg alkali salt, such as sodium).
  • alkali salt such as sodium
  • 2,2'-dihydroxy-4,4'-dimethoxybenzophenon- 5 , 5'-sulfonic acid and its salts eg alkali salt, such as sodium
  • benzophenones which contain a sulfonic acid group (also called sulfonic acid derivative of benzophenones).
  • the sulfonic acid group may be in the acid form or as a salt, with the salt form being preferred.
  • UV absorbers containing a polyalkylene oxide group are well known.
  • the polyalkylene oxide group preferably contains ethylene oxide in polymerized form. At least 50 mol%, in particular at least 80 mol%, of the alkylene oxide groups are preferably ethylene oxide.
  • Examples are 4-bis (polyethoxy) 4-amino benzoic acid thoxyethyl polyether ester (Uvinul ® P 25, BASF SE).
  • the amount of UV absorber is usually 0.5 to 500 wt.% With respect to the amount of pesticide. It is preferably from 1 to 300% by weight, more preferably from 5 to 100% by weight and in particular from 5 to 80% by weight, in each case with respect to the amount of pesticide.
  • an antioxidant also referred to as antioxidant
  • an antioxidant is used in addition to the UV absorber.
  • Antioxidants having a solubility in water at 20 ° C. of at least 0.01 g / l, preferably at least 0.1 g / l, and particularly preferably at least 1 g / l, are preferred.
  • antioxidants are suitable having a solubility in water at 20 ° C. of at least 5.0 g / l, preferably at least 20 g / l, and particularly preferably at least 100 g / l.
  • Antioxidants are, for example, amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (e.g., urocanic acid), peptides such as e.g. D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg 6. ⁇ -carotene, ⁇ -carotene, lycopene) and their derivatives,
  • amino acids e.g., glycine, histidine, tyrosine, tryptophan
  • imidazole and imidazole derivatives e.g., urocanic acid
  • peptides such as e.g. D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine)
  • carotenoids eg
  • Lipoic acid and its derivatives eg dihydrolipoic acid), aurothioglucose,
  • Propylthiouracil and other thio compounds e.g., thioglycerol, thiosorbitol,
  • Glycosyl N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and salts thereof, dilauryl thiodipropionate, Distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages, further
  • Metal chelators e.g., ⁇ -hydroxy fatty acids, EDTA, EGTA, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g., citric acid, lactic acid, malic acid
  • humic acids
  • Bile acid bile extracts, gallic acid esters (eg propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and their derivatives, unsaturated fatty acids and their derivatives (eg ⁇ -linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and their derivatives, hydroquinone and its derivatives (eg arbutin), ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (eg ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphates, sodium and magnesium ascorbate , Disodium ascorbyl phosphate and sulfate,
  • gallic acid esters eg propyl, octyl and dodecyl gallate
  • flavonoids eg ⁇ -linolenic acid
  • antioxidants are vitamin C and its derivatives, tocopherols and their derivatives, monovalent copper salts, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 770), 2- (2H-benzotriazole) 2-yl) -6-dodecyl-4-methyl-phenol
  • the weight ratio of UV absorber to antioxidant is usually in the range of 1/10 to 100/1, preferably in the range of 1/5 to 10/1, more preferably in the range of 1/1 to 5/1.
  • the present invention further relates to a composition comprising an E and / or a Z isomer of a pesticide containing a double bond and a UV absorber. Suitable and preferred pesticides containing a double bond are present standing described.
  • the E-isomer or the Z-isomer of the pesticide is usually present at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of the E and Z isomers of the pesticide.
  • the isomer is present in excess, which has the higher pesticidal activity.
  • Suitable UV absorbers are as described above.
  • the UV absorber is a derivative of benzophenone or a derivative of stilbene.
  • at least two UV absorbers are used.
  • Suitable weight ratios of UV absorber to pesticide which is metaflumizone are as described above.
  • an antioxidant can be used as described above.
  • the E isomer of metaflumizone is usually present at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of the E and Z isomers of the metaflumizone.
  • the pesticides such as metaflumizone
  • composition types eg. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the type depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • composition types are suspensions (SC, OD, OESC), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, capsules (CS), wettable powders or dusts (WP, SP, SS, WS , DP, DS) or granules (GR, FG, GG, MG), which may be either water-soluble or dispersible, or LLIN (long-lasting insecticidal nets), baits for animals such as ants or rats.
  • the baits may be in various of the aforementioned composition types, preferably as powders, pastes, granules or gels.
  • composition types eg SC, EC OD, WG, SG, WP, SP, SS, WS,
  • Composition types such as DP, DS, GR, FG, GG, MG or bait are generally used undiluted.
  • Preferred types of compositions are suspensions.
  • aqueous composition types are suitable, such as aqueous suspension concentrates, or oil-containing suspension concentrates
  • the pH of the aqueous composition types is usually greater than 1.0, more preferably greater than 3.0, and particularly preferably greater than 3.5.
  • the pH is usually below 6.0, preferably below 5.0, and more preferably below 4.5. Suitable ranges for the pH are, for example, 2.5 to 5.5, preferably 3.0 to 5.0.
  • the UV absorber and / or the antioxidants can already be brought into contact with the pesticide during the preparation of the agrochemical formulation.
  • the agrochemical formulations may furthermore also contain auxiliaries customary for crop protection agents, the choice of auxiliaries being directed to the specific application form or the active substance.
  • auxiliaries are solvents, solid carriers, surface-active substances (such as further solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate dyes and adhesives (for example for seed treatment) or customary Aid for bait formulation (eg attractants, feeds, bitter substances).
  • Suitable solvents include water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
  • Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nut
  • surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulf
  • thickeners ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion
  • thickeners are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ®, CP Kelco, U.S.A.), Rhodopol ® 23 (Rho dia, France) or Veegum ® (RT Vanderbilt, USA) or attaclay ® (Engelhard Corp., NJ, USA).
  • Bactericides may be added to stabilize the composition.
  • bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ® MBS from Thor Chemie).
  • Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
  • defoamers examples include silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • the agrochemical formulations may be used in the form of their compositions, e.g. B. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, misting, dusting, scattering, laying bait, painting, dipping or pouring are applied.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • the active substances or the compositions containing them may contain oils of various types, wetting agents, adjuvants, herbicides, bactericides, other fungicides and / or pesticides, if appropriate also immediately before Application (ie as a tank mix) to be added. These agents can be mixed into the compositions in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • the UV absorber and / or the antioxidants can also be brought into contact with the pesticide only immediately before use (ie as a tank mix).
  • adjuvants in this sense are in particular: organically modified polysiloxanes, eg. B. Break Thru S 240®; Alcohol alkoxylates, eg. Atplus® 245, Atplus® MBA 1303, Plurafac® LF 300 and Lutensol® ON 30; EO-PO block polymerizates, eg. Pluronic® RPE 2035 and Genapol® B; Alcohol ethoxylates, eg. Eg Lutensol® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen® RA.
  • organically modified polysiloxanes eg. B. Break Thru S 240®
  • Alcohol alkoxylates eg. Atplus® 245, Atplus® MBA 1303, Plurafac® LF 300 and Lutensol® ON 30
  • EO-PO block polymerizates eg. Pluronic® RPE 2035 and Genapol® B
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the application rates in the application in crop protection depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha. In the treatment of plant propagation materials, eg. B. State, are generally used amounts of active ingredient from 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of propagating material or seed. When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
  • the present invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to the invention on the respective pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
  • the present invention has many advantages: the rate of E / Z isomerization is significantly reduced.
  • the applied isomer stays active longer in sunlight.
  • the rate of application of the active substance, such as metaflumizone can be reduced.
  • the applied drug has a significantly longer residual effect because the applied active isomer is converted more slowly into the less active isomer.
  • the practice of the invention is readily practicable industrially, as the UV absorber can be easily contacted with the pesticide during preparation of the agrochemical formulation, or immediately before use by the user as a tank mix.
  • the addition of antioxidants can kung of the UV absorber to reduce the E / Z isomerization further increased.
  • Water-soluble UV absorbers are particularly advantageous, since such compositions are very stable on storage, and can also easily be added by the user as a tank mix (since the absorber dissolves easily in the aqueous tank mix and distributes it evenly). Water-soluble UV absorbers are easier to incorporate into the formulation, since they are simply added to the aqueous formulation, while, for example, water-insoluble UV absorbers must be ground separately with the active ingredient.
  • the following examples illustrate the invention without limiting it.
  • Metaflumizone SC aqueous suspension concentrate containing 240 g / l (22.2 wt.%) Of metaflumizone, 2 wt.% Of sodium dioctylsulfosuccinate, 3.5 wt.% Of ethoxylated Cg-
  • UV absorbers used (all commercially available from BASF SE):
  • Uvinul® 4050H N, N'-bisformyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine
  • Tinuvin® 770 bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate
  • Tinuvin® 171 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol
  • Z-Cote® zinc oxide, micronised
  • Metaflumizone SC was mixed with a certain amount (in each case% by weight with respect to metaflumizone) of the UV absorber and / or stabilizer, diluted with water in a weight ratio of 1:18 and stirred for one hour at room temperature.
  • Example 2 20 mg of the mixture prepared in Example 1 was dropped on a glass plate and allowed to dry at room temperature for one hour. Then, the sample was irradiated with UV light for 0, 30, and 120 minutes, respectively (Sun Test CPS +, Atlas Co., 750 watts, wavelength 300 to 800 nm). The sample was removed from the glass plate after irradiation with 2.0 ml Washed off DMSO and homogenized with stirring and by means of ultrasound (15 s). The sample was fractionated by means of UPLC (Ultra Performance Liquid Chromatography, BEH C18 column, detection at 225 nm) into the E and Z isomers of metaflumizone and quantitated over the peak areas. The proportion of E-isomer is indicated in each case and the proportion of Z-isomer corresponds to 100% less the proportion E-isomer.
  • UPLC Ultra Performance Liquid Chromatography, BEH C18 column, detection at 225 nm
  • Example 1 The mixtures were prepared as in Example 1 and tested as in Example 2 (Table 1). It has been shown that a wide variety of UV absorbers reduce E / Z isomerization compared to a mixture that does not contain a UV absorber.
  • Example 4 Mixture of UV absorbers with antioxidants or with further UV absorbers
  • Example 2 The blends were prepared as in Example 1 and tested as in Example 2 (Table 2). It has been shown that mixtures of UV absorbers with antioxidants (such as tocopherol, ascorbic acid, Uvinul 4050H, Tinuvin 770) or with other UV absorbers (such as Z-Cote) reduce E / Z isomerization compared to a mixture containing does not contain a UV absorber.
  • antioxidants such as tocopherol, ascorbic acid, Uvinul 4050H, Tinuvin 770
  • other UV absorbers such as Z-Cote
  • An aqueous suspension concentrate of metaflumizone was prepared by mixing and milling the following components: 180 g / l metaflumizone, 27 g / l sodium diol sulfosuccinate, 54 g / l propylene glycol, 1 g / l xanthan gum, 33 g / l ethoxylated tristy rylphenol.
  • Water-insoluble UV absorbers or stabilizers were added before milling, while water-soluble UV absorbers or stabilizers were added after grinding and dissolved with stirring. The amount of UV absorber or stabilizer was in each case given in% by weight with respect to metaflumizone.
  • the particle size was D90 ⁇ 2.0
  • Example 5 The suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 3). The results with formulations prepared according to Example 5 were shown to be as good as the formulations prepared by simple mixing in Example 1.
  • Example 5 The suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 4).
  • the 1:18 dilution with water in Example 2 resulted in a formulation in water of 5%.
  • the content was reduced even further here to 1% by more dilution with water.
  • This dilution corresponds to a dilution, which is customary in practice, of a commercial active substance concentrate in order to obtain the spray-ready tank mixture. It has also been shown that the diluted formulations also reduce E / Z isomerization.
  • Example 8 field trials of white cabbage
  • An aqueous suspension concentrate "SC-A" of metaflumizone was prepared by mixing and milling the following components: 180 g / l of metaflumizone, 22 g / l of sodium dioctylsulfosuccinate, 35 g / l of ethoxylated Cg-n-alcohol, 30 g / l of polyarylphenolethoxy lat, 1 g / l xanthan gum (thickener), and 50 g / l alkanediol (antifreeze).
  • An aqueous suspension concentrate "SC-A + UV1" was prepared from SC-A by adding 108 g / L of Uvinul® MS 40.
  • An aqueous suspension concentrate "SC-A + UV2" was prepared from SC-A by adding 25 g / L of Uvinul® MS 40.
  • An aqueous suspension concentrate "SC-A + UV3" was prepared from SC-A by adding 50 g / L of Uvinul® MS 40.
  • SC-A + UV4 An aqueous suspension concentrate "SC-A + UV4" was prepared from SC-A by adding 108 g / l Uvitex® NFW and white cabbage was grown on a field test in the phillipines at a rate of 160 g metaflumizone per ha After 14 days, the cumulative feeding damage was assessed by Crocidolomia binotalis ( belle 5). Due to the addition of UV absorber, the active ingredient had a longer efficacy.
  • White cabbage was grown on a test field in California. The field was sprayed at a rate of 160 g metaflumizone per ha with the suspension concentrations according to Example 8. After 14 days, the mortality of the larvae of Lepidoptera was subsequently determined (Table 6). Due to the addition of UV absorber, the active ingredient had a longer efficacy.
  • Example 1 1 UV chamber lima bean

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Abstract

The present invention relates to the use of a UV absorber for reducing the E/Z isomerization of pesticides containing a double bond. The invention further relates to a composition comprising an E isomer and/or a Z isomer of a pesticide containing a double bond, and to a UV absorber.

Description

UV-Absorber zur Verringerung der E/Z-Isomerisierung von Pestiziden  UV absorber to reduce the E / Z isomerization of pesticides
Gegenstand der vorliegenden Erfindung ist die Verwendung eines UV-Absorbers zur Verringerung der E/Z-Isomerisierung von Pestiziden enthaltend eine Doppelbindung. Weiterhin betrifft sie eine Zusammensetzung umfassend ein E- und/oder ein Z-Isomer eines Pestizids enthaltend eine Doppelbindung und einen UV-Absorber. Kombinationen bevorzugter Merkmale mit anderen bevorzugten Merkmalen werden von der vorliegenden Erfindung umfasst. Agrochemische Wirkstoffe wie Pestizide sind besonders nach der Applikation im freien Feld der Sonneneinstrahlung ausgesetzt. Dies führt bei einigen Wirkstoffen zur Verringerung ihrer Pestiziden Wirksamkeit. The present invention is the use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond. Furthermore, it relates to a composition comprising an E and / or a Z isomer of a pesticide containing a double bond and a UV absorber. Combinations of preferred features with other preferred features are encompassed by the present invention. Agrochemical active substances such as pesticides are exposed to sunlight, especially after application in the open field. This results in some agents to reduce their pesticides effectiveness.
So wurde festgestellt, dass beispielsweise Metaflumizon durch Lichteinstrahlung seine Wirksamkeit verliert (Takagi et al., Veterinary Parasitology, 2007, 150, 177-181 ). Metaflumizon kann als E- und als Z-Isomer vorliegen, wobei das E-Isomer eine bis zu10- fach höhere Pestizide Wirksamkeit hat als das Z-Isomer. Durch Lichteinstrahlung kommt es zur Isomerisierung des ursprünglich applizierten E-Isomers zum Z-Isomer. For example, it has been found that metaflumizone loses its efficacy upon exposure to light (Takagi et al., Veterinary Parasitology, 2007, 150, 177-181). Metaflumizone can exist as an E and a Z isomer, with the E isomer having up to 10 times higher pesticidal activity than the Z isomer. Light irradiation leads to isomerization of the originally applied E isomer to the Z isomer.
Aufgabe der vorliegenden Erfindung war, die E/Z-Isomerisierung von agrochemischen Wirkstoffen, wie Metaflumizon, zu unterdrücken. Eine weitere Aufgabe war, ein kostengünstiges Verfahren dafür zu finden. Die Aufgabe wurde gelöst durch die Verwendung eines UV-Absorbers zur Verringerung der E/Z-Isomerisierung von Pestiziden enthaltend eine Doppelbindung. Unter einer E/Z-Isomerisierung versteht man üblicherweise die Umwandlung einer Doppelbindung vom E-Isomer in das Z-Isomer oder vom Z-Isomer in das E-Isomer. E/Z-Isomerisierung tritt meist bei unsymmetrisch substituierten Doppelbindungen auf, d.h. bei Doppelbindungen, die als E-Isomer und als Z-Isomer vorliegen können. Aromatische Doppelbindungen, wie sie in Benzolringen vorliegen, können naturgemäß keine E/Z-Isomerisierung eingehen. Eine Verringerung der E/Z-Isomerisierung ist üblicherweise erreicht, wenn das Gewichtsverhältnis von E- zu Z-Isomer sich in einer Zusammensetzung langsamer verändert im Vergleich zur selben Zusammensetzung ohne den jeweils eingesetzten UV-Absorber. Der Begriff Pestizid bezeichnet mindestens einen Wirkstoff ausgewählt aus der Gruppe der Fungizide, Insektizide, Nematizide, Herbizide, Safener, Pheromone und/oder Wachstumsregulatoren. Bevorzugte Pestizide sind Fungizide, Insektizide und Herbizide. Auch Mischungen von Pestiziden aus zwei oder mehr der vorgenannten Klassen können verwendet werden. Der Fachmann ist vertraut mit solchen Pestiziden, die bei- spielsweise in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London, gefunden werden können. Geeignete Insektizide sind Insektizide der Klasse der Carbamate, Organophosphate, Organochlor-Insektizide, Phenylpyrazole, Py- rethroide, Neonicotinoide, Spinosine, Avermectine, Milbemycine, Juvenil Hormon Analoga, Alkylhalide, Organozinn-Verbindungen, Nereistoxin-Analoga, Benzoylharnstoffe, Diacylhydrazine, METI Akarizide, sowie Insektizide wie Chloropicrin, Pymetrozin, Flo- nicamid, Clofentezin, Hexythiazox, Etoxazol, Diafenthiuron, Propargit, Tetradifon, Chlorfenapyr, DNOC, Buprofezin, Cyromazin, Amitraz, Hydramethylnon, Acequinocyl, Fluacrypyrim, Rotenon, oder deren Derivate. Geeignete Fungizide sind Fungizide der Klassen Dinitroaniline, Allylamine, Anilinopyrimidine, Antibiotica, aromatische Kohlen- Wasserstoffe, Benzenesulfonamide, Benzimidazole, Benzisothiazole, Benzophenone, Benzothiadiazole, Benzotriazine, Benzylcarbamate, Carbamates, Carboxamide, Carbonsäureamdide, Chloronitrile, Cyanoacetamideoxime, Cyanoimidazole, Cyclopropa- necarboxamide, Dicarboximide, Dihydrodioxazine, Dinitrophenylcrotonate, Dithiocar- bamate, Dithiolane, Ethylphosphonate, Ethylaminothiazolcarboxamide, Guanidines, Hydroxy-(2-amino-)pyrimidine, Hydroxyanilides, Imidazole, Imidazolinone, Anorganika, Isobenzofuranone, Methoxyacrylate, Methoxycarbamates, Morpholines, N- Phenylcarbamate, Oxazolidinedione, Oximinoacetate, Oximinoacetamide, Peptidylpy- rimidinnucleoside, Phenylacetamide, Phenylamide, Phenylpyrrole, Phenylharnstoffe, Phosphonate, Phosphorothiolate, Phthalamsäuren, Phthalimide, Piperazine, Piperidi- ne, Propionamide, Pyridazinone, Pyridine, Pyridinylmethylbenzamide, Pyrimidinamine, Pyrimidine, Pyrimidinonehydrazone, Pyrroloquinolinone, Quinazolinone, Chinoline, Chinone, Sulfamide, Sulfamoyltriazole, Thiazolecarboxamide, Thiocarbamate, Thiocar- bamate, Thiophanate, Thiophenecarboxamide, Tolua-mide, Triphenylzinn Verbindungen, Triazine, Triazole. Geeignete Herbizide sind Herbizide der Klassen der Acetami- de, Amide, Aryloxyphenoxypropionate, Benzamide, Benzofuran, Benzoesäuren, Ben- zothiadiazinone, Bipyridylium, Carbamate, Chloroacetamide, Chlorcarbonsäuren, Cyc- lohexanedione, Dinitroaniline, Dinitrophenol, Diphenylether, Glycine, Imidazolinone, Isoxazole, Isoxazolidinone, Nitrile, N-phenylphthalimide, Oxadiazole, Oxazolidinedione, Oxyacetamide, Phenoxycarbonsäuren, Phenylcarbamate, Phenylpyrazole, Phenylpy- razoline, Phenylpyridazine, Phosphinsäuren, Phosphoroamidate, Phosphorodithioate, Phthalamate, Pyrazole, Pyridazinone, Pyridine, Pyridincarbonsäuren, Pyridinecarbo- xamide, Pyrimidindione, Pyrimidinyl(thio)benzoate, Chinolincarbonsäuren, Semicarba- zone, Sulfonylaminocarbonyltriazolinone, Sulfonylharnstoffe, Tetrazolinone, Thiadiazo- le, Thiocarbamate, Triazine, Triazinone, Triazole, Triazolinone, Triazolinone, Triazolo- carboxamide, Triazolopyrimidine, Triketone, Uracile, Harnstoffe. Pestizide enthaltend eine Doppelbindung sind üblicherweise solche Pestizide, die eine C-C-Doppelbindung und/oder eine C-N-Doppelbindung enthalten. Meist ist die Doppelbindung isoliert von einer anderen Mehrfachbindung oder konjugiert zu einer anderen Mehrfachbindung. Bevorzugte Pestizide enthaltend eine Doppelbindung sind Abamectin, Acetamiprid, Acrinathrin, Azoxystrobin, Bifenthrin, Butoxycarboxim, Chlorfenvinfos, Cyhalothrin, 1 ,3 Dichlorpropen, Dicrotophos, Dimethomorph, Diniconnazol, Emamectin, Empenthrin, Fenpyroximat, Flucycloxuron, Flumethrin, Flumorph, Fluoxastrobin, Hydroprene, Ki- noprene, Kresoxim-methyl, Lambda Cyhalothrin, Metaflumizone, Metominostrobin, Metoprene, Mevinphos, Monocrotophos, Nitenpyram, Oxabetrinil, Phosphamidon, Pi- coxystrobin, Propetamphos, Pyrethrin, Pyrifenox, Tefluthrin, Tetrachlorvinphos, Triflo- xystrobin, Triflumizole, Triticonazole, Uniconazole, und die Pheromone Codlemon, Do- dec-8-enylacetat, Dodec-9-enylacetat, Dodeca-7,9-dienylacetat, Farnesol, Nerolidol, Gossyplure, Grandlure II, Grandlure III, Hexadec-1 1 -enal, Hexadec-1 1 -enylacetat, He- xadec-13-en-1 1 -ynylacetat, Japonilure, Muscalure, Tetradeca-9,12-dienylacetat, Tetra- deca-1 1 -enylacetat, Tetradeca-9-enylacetat, und Tridec-4-enylacetat. The object of the present invention was to suppress the E / Z isomerization of agrochemical active substances, such as metaflumizone. Another task was to find a cost-effective method for doing so. The object has been achieved by the use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond. E / Z isomerization is usually understood to mean the conversion of a double bond from the E isomer to the Z isomer or from the Z isomer to the E isomer. E / Z isomerization usually occurs in unsymmetrically substituted double bonds, ie in double bonds, which may be present as E-isomer and as Z-isomer. Aromatic double bonds, as present in benzene rings, can not naturally undergo E / Z isomerization. A reduction in E / Z isomerization is usually achieved when the weight ratio of E to Z isomer in a composition changes more slowly compared to the same composition without the UV absorber used in each case. The term pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners, pheromones and / or growth regulators. Preferred pesticides are fungicides, insecticides and herbicides. Also, mixtures of pesticides of two or more of the above classes may be used. One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flavinamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides , Dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganics, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates , Oximinoacetamides, peptidyl-pyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, P yrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulphamides, sulphamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiocarbons bamate, thiophanate, thiophenecarboxamide, toluenamide, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides of the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones , Nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio ) benzoates, quinolinecarboxylic acids, semicarbazone, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas. Pesticides containing a double bond are usually those pesticides containing a CC double bond and / or a CN double bond. Mostly the double bond is isolated from another multiple bond or conjugated to another multiple bond. Preferred pesticides containing a double bond are abamectin, acetamiprid, acrinathrin, azoxystrobin, bifenthrin, butoxycarboxim, chlorfenvinfos, cyhalothrin, 1, 3 dichloropropene, dicrotophos, dimethomorph, diniconnazol, emamectin, empenthrin, fenpyroximate, flucycloxuron, flumethrin, flumorph, fluoxastrobin, hydroprene, Ki - noprene, kresoxim-methyl, lambda cyhalothrin, metaflumizone, metominostrobin, metoprene, mevinphos, monocrotophos, nitenpyram, oxabetrinil, phosphamidone, picoxystrobin, propetamphos, pyrethrin, pyrifenox, tefluthrin, tetrachlorovinphos, trifloxystrobin, triflumizole, triticonazole, uniconazole, and the pheromones codlemon, dodec-8-enyl acetate, dodec-9-enyl acetate, dodeca-7,9-dienyl acetate, farnesol, nerolidol, gossyplurene, Grandlure II, Grandlure III, hexadec-1 1-enal, hexadec-1 1 -enyl acetate, hexadec-13-en-1 1 -ynylacetate, japoniluronic acid, muscalure, tetradeca-9,12-dienylacetate, tetradeca-11-enylacetate, tetradeca-9-enylacetate, and tridec-4-enylacetate.
Besonders bevorzugte Pestizide enthaltend eine Doppelbindung sind Abamectin, Acetamiprid, Azoxystrobin, Bifenthrin, Cyhalothrin, Dimethomorph, Diniconnazol, Ema- mectin, Flucycloxuron, Fluoxastrobin, Kresoxim-methyl, Lambda Cyhalothrin, Metaflumizone, Picoxystrobin, Trifloxystrobin, Triflumizole, und Triticonazole. Particularly preferred pesticides containing a double bond are abamectin, acetamiprid, azoxystrobin, bifenthrin, cyhalothrin, dimethomorph, diniconnazole, ememectin, flucycloxuron, fluoxastrobin, kresoxim-methyl, lambda cyhalothrin, metaflumizone, picoxystrobin, trifloxystrobin, triflumizole, and triticonazole.
Speziell bevorzugtes Pestizid enthaltend eine Doppelbindung ist Metaflumizon. In einer weiteren bevorzugten Ausführungsform sind Pestizide enthaltend eine Doppelbindung geeignet, wobei das E- oder das Z-Isomer des Pestizides eine höhere Wirksamkeit hat als das jeweils andere Isomer. Der Ausdruck„höhere Wirksamkeit" bezieht sich jeweils auf eine bestimmte biologische Wirksamkeit bei einem bestimmten Zielorganismus. Diese Wirksamkeiten der E- und der Z-lsomere des Pestizides sind meist literaturbekannt. Eine höhere Wirksamkeit gilt dann als vorhanden, wenn eines der Isomere eine Wirksamkeit hat, die mindestens das 1 ,1 -fache (bevorzugt mindestens das 2-fache, besonders bevorzugt mindestens das 4-fache) der Wirksamkeit des anderen Isomers beträgt. Especially preferred pesticide containing a double bond is metaflumizone. In a further preferred embodiment, pesticides containing a double bond are suitable, wherein the E or the Z isomer of the pesticide has a higher activity than the respective other isomer. The term "higher effectiveness" refers each on a specific biological activity in a particular target organism. These efficiencies of the E and Z isomers of the pesticide are mostly known from the literature. Higher efficacy is considered to be present if one of the isomers has an activity which is at least 1, 1-fold (preferably at least 2-fold, more preferably at least 4-fold) the activity of the other isomer.
Bevorzugt liegt das E- oder das Z-Isomer des Pestizides enthaltend eine Doppelbindung zu mindestens 60 Gew.% , bevorzugt zu mindestens 75 Gew.%, besonders be- vorzugt zu mindestens 90 Gew.% vor, bezogen auf die Gesamtmenge der E- und Z- Isomere des Pestizides. Diese Werte beziehen sich auf den Zeitpunkt wenn der UV- Absorber mit dem Pestizid gemischt wird. The E or Z isomer of the pesticide containing a double bond is preferably at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of E- and Z-isomers of the pesticide. These values refer to the time when the UV absorber is mixed with the pesticide.
Der Ausdruck "UV-Absorber" bezieht sich auf alle chemischen Verbindungen, die UV- Licht absorbieren können. Der UV-Absorber kann UV-Licht streuen (wie anorganische UV-Absorber) oder absorbieren. Meist ist der Extinktionskoeffizient des UV-Absorbers von UV-Licht größer als der Extinktionskoeffizient des Pestizides bei derselben Wellenlänge. Die UV-Absorber können öllöslich oder wasserlöslich sein. Sie können auch eingebunden in Polymeren vorliegen, beispielsweise als copolymerisiert. Die UV- Absorber können UV-A Absorber, UV-B Absorber, Breitband Absorber (d.h. UV-A und UV-B), oder optische Aufheller sein. Der UV-Absorber kann in Reinform, als technische Mischung, oder als Mischung von verschiedenen UV-Absorbern eingesetzt werden. Bevorzugt sind UV-Absorber mit einer Löslichkeit in Wasser bei 20 °C von mindestens 0,01 g/L, bevorzugt mindestens 0,1 g/L, und besonders bevorzugt mindestens 1 g/L. The term "UV absorber" refers to all chemical compounds that can absorb UV light. The UV absorber can scatter UV light (such as inorganic UV absorbers) or absorb it. In most cases, the extinction coefficient of the UV absorber of UV light is greater than the extinction coefficient of the pesticide at the same wavelength. The UV absorbers may be oil-soluble or water-soluble. They may also be present in polymers, for example as copolymerized. The UV absorbers may be UV-A absorbers, UV-B absorbers, broadband absorbers (i.e., UV-A and UV-B), or optical brighteners. The UV absorber can be used in pure form, as a technical mixture, or as a mixture of different UV absorbers. Preference is given to UV absorbers having a solubility in water at 20 ° C. of at least 0.01 g / L, preferably at least 0.1 g / L, and particularly preferably at least 1 g / L.
In einer bevorzugten Ausführungsform ist der UV-Absorber wasserlöslich. In einer weiteren bevorzugten Ausführungsform enthält die Zusammensetzung einen weiteren UV- Absorber, wobei der weitere UV-Absorber öllöslich ist. Insbesondere ist mindestens ein UV-Absorber wasserlöslich und mindestens ein UV-Absorber ist öllöslich. In a preferred embodiment, the UV absorber is water-soluble. In a further preferred embodiment, the composition contains a further UV absorber, wherein the further UV absorber is oil-soluble. In particular, at least one UV absorber is water-soluble and at least one UV absorber is oil-soluble.
In einer besonders bevorzugten Ausführungsform sind wasserlöslich UV-Absorber geeignet mit einer Löslichkeit in Wasser bei 20 °C von mindestens 5.0 g/L, bevorzugt mindestens 10.0 g/L, besonders bevorzugt mindestens 50 g/L, und speziell mindestens 100 g/l. In a particularly preferred embodiment, water-soluble UV absorbers are suitable having a solubility in water at 20 ° C. of at least 5.0 g / l, preferably at least 10.0 g / l, more preferably at least 50 g / l, and especially at least 100 g / l.
Der weitere, öllöslich UV-Absorber hat üblicherweise eine Löslichkeit in Wasser bei 20 °C von unter 5.0 g/L, bevorzugt unter 1.0 g/L, besonders bevorzugt unter 0.5 g/L, und speziell unter 0.1 g/l. Anorganische UV-Absorber sind ebenfalls geeignete öllösliche UV-Absorber im Sinne dieser Anmeldung. The further oil-soluble UV absorber usually has a solubility in water at 20 ° C. of below 5.0 g / l, preferably below 1.0 g / l, more preferably below 0.5 g / l, and especially below 0.1 g / l. Inorganic UV absorbers are likewise suitable oil-soluble UV absorbers in the context of this application.
Geeignete UV-Absorber sind beispielsweise: A) Benzotriazole, wie 2-(2H-benzotriazol-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phe- nol (Tinuvin® 900, BASF SE), [3-[3-(2H-benzotriazol-2-yl)-5-(1 ,1 -dimethylethyl)- 4-hydroxyphenyl]-1 -oxopropyl]-w-[3-[3-(2Hbenzotriazol-2-yl)-5-(1 ,1 -dimethyl- ethyl)-4-hydroxyphenyl]-1 -oxopropoxy]poly(oxy-1 ,2-ethanediyl) (Tinuvin® 1 130, BASF SE), 6-tert.-butyl-2-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (Tinuvin® 326, BASF SE), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotnazol-2-yl)-phenol (Tinuvin® 327, BASF SE), 2-(2H-benzotriazol-2-yl)-4,6-di-tert.-pentylphenol (Tinuvin® 320, BASF SE), 2-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)- phenol(Tinuvin® 329, BASF SE), 2-(2H-benzotriazol-2-yl)-4-methylphenol (Tinu- vin® P, BASF SE), 2-(2H-benzotriazol-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phe- nol (Tinuvin® 234, BASF SE), 2,2-Methylenbis(6-(benzotriazol-2-yl)-4-tert-octyl- phenol, (Tinuvin® 360, BASF SE); 2-(2H-benzotriazol-2-yl)-2-(2-methylpropyl)- phenol-4sulfosäurenatriumsalz (Tinogard H® P, BASF SE), Phenol, 2-(2H- benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (Tinuvin® 171 , BASF SE); Suitable UV absorbers are, for example: A) Benzotriazoles, such as 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Tinuvin® 900, BASF SE), [3- [3- ( 2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1 -oxopropyl] -w- [3- [3- (2-benzotriazol-2-yl) -5- (1, 1-dimethyl-ethyl) -4-hydroxyphenyl] -1-oxopropoxy] poly (oxy-1,2-ethanediyl) (Tinuvin® 1 130, BASF SE), 6-tert-butyl-2- (5-chloro-1-one) 2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® 326, BASF SE), 2,4-di-tert-butyl-6- (5-chloro-2H-benzotnazol-2-yl) -phenol (Tinuvin ® 327, BASF SE), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (Tinuvin® 320, BASF SE), 2- (2H-benzotriazol-2-yl) - 4- (1,1,3,3-tetramethylbutyl) phenol (Tinuvin® 329, BASF SE), 2- (2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® P, BASF SE), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Tinuvin® 234, BASF SE), 2,2-methylenebis (6- (benzotriazole-2 -yl) -4-tert-octylphenol, (Tinuvin® 360, BASF SE); 2- (2H-benzotriazol-2-yl) -2- (2-methylpropyl) -phenol-4-sulfonic acid sodium salt (Tinogard H® P, BASF SE), phenol, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl, branched and linear (Tinuvin® 171, BASF SE);
B) Cyanoacrylate, wie 2-Cyano-3-phenylcinnamat ethylester (Uvinul® 3035, BASF SE), 2-cyano-3,3-diphenylacrylsäure-2'-ethylhexyl ester oder 2-ethylhexyl-2- cyano-3-phenylcinnamat (Octocrylene, Uvinul® 539 T, Uvinul 3039, BASF SE);B) cyanoacrylates, such as 2-cyano-3-phenylcinnamate ethyl ester (Uvinul ® 3035, BASF SE), 2-cyano-3,3-diphenylacrylate 2'-ethylhexyl ester or 2-ethylhexyl-2-cyano-3-phenylcinnamate ( Octocrylene, Uvinul ® 539 T, Uvinul 3039, BASF SE);
C) Para-aminobenzoesäure (PABA) Derivative, besonders Ester, wie Ethyl-PABA, ethoxyliertes PABA, Ethyl-dihydroxypropyl-PABA, Glycerol-PABA, 2-EthylhexylC) Para-aminobenzoic acid (PABA) derivatives, especially esters such as ethyl-PABA, ethoxylated PABA, ethyl-dihydroxypropyl-PABA, glycerol-PABA, 2-ethylhexyl
4-(dimethylamino)benzoat (Uvinul® MC 80), 2-Octyl 4-(dimethylamino)benzoat, Amyl 4-(dimethylamino)benzoat, 4-bis(polyethoxy) 4-amino benzoesäure polye- thoxyethyl ester (Uvinul® P 25, BASF SE); 4- (dimethylamino) benzoate (Uvinul ® MC 80), 2-octyl 4- (dimethylamino) benzoate, amyl 4- (dimethylamino) benzoate, 4-bis (polyethoxy) 4-amino benzoic acid thoxyethyl polyether ester (Uvinul ® P 25 , BASF SE);
D) Ester von Salicylsäure, wie 2-Ethylhexyl salicylat, 4-lsopropylbenzyl salicylat, Homomenthyl salicylat, TEA salicylate(Neo Heliopan® TS, Haarmann and Reimer), dipropyleneglycol salicylat; D) esters of salicylic acid, such as 2-ethylhexyl salicylate, 4-lsopropylbenzyl salicylate, homomenthyl salicylate, TEA salicylate (Neo Heliopan TS ®, Haarmann and Reimer), Dipropyleneglycol salicylate;
E) Ester von Zimtsäuren, wie 2-Ethylhexyl 4-methoxycinnamat (Uvinul® MC 80), Octyl-p-methoxycinnamat, Propyl 4-methoxycinnamat, Isoamyl 4-methoxycinnamat, Conoxate, Diisopropyl methylcinnamat, Etocrylen (Uvinul® N 35, BASF SE);  E) esters of cinnamic acids, such as 2-ethylhexyl 4-methoxycinnamate (Uvinul® MC 80), octyl-p-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, conoxates, diisopropyl methyl cinnamate, etocrylene (Uvinul® N 35, BASF SE );
F) Derivative von Benzophenon, wie 2-Hydroxy-4-methoxybenzophenon (Uvinul® M 40, BASF SE), 2-hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-dihydroxy-4- methoxybenzophenon, 2-(4-diethylamino-2-hydroxybenzoyl)-benzoesäure hexy- lester (Uvinul® A Plus, BASF SE), 4-n-octyloxy-2-hydroxy-benzophenon (Uvi- nul® 3008, BASF SE), 2-Hydroxybenzophenon Derivate wie 4-hydroxy-, 4-meth- oxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4, 2', 4'- trihydroxy-, 2'-hydroxy-4,4'-dimethoxy-2-hydroxybenzophenone, Sulfonsäurederivative von Benzophenonen, wie 2-Hydroxy-4-methoxybenzo-phenone-5-sulfonsäure (Uvinul® MS 40, BASF SE) und seine Salze, 2,2'-dihydroxy-4,4'- dimethoxybenzophenone-5,5'-sulfonsäure und seine Salze (Dinatriumsalz: Uvinul® DS 49, BASF SE); G) 3-Benzylidenecamphor dessen Derivate, wie 3-(4'-methylbenzylidene)c/-1 - camphor, benzylidiene camphor sulfonsäure (Mexoryl® SO, Chimex); F) Derivatives of benzophenone, such as 2-hydroxy-4-methoxybenzophenone (Uvinul® M 40, BASF SE), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2- Hexyl (4-diethylamino-2-hydroxybenzoyl) benzoate (Uvinul® A Plus, BASF SE), 4-n-octyloxy-2-hydroxybenzophenone (Uvinul® 3008, BASF SE), 2-hydroxybenzophenone derivatives such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy, 2'-hydroxy-4 , 4'-dimethoxy-2-hydroxybenzophenones, Sulfonsäurederivative of benzophenones, such as 2-hydroxy-4-methoxybenzo-phenone-5-sulfonic acid (Uvinul ® MS 40, BASF SE) and its salts, 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone-5,5'-sulfonic acid and its salts (disodium salt: Uvinul ® DS 49, BASF SE); G) 3-Benzylidenecamphor derivatives thereof, such as 3- (4'-methylbenzylidene) c / -1 - camphor, benzylidiene camphor sulfonic acid (Mexoryl SO ®, Chimex);
H) Sulfonsäure Derivative von 3-Benzylidenecamphor, wie 4-(2-oxo-3-bornyl- idenemethyl)benzenesulfonsäure und 2-Methyl-5-(2-oxo-3-bornylidene)- sulfonsäure und dessen Salze;  H) sulfonic acid Derivative of 3-Benzylidenecamphor, such as 4- (2-oxo-3-bornyl-idenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bionylidenes) - sulfonic acid and its salts;
I) Ester von Benzalmalonsäure, wie 2-Ethylhexyl 4-methoxybenzmalonat;  I) esters of benzalmalonic acid, such as 2-ethylhexyl 4-methoxybenzmalonate;
J) Triazin Derivative, wie Dioctylbutamidotriazon (Uvasorb® HEB, Sigma), 2,4,6- trinanilino-p-(carbo-2'-ethyl-hexyl-1 '-oxy)-1 ,3,5-triazin (Uvinul® T 150, BASF SE), 2-[4-[(2-Hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazin (Tinuvin® 405, BASF SE), anisotriazin (Tinosorb® S, BASF J) triazine derivatives, such as dioctylbutamidotriazone (Uvasorb® HEB, Sigma), 2,4,6-trinanilino-p- (carbo-2'-ethylhexyl-1'-oxy) -1, 3,5-triazine (Uvinul T 150, BASF SE), 2- [4 - [(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl ) -1, 3,5-triazine (Tinuvin® 405, BASF SE), anisotriazine (Tinosorb® S, BASF
SE), 2,4,6-tris(diisobutyl 4'-aminobenzalmalonate)-s-triazin; SE), 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine;
K) Propane-1 ,3-dione, wie 1 -(4-tert-butylphenyl)-3-(4'-methoxyphenyl)propane-1 ,3- dione;  K) propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;
L) 2-Phenylbenzimidazole-5-sulfonsäure oder 2-Phenylbenzimidazol-4-sulfonsäure und Alkalimetall-, Erdalkalimetall-, Ammonium-, Alkylammonium-, Alkanolammo- nium- und Glucammonium-Salze davon;  L) 2-phenylbenzimidazole-5-sulfonic acid or 2-phenylbenzimidazole-4-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof;
M) Derivative von Benzoylmethan, wie 1 -(4'-tert-butylphenyl)-3-(4'-methoxy- phenyl)propane-1 ,3-dion, 4-tert-butyl-4'-methoxydibenzoylmethan or 1 -phenyl-3- (4'-isopropylphenyl)propane-1 ,3-dion;  M) Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane or 1-phenyl -3- (4'-isopropylphenyl) propane-1,3-dione;
N) Aminohydroxy-substituierte Derivative von Benzophenonen, wie N,N-diethyl- aminohydroxybenzoyl-n-hexylbenzoat;  N) aminohydroxy-substituted derivatives of benzophenones, such as N, N-diethylaminohydroxybenzoyl-n-hexylbenzoate;
O) Derivate von Stilben, beispielsweise Salze von Distyrylbiphenyldisulfonat, wie Dinatriumdistyrylbiphenyldisulfonat (Uvitex® NFW, BASF SE), 2,2'-[1 ,2- Ethendiylbis[(3-sulfo-4,1 -phenylen)imono-[6-(diethylamino)-1 ,3,5-triazin-4,2- diyl]imino]] bis-1 ,4-benzoldisulfonsäurehexanatriumsalz (Tinopal® SFP, BASF O) derivatives of stilbene, for example salts of distyrylbiphenyl disulphonate, such as disodium dististylbiphenyl disulphonate (Uvitex® NFW, BASF SE), 2,2 '- [1,2-ethenediylbis [(3-sulfo-4,1-phenylene) imono [6- (diethylamino) -1, 3,5-triazine-4,2-diyl] imino]] bis-1,4-benzenedisulfonic acid hexasodium salt (Tinopal® SFP, BASF
SE); SE);
P) Anorganische UV-Absorber, beispielsweise solche basierend auf ZnO (wie Z- Cote® Produkte, BASF SE), Ti02 (wie T-Lite™ Producte, BASF SE) oder Ce02, sowie die UV-Absorber wie in WO 2009/153231 , Seite 2, Zeile 24 bis Seite 6, Zeile 18 beschrieben. P), inorganic UV absorbers, for example those based on ZnO (like Z Cote ® products, BASF SE), Ti0 2 (such as T-Lite ™ productions, BASF SE) or Ce0 2, as well as the UV absorber as described in WO 2009 / 153231, page 2, line 24 to page 6, line 18 described.
Bevorzugte UV-Absober sind solche der Gruppe F) (Derivate von Benzophenon) und der Gruppe O) (Derivate von Stilben), besonders bevorzugt 2-Hydroxybenzophenon Derivate, Sulfonsäurederivative von Benzophenonen und Salze von Distyrylbiphenyldi- sulfonat, insbesondere 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy- benzophenon-5-sulfonsäure, Dinatriumdistyrylbiphenyldisulfonat und 2-Hydroxy-4- octoxybenzophenone. Preferred UV absorbers are those of the group F) (derivatives of benzophenone) and the group O) (derivatives of stilbene), particularly preferably 2-hydroxybenzophenone derivatives, sulfonic acid derivatives of benzophenones and salts of distyrylbiphenyl disulfonate, in particular 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, disodium distyrylbiphenyl disulfonate and 2-hydroxy-4-octoxybenzophenone.
In einer weiteren bevorzugten Ausführungsform werden mindestens zwei UV-Absorber verwendet. Bevorzugt wird dabei ein UV-Absorber aus der Gruppe A) bis N) und ein UV-Absorber aus der Gruppe O) eingesetzt. In einer besonders bevorzugten Ausführungsform werden UV-Absorber verwendet, die eine Sulfonsauregruppe oder ein Polyalkylenoxidgruppe enthalten. Bevorzugt werden UV-Absorber, die eine Sulfonsauregruppe enthalten. UV-Absorber, die eine Sulfonsauregruppe enthalten, sind allgemein bekannt. Beispiele sind 2-Hydroxy-4-methoxybenzo-phenon-5-sulfonsäure (Uvinul® MS 40, BASF SE) und seine Salze (z.B. Alkalisalz, wie Natrium), 2,2'-dihydroxy-4,4'-dimethoxybenzophenon- 5,5'-sulfonsäure und seine Salze (z.B. Alkalisalz, wie Natrium). Bevorzugt sind Ben- zophenone, die eine Sulfonsauregruppe enthalten (auch Sulfonsäurederivat von Ben- zophenonen genannt). Die Sulfonsauregruppe kann in der Säureform oder als Salz vorliegen, wobei die Salzform bevorzugt wird. In a further preferred embodiment, at least two UV absorbers are used. Preference is given to using a UV absorber from group A) to N) and a UV absorber from group O). In a particularly preferred embodiment, UV absorbers are used which contain a sulfonic acid group or a polyalkylene oxide group. Preference is given to UV absorbers which contain a sulfonic acid group. UV absorbers containing a sulfonic acid group are well known. Examples are 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul ® MS 40, BASF SE) and its salts (for example, alkali salt such as sodium), 2,2'-dihydroxy-4,4'-dimethoxybenzophenon- 5 , 5'-sulfonic acid and its salts (eg alkali salt, such as sodium). Preference is given to benzophenones which contain a sulfonic acid group (also called sulfonic acid derivative of benzophenones). The sulfonic acid group may be in the acid form or as a salt, with the salt form being preferred.
UV-Absorber, die eine Polyalkylenoxidgruppe enthalten, sind allgemein bekannt. Die Polyalkylenoxidgruppe enthält bevorzugt Ethylenoxid in polymerisierter Form. Bevor- zugt sind mindestens 50 mol%, insbesondere mindestens 80 mol% der Alkyleno- xidgruppen Ethylenoxid. Beispiele sind 4-bis(polyethoxy) 4-amino benzoesäure polye- thoxyethyl ester (Uvinul® P 25, BASF SE). UV absorbers containing a polyalkylene oxide group are well known. The polyalkylene oxide group preferably contains ethylene oxide in polymerized form. At least 50 mol%, in particular at least 80 mol%, of the alkylene oxide groups are preferably ethylene oxide. Examples are 4-bis (polyethoxy) 4-amino benzoic acid thoxyethyl polyether ester (Uvinul ® P 25, BASF SE).
Die Menge des UV-Absorbers liegt meist bei 0,5 bis 500 Gew.% bezüglich der Menge des Pestizides. Bevorzugt liegt sie bei 1 bis 300 Gew.%, besonders bevorzugt bei 5 bis 100 Gew.% und insbesondere bei 5 bis 80 Gew.%, jeweils bezüglich der Menge des Pestizides. The amount of UV absorber is usually 0.5 to 500 wt.% With respect to the amount of pesticide. It is preferably from 1 to 300% by weight, more preferably from 5 to 100% by weight and in particular from 5 to 80% by weight, in each case with respect to the amount of pesticide.
In einer bevorzugten Ausführungsform wird zusätzlich zum UV-Absorber ein Antioxida- tionsmittel (auch als Antioxidans bezeichnet) verwendet. Bevorzugt sind Antioxidatien mit einer Löslichkeit in Wasser bei 20 °C von mindestens 0,01 g/L, bevorzugt mindestens 0,1 g/L, und besonders bevorzugt mindestens 1 g/L. In einer weiteren bevorzugten Ausführungsform sind Antioxidatien geeignet mit einer Löslichkeit in Wasser bei 20 °C von mindestens 5.0 g/L, bevorzugt mindestens 20 g/L, und besonders bevorzugt min- destens 100 g/L. In a preferred embodiment, an antioxidant (also referred to as antioxidant) is used in addition to the UV absorber. Antioxidants having a solubility in water at 20 ° C. of at least 0.01 g / l, preferably at least 0.1 g / l, and particularly preferably at least 1 g / l, are preferred. In a further preferred embodiment, antioxidants are suitable having a solubility in water at 20 ° C. of at least 5.0 g / l, preferably at least 20 g / l, and particularly preferably at least 100 g / l.
Antioxidantien sind beispielsweise Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazol und Imidazolderivate (z.B. Urocaninsäure), Peptide wie z.B. D,L-Carnosin, D-Carnosin, L-Carnosin und deren Derivate (z. B. Anserin), Carotinoide, Carotine (z. 6. α-Carotin, ß-Carotin, Lycopin) und deren Derivate, Antioxidants are, for example, amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (e.g., urocanic acid), peptides such as e.g. D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg 6. α-carotene, β-carotene, lycopene) and their derivatives,
Liponsäure und deren Derivate (z. B. Dihydroliponsäure), Aurothioglucose, Lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose,
Propylthiouracil und weitere Thioverbindungen (z.B. Thioglycerin, Thiosorbitol, Propylthiouracil and other thio compounds (e.g., thioglycerol, thiosorbitol,
Thioglycolsäure, Thi redoxin, Glutathion, Cystein, Cystin, Cystamin und deren Thioglycolic acid, thi redoxin, glutathione, cysteine, cystine, cystamine and theirs
Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl-, Butyl-, Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Glycerylester) sowie deren Salze, Dilauryl- thiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, N kleoside und Salze) sowie Sulfoximinverbindungen (z. 6. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptathionin- sulfoximin) in sehr geringen verträglichen Dosierungen , ferner Glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and salts thereof, dilauryl thiodipropionate, Distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages, further
Metallchelatoren (z.B. α-Hydroxyfettsäuren, EDTA, EGTA, Phytinsäure, Lactoferrin), a- Hydroxysäuren (z. B. Zitronensäure, Milchsäure, Äpfelsäure), Huminsäuren, Metal chelators (e.g., α-hydroxy fatty acids, EDTA, EGTA, phytic acid, lactoferrin), α-hydroxy acids (e.g., citric acid, lactic acid, malic acid), humic acids,
Gallensäure, Gallenextrakte, Gallussäureester (z. B. Propyl-, Octyl- und Dodecylgallat), Flavonoide, Catechine, Bilirubin, Biliverdin und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z.B. γ-Linolensäure, Linolsäure, Arachidonsäure, Ölsäure), Folsäure und deren Derivate, Hydrochinon und dessen Derivate (z. B. Arbutin), Ubichinon und Ubichinol sowie deren Derivate, Vitamin C und dessen Derivate (z. B. Ascorbylpalmitat, -stearat, -dipalmitat, acetat, Mg-Ascorbylphosphate, Natrium- und Magnesiumascorbat, Dinatriumascorbylphosphat und -sulfat, Bile acid, bile extracts, gallic acid esters (eg propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and their derivatives, hydroquinone and its derivatives (eg arbutin), ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (eg ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphates, sodium and magnesium ascorbate , Disodium ascorbyl phosphate and sulfate,
Kaliumascorbyltocopherylphosphat, Chitosanascorbat), Isoascorbinsäure und deren Derivate, Tocopherole und deren Derivate (z.B. Tocopherylacetat, -linoleat, -oleat und - succinat, Tocophereth-5, Tocophereth-10, Tocophereth-12, Tocophereth-18, Potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and its derivatives, tocopherols and their derivatives (e.g., tocopheryl acetate, linoleate, oleate and succinate, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18,
Tocophereth-50, Tocophersolan), Vitamin A und Derivate (z. B. Vitamin-A-Palmitat), das Coniferylbenzoat des Benzoeharzes, Rutin, Rutinsäure und deren Derivate, Dinatriumrutinyldisulfat, Zimtsäure und deren Derivate (z. B. Ferulasäure, Ethylferulat, Kaffeesäure), Gallussäure und ihre Ester, beispielswei-se Propylgallat, Kojisäure, Chitosanglycolat und -salicylat, Butylhydroxytoluol, Butylhy-droxyanisol, Tetrakis Tocophereth-50, tocopherolan), vitamin A and derivatives (eg, vitamin A palmitate), the benzylic resin coniferyl benzoate, rutin, rutinic acid and derivatives thereof, disodium rubinyldisulfate, cinnamic acid and its derivatives (eg, ferulic acid, ethyl ferulate, Caffeic acid), gallic acid and its esters, for example propyl gallate, kojic acid, chitosan glycolate and salicylate, butylhydroxytoluene, butylhydroxyanisole, tetrakis
[Methylen (3, 5 di-t-butyl-4-hydroxyhydrocinnamate)]Methan (lr-ganox® 1010, BASF SE), Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Zink und Zink- Derivate (z. B. ZnO, ZnS04), Selen und Selen-Derivate (z. B. Selenmethionin), Stilbene und Stilben-Derivate (z. B. Stilbenoxid, trans-Stilbenoxid), Salze des einwertigen Kupfers, beispielsweise Kupfer-(l)-chlorid, Bis(2,2,6,6-Tetramethyl-4-piperidinyl)sebacate[Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (Ir-ganox® 1010, BASF SE), nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and zinc derivatives (eg ZnO, ZnSO 4), selenium and selenium derivatives (eg selenium methionine), stilbenes and stilbene derivatives (eg stilbene oxide, trans-stilbene oxide), salts of monovalent copper, for example copper (l ) chloride, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate
(Tinuvin® 770), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol (Tinuvin® 171 ), N,N'-Bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)- hexamethylendiamin (Uvinul® 4050 H, BASF SE). Bevorzugte Antioxidatien sind Vitamin C und dessen Derivate, Tocopherole und deren Derivate, Salze des einwertigen Kupfers, Bis(2,2,6,6-Tetramethyl-4-piperidinyl)- sebacate (Tinuvin® 770), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol (Tinuvin® 770), 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol (Tinuvin® 171), N, N'-bis-formyl-N, N'-bis (2, 2,6,6-tetramethyl-4-piperidinyl) - hexamethylenediamine (Uvinul® 4050 H, BASF SE). Preferred antioxidants are vitamin C and its derivatives, tocopherols and their derivatives, monovalent copper salts, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 770), 2- (2H-benzotriazole) 2-yl) -6-dodecyl-4-methyl-phenol
(Tinuvin® 171 ), N,N'-Bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)- hexamethylendiamin (Uvinul® 4050 H, BASF SE). (Tinuvin® 171), N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine (Uvinul® 4050 H, BASF SE).
Das Gewichtsverhältnis von UV-Absorber zu Antioxidationsmittel liegt meist im Bereich von 1 / 10 bis 100 / 1 , bevorzugt im Bereich von 1 / 5 bis 10 / 1 , besonders bevorzugt im Bereich von 1 / 1 bis 5 / 1 . Die vorliegende Erfindung betrifft weiterhin eine Zusammensetzung umfassend ein E- und/oder ein Z-Isomer eines Pestizids enthaltend eine Doppelbindung und einen UV- Absorber. Geeignete und bevorzugte Pestizid enthaltend eine Doppelbindung sind vor- stehend beschrieben. Das E-Isomer oder das Z-Isomer des Pestizides liegt meist zu mindestens 60 Gew.% vor, bevorzugt zu mindestens 75 Gew.%, besonders bevorzugt zu mindestens 90 Gew.% vor, bezogen auf die Gesamtmenge der E- und Z-Isomere des Pestizides. Bevorzugt liegt dasjenige Isomer im Überschuss vor, welches die hö- here Pestizide Aktivität hat. The weight ratio of UV absorber to antioxidant is usually in the range of 1/10 to 100/1, preferably in the range of 1/5 to 10/1, more preferably in the range of 1/1 to 5/1. The present invention further relates to a composition comprising an E and / or a Z isomer of a pesticide containing a double bond and a UV absorber. Suitable and preferred pesticides containing a double bond are present standing described. The E-isomer or the Z-isomer of the pesticide is usually present at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of the E and Z isomers of the pesticide. Preferably, the isomer is present in excess, which has the higher pesticidal activity.
Geeignete UV-Absorber sind wie vorstehend beschrieben. Bevorzugt ist der UV- Absorber ein Derivat von Benzophenon oder ein Derivate von Stilben. In einer weiteren bevorzugten Ausführungsform werden mindestens zwei UV-Absorber verwendet. Ge- eignete Gewichtsverhältnisse von UV-Absorber zu Pestizid, das Metaflumizon ist, sind wie vorstehend beschrieben. Zusätzlich zum UV-Absorber kann ein Antioxidationsmit- tel wie oben beschrieben verwendet werden. Suitable UV absorbers are as described above. Preferably, the UV absorber is a derivative of benzophenone or a derivative of stilbene. In a further preferred embodiment, at least two UV absorbers are used. Suitable weight ratios of UV absorber to pesticide which is metaflumizone are as described above. In addition to the UV absorber, an antioxidant can be used as described above.
Das E-Isomer von Metaflumizon liegt meist zu mindestens 60 Gew.% vor, bevorzugt zu mindestens 75 Gew.%, besonders bevorzugt zu mindestens 90 Gew.% vor, bezogen auf die Gesamtmenge der E- und Z-Isomere des Metaflumizons. The E isomer of metaflumizone is usually present at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of the E and Z isomers of the metaflumizone.
Die Pestizide, wie Metaflumizon, liegen typischerweise in für agrochemische Formulierungen üblichen Zusammensetzungstypen vor, z. B. Lösungen, Emulsionen, Suspen- sionen, Stäube, Pulver, Pasten und Granulate. Der Typ richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindung gewährleisten. Beispiele für Zusammensetzungstypen sind Suspensionen (SC, OD, OESC,), emulgierbare Konzentrate (EC), Emulsionen (EW, EO, ES), Pasten, Pastillen, Kapseln (CS), benetzbare Pulver oder Stäube (WP, SP, SS, WS, DP, DS) oder Granulate (GR, FG, GG, MG), die entweder in Wasser löslich oder dispergierbar sein können, oder LLIN (long lasting insecticidal nets), Köder für Tiere, wie Ameisen oder Ratten. Die Köder können in verschiedenen der vorgenannten Zusammensetzungtypen vorliegen, bevorzugt als Pulver, Pasten, Granulate oder Gele. Im Allgemeinen werden die Zusammensetzungstypen (z. B. SC, EC OD, WG, SG, WP, SP, SS, WS,) verdünnt eingesetzt. Zusammensetzungstypen wie DP, DS, GR, FG, GG, MG oder Köder werden in der Regel unverdünnt eingesetzt. Bevorzugte Zusammensetzungstypen sind Suspensionen. The pesticides, such as metaflumizone, are typically present in typical for agrochemical formulations composition types, eg. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The type depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention. Examples of composition types are suspensions (SC, OD, OESC), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, capsules (CS), wettable powders or dusts (WP, SP, SS, WS , DP, DS) or granules (GR, FG, GG, MG), which may be either water-soluble or dispersible, or LLIN (long-lasting insecticidal nets), baits for animals such as ants or rats. The baits may be in various of the aforementioned composition types, preferably as powders, pastes, granules or gels. In general, the composition types (eg SC, EC OD, WG, SG, WP, SP, SS, WS,) are used diluted. Composition types such as DP, DS, GR, FG, GG, MG or bait are generally used undiluted. Preferred types of compositions are suspensions.
In einer bevorzugten Ausführungsform sind wässrige Zusammensetzungsypen geeig- net, wie wässrige Suspensionskonzentrate, oder Ölhaltige SuspensionskonzentrateIn a preferred embodiment, aqueous composition types are suitable, such as aqueous suspension concentrates, or oil-containing suspension concentrates
(OESC). Der pH-Wert der wässrigen Zusammensetzungsypen ist üblicherweise größer 1 ,0, bevorzugt größer 3,0 und besonders bevorzugt größer 3,5. Der pH-Wert ist meist unter 6,0, bevorzugt unter 5,0 und besonders bevorzugt unter 4,5. Geeignete Bereiche für den pH-Wert sind beispielsweise 2,5 bis 5,5, bevorzugt 3,0 bis 5,0. (DESC). The pH of the aqueous composition types is usually greater than 1.0, more preferably greater than 3.0, and particularly preferably greater than 3.5. The pH is usually below 6.0, preferably below 5.0, and more preferably below 4.5. Suitable ranges for the pH are, for example, 2.5 to 5.5, preferably 3.0 to 5.0.
Der UV-Absorber und/oder die Antioxidatien können bereits während der Herstellung der agrochemischen Formulierung mit dem Pestizid in Kontakt gebracht werden. Die agrochemischen Formulierungen können weiterhin auch für Pflanzenschutzmittel übliche Hilfsmittel enthalten, wobei sich die Wahl der Hilfsmittel nach der konkreten Anwendungsform bzw. dem Wirkstoff richtet. Beispiele für geeignete Hilfsmittel sind Lösungsmittel, feste Trägerstoffe, oberflächenaktive Stoffe (wie weitere Solubilisatoren, Schutzkolloide, Netzmittel und Haftmittel), organische und anorganische Verdicker, Bakterizide, Frostschutzmittel, Entschäumer, ggf. Farbstoffe und Kleber (z. B. für Saatgutbehandlung) oder übliche Hilfsmittel für Köderformulierung (z. B. Lockstoffe, Futtermittel, Bitterstoffe). The UV absorber and / or the antioxidants can already be brought into contact with the pesticide during the preparation of the agrochemical formulation. The agrochemical formulations may furthermore also contain auxiliaries customary for crop protection agents, the choice of auxiliaries being directed to the specific application form or the active substance. Examples of suitable auxiliaries are solvents, solid carriers, surface-active substances (such as further solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate dyes and adhesives (for example for seed treatment) or customary Aid for bait formulation (eg attractants, feeds, bitter substances).
Als Lösungsmittel kommen Wasser, organische Lösungsmittel wie Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol, Gykole, Ketone wie Cyclohexanon, gamma-Butyrolacton, Dimethylfettsäureamide, Fettsäuren und Fettsäureester und stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon, in Betracht. Grundsätzlich können auch Lösungsmittelgemische verwendet werden sowie Gemische aus den vorstehend genannten Lösungsmitteln und Wasser. Suitable solvents include water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, gycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters, and strong polar solvents, e.g. Amines such as N-methylpyrrolidone, into consideration. In principle, solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Am- moniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe. Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
Als oberflächenaktive Stoffe (Adjuvantien, Netz-, Haft-, Dispergier- oder Emulgiermittel) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z. B. von Lignin-(Borresperse®-Typen, Borregaard, Norwegen), Phenol-, Naphthalin- (Morwet®-Typen, Akzo Nobel, USA) und Dibutylnaphthalinsulfonsäure (Nekal®-Typen, BASF, Deutschland), sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Lau- rylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octade- canole sowie von Fettalkoholglykolethern, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethyle- noctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tribu- tylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethy- lenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder Polyoxypropylenal- kylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen sowie Proteine, denaturierte Proteine, Polysaccharide (z.B. Methylcellulose), hydrophob mo- difizierte Stärken, Polyvinylalkohol (Mowiol®-Typen, Clariant, Schweiz), Polycarboxyla- te (Sokalan®-Typen, BASF, Deutschland), Polyalkoxylate, Polyvinylamin (Lupamin®- Typen, BASF, Deutschland), Polyethylenimin (Lupasol®-Typen, BASF, Deutschland), Polyvinylpyrrolidon und deren Copolymere in Betracht. As surfactants (adjuvants, wetting agents, adhesives, dispersants or emulsifiers) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and Formaldehyde, polyoxyethylene noctylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulphite liquors and Proteins, denatured proteins, polysaccharides (eg methylc cellulose), hydrophobic mo- difizierte strengths, polyvinyl alcohol (Mowiol ® types, Clariant, Switzerland), Polycarboxyla- te (Sokalan ® types, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin ® - types, BASF, Germany), polyethyleneimine (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and their copolymers into consideration.
Beispiele für Verdicker (d. h. Verbindungen, die der Zusammensetzung ein modifiziertes Fließverhalten verleihen, d. h. hohe Viskosität im Ruhezustand und niedrige Viskosität im bewegten Zustand) sind Polysaccharide sowie organische und anorganische Schichtmineralien wie Xanthan Gum (Kelzan®, CP Kelco, USA), Rhodopol® 23 (Rho- dia, Frankreich) oder Veegum® (R.T. Vanderbilt, USA) oder Attaclay® (Engelhard Corp., NJ, USA). Examples of thickeners (ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion) are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ®, CP Kelco, U.S.A.), Rhodopol ® 23 (Rho dia, France) or Veegum ® (RT Vanderbilt, USA) or attaclay ® (Engelhard Corp., NJ, USA).
Bakterizide können zur Stabilisierung der Zusammensetzung zugesetzt werden. Beispiele für Bakterizide sind solche basierend auf Diclorophen und Benzylalkoholhemi- formal sowie Isothiazolinonderivaten wie Alkylisothiazolinonen und Benzisothiazolino- nen (Acticide® MBS der Fa. Thor Chemie). Bactericides may be added to stabilize the composition. Examples of bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ® MBS from Thor Chemie)..
Beispiele für geeignete Frostschutzmittel sind Ethylenglycol, Propylenglycol, Harnstoff und Glycerin. Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
Beispiele für Entschäumer sind Silikonemulsionen (wie z. B. Silikon® SRE, Wacker, Deutschland oder Rhodorsil®, Rhodia, Frankreich), langkettige Alkohole, Fettsäuren, Salze von Fettsäuren, fluororganische Verbindungen und deren Gemische. Die agrochemischen Formulierungen können in Form ihrer Zusammensetzungen, z. B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen, Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen, Auslegen von Ködern, Einstreichen, Eintauchen oder Gießen angewendet werden. Examples of defoamers are silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof. The agrochemical formulations may be used in the form of their compositions, e.g. B. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, misting, dusting, scattering, laying bait, painting, dipping or pouring are applied.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind. Zu den Wirkstoffen oder den diese enhaltenden Zusammensetzungen können Öle verschiedenen Typs, Netzmittel, Adjuvanzien, Herbizide, Bakterizide, andere Fungizide und/oder Schädlingsbekämpfungsmittel, gegebenenfalls auch erst unmittelbar vor der Anwendung (d.h. als Tankmix), zugesetzt werden. Diese Mittel können zu den Zusammensetzungen im Gewichtsverhältnis 1 :100 bis 100:1 , bevorzugt 1 :10 bis 10:1 zugemischt werden. Der UV-Absorber und/oder die Antioxidatien können auch erst unmittelbar vor der Anwendung (d.h. als Tankmix) mit dem Pestizid in Kontakt gebracht werden. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water. The active substances or the compositions containing them may contain oils of various types, wetting agents, adjuvants, herbicides, bactericides, other fungicides and / or pesticides, if appropriate also immediately before Application (ie as a tank mix) to be added. These agents can be mixed into the compositions in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1. The UV absorber and / or the antioxidants can also be brought into contact with the pesticide only immediately before use (ie as a tank mix).
Als Adjuvantien in diesem Sinne kommen insbesondere in Frage: organisch modifizierte Polysiloxane, z. B. Break Thru S 240®; Alkoholalkoxylate, z. B. Atplus® 245, Atplus® MBA 1303, Plurafac® LF 300 und Lutensol® ON 30; EO-PO-Block- polymerisate, z. B. Pluronic® RPE 2035 und Genapol® B; Alkoholethoxylate, z. B. Lutensol® XP 80; und Natriumdioctylsulfosuccinat, z. B. Leophen® RA. As adjuvants in this sense are in particular: organically modified polysiloxanes, eg. B. Break Thru S 240®; Alcohol alkoxylates, eg. Atplus® 245, Atplus® MBA 1303, Plurafac® LF 300 and Lutensol® ON 30; EO-PO block polymerizates, eg. Pluronic® RPE 2035 and Genapol® B; Alcohol ethoxylates, eg. Eg Lutensol® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen® RA.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im Allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1 %. Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha. Bei der Behandlung von pflanzlichen Vermehrungsmaterialien, z. B. Staatgut, werden im allgemeinen Wirkstoffmengen von 1 bis 1000 g/100 kg, vor- zugsweise 5 bis 100 g/100 kg Vermehrungsmaterial bzw. Saatgut verwendet. Bei der Anwendung im Material- bzw. Vorratsschutz richtet sich die Aufwandmenge an Wirkstoff nach der Art des Einsatzgebietes und des gewünschten Effekts. Übliche Aufwandmengen sind im Materialschutz beispielsweise 0,001 g bis 2 kg, vorzugsweise 0,005 g bis 1 kg Wirkstoff pro Kubikmeter behandelten Materials. The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha. In the treatment of plant propagation materials, eg. B. State, are generally used amounts of active ingredient from 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of propagating material or seed. When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
Die vorliegende Erfindung betrifft weiterhin ein Verfahren zur Bekämpfung von phyto- pathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die erfindungsgemäße Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. The present invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to the invention on the respective pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
Die vorliegende Erfindung weist verschiedenste Vorteile auf: Die Geschwindigkeit der E/Z-Isomerisierung wird deutlich verringert. Das applizierte Isomer gleibt länger im Sonnenlicht aktiv. Dadurch kann die Applikationsrate des Wirkstoff, wie Metaflumizon, verringert werden. Der applizierte Wirkstoff hat eine deutlich längere Residualwirkung, weil das applizierte aktivere Isomer langsamer in das weniger aktive Isomer umgewandelt wird. Die praktische Umsetzung der Erfindung ist industriell leicht umsetzbar, da der UV-Absorber einfach während der Herstellung der agrochemischen Formulierung mit dem Pestizid in Kontakt gebracht werden kann, oder unmittelbar vor der Anwendung vom Anwender als Tankmix. Durch den Zusatz von Antioxidatien kann die Wir- kung des UV-Absorbers zur Verringerung der E/Z-Isomerisierung weiter gesteigert werden. Wasserlösliche UV-Absorber sind besonders vorteilhaft, da solche Zusammensetzungen sehr lagerstabil sind, und auch vom Anwender leicht als Tankmix zugesetzt werden können (da sich der Absorber in dem wässrigen Tankmix leicht löst und gleichmäßig verteilt). Wasserlösliche UV-Absorber lassen sich leichter in die Formulierung einarbeiten, da sie einfach in die wässrige Formulierung zugesetzt werden, während beispielsweise wasserunlösliche UV-Absorber extra mitgemahlen werden müssen mit dem Wirkstoff. Nachfolgende Beispiele erläutern die Erfindung ohne sie einzuschränken. The present invention has many advantages: the rate of E / Z isomerization is significantly reduced. The applied isomer stays active longer in sunlight. As a result, the rate of application of the active substance, such as metaflumizone, can be reduced. The applied drug has a significantly longer residual effect because the applied active isomer is converted more slowly into the less active isomer. The practice of the invention is readily practicable industrially, as the UV absorber can be easily contacted with the pesticide during preparation of the agrochemical formulation, or immediately before use by the user as a tank mix. The addition of antioxidants can kung of the UV absorber to reduce the E / Z isomerization further increased. Water-soluble UV absorbers are particularly advantageous, since such compositions are very stable on storage, and can also easily be added by the user as a tank mix (since the absorber dissolves easily in the aqueous tank mix and distributes it evenly). Water-soluble UV absorbers are easier to incorporate into the formulation, since they are simply added to the aqueous formulation, while, for example, water-insoluble UV absorbers must be ground separately with the active ingredient. The following examples illustrate the invention without limiting it.
Beispiele Examples
Metaflumizon SC: wässriges Suspensionskonzentrat enthaltend 240 g/l (22,2 Gew.%) Metaflumizon, 2 Gew.% Natriumdioctylsulfosuccinat, 3,5 Gew.% ethoxylierten Cg- Metaflumizone SC: aqueous suspension concentrate containing 240 g / l (22.2 wt.%) Of metaflumizone, 2 wt.% Of sodium dioctylsulfosuccinate, 3.5 wt.% Of ethoxylated Cg-
C11 Alkohol und 3 Gew.% Polyaryphenolethoxylat. C11 alcohol and 3% by weight polyaryphenol ethoxylate.
Eingesetzte UV-Absorber (alle kommerziell erhältlich von BASF SE): UV absorbers used (all commercially available from BASF SE):
Uvitex® NFW: 4,4'-Bis(2-sulfostyryl)-biphenyl-dinatriumsalz Uvitex® NFW: 4,4'-bis (2-sulfostyryl) biphenyl disodium salt
Uvinul® 3050: 2,2',4,4'-Tetrahydroxybenzophenon Uvinul® 3050: 2,2 ', 4,4'-tetrahydroxybenzophenone
Uvinul® M40: 2-Hydroxy-4-methoxybenzophenon Uvinul® M40: 2-hydroxy-4-methoxybenzophenone
Uvinul® 4050H: N,N'-Bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)- hexamethylendiamin  Uvinul® 4050H: N, N'-bisformyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine
Uvinul® A Plus: 2-(4-Diethylamino-2-hydroxybenzoyl)- benzoesäurehexylester Uvinul® A Plus: 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester
Uvinul® 3008: 2-Hydroxy-4-octyloxybenzophenon Uvinul® 3008: 2-hydroxy-4-octyloxybenzophenone
Uvinul® MS 40: 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure  Uvinul® MS 40: 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid
Tinuvin® 770: Bis(2,2,6,6,-tetramethyl-4-piperidyl)sebaceat Tinuvin® 770: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate
Tinuvin® 171 :2-(2H-Benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol Tinuvin® 171: 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol
Z-Cote®: Zinkoxid, mikronisiert Z-Cote®: zinc oxide, micronised
Beispiel 1 - Herstellung von Mischungen Example 1 - Preparation of mixtures
Metaflumizon SC wurde mit einer bestimmten Menge (jeweils Gew.% bezüglich Metaflumizon) des UV-Absorbers und/oder Stabilisators vermischt, im Gewichtsverhältnis 1 : 18 mit Wasser verdünnt und eine Stunde bei Raumtemperatur gerührt.  Metaflumizone SC was mixed with a certain amount (in each case% by weight with respect to metaflumizone) of the UV absorber and / or stabilizer, diluted with water in a weight ratio of 1:18 and stirred for one hour at room temperature.
Beispiel 2 - Bestrahlung und Analyse der Isomerisierung Example 2 - Irradiation and Analysis of Isomerization
20 mg der in Beispiel 1 hergestellten Mischung wurden auf eine Glasplatte getropft und eine Stunde bei Raumtemperatur trocknen gelassen. Dann wurde die Probe 0, 30 bzw. 120 min mit UV-Licht bestrahlt (Sun Test CPS+, Atlas Co.,750 Watt, Wellelänge 300 bis 800 nm). Die Probe wurde von der Glasplatte nach der Bestrahlung mit 2,0 ml DMSO abgewaschen und unter Rühren und mittels Ultraschall (15 s) homogenisiert. Die Probe wurde mittels UPLC (Ultra Performance Liquid Chromatography, BEH C18 Säule, Detektion bei 225 nm) in die E- und Z-Isomeren von Metaflumizon aufgetrennt und über die Peakflächen quantifiziert. Der Anteil E-Isomer ist jeweils angegeben und der Anteil Z-Isomer entspricht 100 % abzüglich des Anteils E-Isomer. 20 mg of the mixture prepared in Example 1 was dropped on a glass plate and allowed to dry at room temperature for one hour. Then, the sample was irradiated with UV light for 0, 30, and 120 minutes, respectively (Sun Test CPS +, Atlas Co., 750 watts, wavelength 300 to 800 nm). The sample was removed from the glass plate after irradiation with 2.0 ml Washed off DMSO and homogenized with stirring and by means of ultrasound (15 s). The sample was fractionated by means of UPLC (Ultra Performance Liquid Chromatography, BEH C18 column, detection at 225 nm) into the E and Z isomers of metaflumizone and quantitated over the peak areas. The proportion of E-isomer is indicated in each case and the proportion of Z-isomer corresponds to 100% less the proportion E-isomer.
Beispiel 3 - Testung verschiedener UV-Absorber Example 3 - Testing of Various UV Absorbers
Die Mischungen wurden wie in Beispiel 1 hergestellt und wie in Beispiel 2 getestet (Ta- belle 1 ). Es wurde gezeigt, dass verschiedenste UV-Absorber die E/Z-Isomerisierung verringern im Vergleich zu einer Mischung, die keinen UV-Absorber enthält.  The mixtures were prepared as in Example 1 and tested as in Example 2 (Table 1). It has been shown that a wide variety of UV absorbers reduce E / Z isomerization compared to a mixture that does not contain a UV absorber.
Tabelle 1 : UV-Absorber Table 1: UV absorber
a) Menge bzgl. Metaflumizon; b) Anteil des E-Isomers an Gesamtmenge der analysierten E- und Z- Isomere.  a) amount with respect to metaflumizone; b) Proportion of E isomer to total amount of analyzed E and Z isomers.
Beispiel 4 - Mischung von UV-Absorber mit Antioxidatien oder mit weiteren UV- Absorbern Example 4 - Mixture of UV absorbers with antioxidants or with further UV absorbers
Die Mischungen wurden wie in Beispiel 1 hergestellt und wie in Beispiel 2 getestet (Tabelle 2). Es wurde gezeigt, dass Mischungen von UV-Absorber mit Antioxidantien (wie Tocopherol, Ascorbinsäure, Uvinul 4050H, Tinuvin 770) oder mit weiteren UV- Absorbern (wie Z-Cote) die E/Z-Isomerisierung verringern im Vergleich zu einer Mischung, die keinen UV-Absorber enthält.  The blends were prepared as in Example 1 and tested as in Example 2 (Table 2). It has been shown that mixtures of UV absorbers with antioxidants (such as tocopherol, ascorbic acid, Uvinul 4050H, Tinuvin 770) or with other UV absorbers (such as Z-Cote) reduce E / Z isomerization compared to a mixture containing does not contain a UV absorber.
Tabelle 2: Mischungen Table 2: Mixtures
UV-Absorber Menge a> E-Isomer [%] b> E-Isomer [%] > E-Isomer [%] > UV absorber Amount a > E isomer [%] b > E isomer [%]> E isomer [%]>
0 min 30 min 120 min  0 min 30 min 120 min
- - 96 58 43  - - 96 58 43
Uvinul® MS 40 60  Uvinul® MS 40 60
100 96 92  100 96 92
a-Tocopherol 10  a-tocopherol 10
Uvinul® MS 40 60 99 91 80 Ascorbinsäure 10 Uvinul® MS 40 60 99 91 80 Ascorbic acid 10
Uvinul® MS 40 60  Uvinul® MS 40 60
99 89 93  99 89 93
Uvinul 4050H 10  Uvinul 4050H 10
Uvinul® MS 40 90  Uvinul® MS 40 90
97 92 85  97 92 85
Tinuvin 770 10  Tinuvin 770 10
Uvinul® MS 40 90  Uvinul® MS 40 90
98 90 85  98 90 85
Z-Cote® 10  Z-Cote® 10
Uvinul® MS 40 30  Uvinul® MS 40 30
97 82 78  97 82 78
Z-Cote® 30  Z-Cote® 30
a) Menge bzgl. Metaflumizon; b) Anteil des E-Isomers an Gesamtmenge der analysierten E- und Z- Isomere.  a) amount with respect to metaflumizone; b) Proportion of E isomer to total amount of analyzed E and Z isomers.
Beispiel 5 - Herstellung von Suspensionskonzentraten Example 5 - Preparation of suspension concentrates
Ein wässriges Suspensionskonzentrat von Metaflumizon wurde durch Mischen und Mahlen folgender Komponenten hergestellt: 180 g/l Metaflumizon, 27 g/l Natriumdioc- tylsulfosuccinat, 54 g/l Propylenglykol, 1 , 1 g/l Xanthan Gum, 33 g/l ethoxyliertes Tristy- rylphenol. Wasserunlösliche UV-Absorber oder Stabilisatoren wurden vor dem Mahlen zugesetzt, während wasserlösliche UV-Absorber oder Stabilisatoren nach dem Mahlen zugesetzt und unter Rühren gelöst wurden. Die Menge an UV-Absorber oder Stabilisatoren wurde jeweils in Gew.% bezüglich Metaflumizon angegeben. Die Partikelgröße betrug D90 < 2,0 An aqueous suspension concentrate of metaflumizone was prepared by mixing and milling the following components: 180 g / l metaflumizone, 27 g / l sodium diol sulfosuccinate, 54 g / l propylene glycol, 1 g / l xanthan gum, 33 g / l ethoxylated tristy rylphenol. Water-insoluble UV absorbers or stabilizers were added before milling, while water-soluble UV absorbers or stabilizers were added after grinding and dissolved with stirring. The amount of UV absorber or stabilizer was in each case given in% by weight with respect to metaflumizone. The particle size was D90 <2.0
Beispiel 6 - Testung von Suspensionskonzentraten Example 6 - Testing of suspension concentrates
Die Suspensionskonzentrate wurden wie in Beispiel 5 hergestellt und wie in Beispiel 2 getestet (Tabelle 3). Es wurde gezeigt, dass die Ergebnisse mit Formulierungen, die nach Beispiel 5 hergestellt wurden, ähnlich gut sind wie die Formulierungen, die durch einfaches Mischen in Beispiel 1 hergestellt wurden.  The suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 3). The results with formulations prepared according to Example 5 were shown to be as good as the formulations prepared by simple mixing in Example 1.
Tabelle 3: UV-Absorber Table 3: UV absorber
a) Menge bzgl. Metaflumizon; b) Anteil des E-Isomers an Gesamtmenge der analysierten E- und Z- Isomere. Beispiel 7 - Testung von verdünnten Suspensionskonzentraten a) amount with respect to metaflumizone; b) Proportion of E isomer to total amount of analyzed E and Z isomers. Example 7 - Testing of Dilute Suspension Concentrates
Die Suspensionskonzentrate wurden wie in Beispiel 5 hergestellt und wie in Beispiel 2 getestet (Tabelle 4). Die 1 :18 Verdünnung mit Wasser in Beispiel 2 führte zu einem Gehalt an Formulierung in Wasser von 5%. Der Gehalt wurde hier noch weiter auf 1 % gesenkt durch stärkere Verdünnung mit Wasser. Diese Verdünnung entspricht einer in der Praxis üblichen Verdünnung eines kommerziellen Wirkstoffkonzentrats, um die sprühfertige Tankmischung zu erhalten. Es wurde gezeigt, dass auch die verdünnten Formulierungen die E/Z-Isomerisierung verringert.  The suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 4). The 1:18 dilution with water in Example 2 resulted in a formulation in water of 5%. The content was reduced even further here to 1% by more dilution with water. This dilution corresponds to a dilution, which is customary in practice, of a commercial active substance concentrate in order to obtain the spray-ready tank mixture. It has also been shown that the diluted formulations also reduce E / Z isomerization.
Tabelle 4: UV-Absorber Table 4: UV absorber
a) Menge bzgl. Metaflumizon; b) Anteil des E-Isomers an Gesamtmenge der analysierten E- und Z- Isomere.  a) amount with respect to metaflumizone; b) Proportion of E isomer to total amount of analyzed E and Z isomers.
Beispiel 8 - Feldversuche Weißkohl Example 8 - field trials of white cabbage
Ein wässriges Suspensionskonzentrat„SC-A" von Metaflumizon wurde durch Mischen und Mahlen folgender Komponenten hergestellt: 180 g/l Metaflumizone, 22 g/l Natri- umdioctylsulfosuccinat, 35 g/l ethoxylierter Cg-n-Alkohol, 30 g/l Polyarylphenolethoxy- lat, 1 g/l Xanthangum (Verdicker), und 50 g/l Alkandiol (Frostschutzmittel).  An aqueous suspension concentrate "SC-A" of metaflumizone was prepared by mixing and milling the following components: 180 g / l of metaflumizone, 22 g / l of sodium dioctylsulfosuccinate, 35 g / l of ethoxylated Cg-n-alcohol, 30 g / l of polyarylphenolethoxy lat, 1 g / l xanthan gum (thickener), and 50 g / l alkanediol (antifreeze).
Ein wässriges Suspensionskonzentrat„SC-A+UV1 " wurde aus SC-A hergestellt, indem 108 g/l Uvinul® MS 40 zugesetzt wurden.  An aqueous suspension concentrate "SC-A + UV1" was prepared from SC-A by adding 108 g / L of Uvinul® MS 40.
Ein wässriges Suspensionskonzentrat„SC-A+UV2" wurde aus SC-A hergestellt, indem 25 g/l Uvinul® MS 40 zugesetzt wurden.  An aqueous suspension concentrate "SC-A + UV2" was prepared from SC-A by adding 25 g / L of Uvinul® MS 40.
Ein wässriges Suspensionskonzentrat„SC-A+UV3" wurde aus SC-A hergestellt, indem 50 g/l Uvinul® MS 40 zugesetzt wurden.  An aqueous suspension concentrate "SC-A + UV3" was prepared from SC-A by adding 50 g / L of Uvinul® MS 40.
Ein wässriges Suspensionskonzentrat„SC-A+UV4" wurde aus SC-A hergestellt, indem 108 g/l Uvitex® NFW zugesetzt wurden. Auf einem Testfeld in den Phillipinen wurde Weißkohl angebaut. Das Feld wurde mit einer Aufwandmenge von 160 g Metaflumizon pro ha besprüht. Nach 14 Tagen wurde anschließend der kumulierte Fraßschaden durch Crocidolomia binotalis bonitiert (Ta- belle 5). Durch den Zusatz von UV-Absorber hatte der Wirkstoff länger eine höhere Wirksamkeit. An aqueous suspension concentrate "SC-A + UV4" was prepared from SC-A by adding 108 g / l Uvitex® NFW and white cabbage was grown on a field test in the phillipines at a rate of 160 g metaflumizone per ha After 14 days, the cumulative feeding damage was assessed by Crocidolomia binotalis ( belle 5). Due to the addition of UV absorber, the active ingredient had a longer efficacy.
Tabelle 5: Table 5:
Beispiel 9 - Feldversuche Weißkohl Example 9 - field trials of white cabbage
Auf einem Testfeld in Kalifornien wurde Weißkohl angebaut. Das Feld wurde mit einer Aufwandmenge von 160 g Metaflumizon pro ha besprüht mit den Suspensionskonzent- raten entsprechend Beispiel 8. Nach 14 Tagen wurde anschließend die Mortalität der Larven von Lepidoptera bestimmt (Tabelle 6). Durch den Zusatz von UV-Absorber hatte der Wirkstoff länger eine höhere Wirksamkeit.  White cabbage was grown on a test field in California. The field was sprayed at a rate of 160 g metaflumizone per ha with the suspension concentrations according to Example 8. After 14 days, the mortality of the larvae of Lepidoptera was subsequently determined (Table 6). Due to the addition of UV absorber, the active ingredient had a longer efficacy.
Tabelle 6: Table 6:
Beispiel 10 - Feldversuche Kartoffel Example 10 - Field trials potato
Auf einem Testfeld in North Carolina (USA) wurden Kartoffeln angebaut (Blockfelder 7*1 m, je drei Blöcke pro Versuchspunkt). Das Feld wurde mit einer Aufwandmenge von 60 g Metaflumizon pro ha besprüht mit den Suspensionskonzentraten entsprechend Beispiel 8. Nach 19 Tagen wurde anschließend die Zahl der Larven von Leptino- tarsa decemlineata (in allen Larvenstadien) und deren Fraßschaden bestimmt (Tabelle 7). Durch den Zusatz von UV-Absorber hatte der Wirkstoff länger eine höhere Wirksamkeit. On a test field in North Carolina (USA) potatoes were cultivated (block fields 7 * 1 m, three blocks per test point). The field was sprayed at a rate of 60 g metaflumizone per ha with the suspension concentrates according to Example 8. After 19 days, the number of larvae of Leptinotarsa decemlineata (in all larval stages) and their feeding damage was then determined (Table 7). Due to the addition of UV absorber, the active ingredient had a longer efficacy.
Tabelle 7: Table 7:
Beispiel 1 1 - UV-Kammer Limabohne Example 1 1 UV chamber lima bean
Limabohnen in der Wachstumsstufe mit ersten Blättern wurden eingesprüht mit 30 g Metaflumizone pro ha in einer Laborsprühkammer. Die Pflanzen wurden dann in eine Wachstumskammer mit UV- und Fluoreszenzlicht platziert mit 24h/Tag Bestrahlung. Nach 3, 10, 14 und 17 Tagen (DAT) wurden Blätter entnommen und in Petrischalen mit einem feuchten Filterpapier gelegt. Pro Schale wurden 5 Spodoptera eridania (Southern Armyworm; 3. Larvenstadium) dazugelegt. Pro Versuch wurden vier Replika ge- macht. Der kumulierte Fraßschaden ist in Tabelle 8 zusammengefasst. Lima beans in the growth stage with first leaves were sprayed with 30 g of metaflumizone per ha in a laboratory spray chamber. The plants were then in one Growth chamber with UV and fluorescent light placed with 24h / day irradiation. After 3, 10, 14 and 17 days (DAT), leaves were removed and placed in Petri dishes with a damp filter paper. Per shell 5 Spodoptera eridania (Southern Armyworm, 3rd instar) were added. Four replicas were made per trial. The cumulative feeding damage is summarized in Table 8.
Tabelle 8: Table 8:
Beispiel 12 - Feldversuche Kartoffel Example 12 - Field trials potato
Auf einem Testfeld in North Carolina (USA) wurde Kartoffeln angebaut (Blockfelder 7*1 m, je drei Blöcke pro Versuchspunkt). Das Feld wurde mit einer Aufwandmenge von 30 bzw. 60 g Metaflumizon pro ha besprüht mit den Suspensionskonzentraten entsprechend Beispiel 8. Nach 19 Tagen wurde anschließend die Zahl der Larven von Leptino- tarsa decemlineata (in allen Larvenstadien) bestimmt (Tabelle 9). Durch den Zusatz von UV-Absorber hatte der Wirkstoff länger eine höhere Wirksamkeit. On a test field in North Carolina (USA) potatoes were grown (block fields 7 * 1 m, three blocks per test point). The field was sprayed at a rate of 30 or 60 g metaflumizone per ha with the suspension concentrates according to Example 8. After 19 days, the number of larvae of Leptinotarsa decemlineata (in all larval stages) was then determined (Table 9). Due to the addition of UV absorber, the active ingredient had a longer efficacy.
Tabelle 9: Mittlere Zahl der Larven pro Block Table 9: Mean number of larvae per block
30 g Metaflumizon/ha 60 g Metaflumizon/ha 30 g metaflumizone / ha 60 g metaflumizone / ha
Ohne Behandlung 150 150 Without treatment 150 150
SC-A 145 105  SC-A 145 105
SC-A+UV1 37 22  SC-A + UV1 37 22
SC-A+UV2 27 12  SC-A + UV2 27 12
SC-A+UV4 123 61  SC-A + UV4 123 61

Claims

Ansprüche claims
1 . Verwendung eines UV-Absorbers zur Verringerung der E/Z-Isomerisierung von Pestiziden enthaltend eine Doppelbindung. 1 . Use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond.
2. Verwendung nach Anspruch 1 , wobei die Doppelbindung eine C-C-Doppelbindung oder eine C-N-Doppelbindung ist. 2. Use according to claim 1, wherein the double bond is a C-C double bond or a C-N double bond.
3. Verwendung nach Anspruch 1 oder 2, wobei das E- oder das Z-Isomer des Pesti- zides zu mindestens 60 Gew.% vorliegt, bezogen auf die Gesamtmenge der E- und Z-Isomere des Pestizides. Use according to claim 1 or 2, wherein the E or Z isomer of the pesticide is at least 60% by weight, based on the total amount of E and Z isomers of the pesticide.
4. Verwendung nach einem der Ansprüche 1 bis 3, wobei der UV-Absorber eine Sul- fonsäuregruppe oder ein Polyalkylenoxidgruppe enthält. 4. Use according to any one of claims 1 to 3, wherein the UV absorber contains a sulfonic acid group or a polyalkylene oxide group.
5. Verwendung nach einem der Ansprüche 1 bis 4, wobei der UV-Absorber eine Sul- fonsäuregruppe enthält. 5. Use according to any one of claims 1 to 4, wherein the UV absorber contains a sulfonic acid group.
6. Verwendung nach einem der Ansprüche 1 bis 5, wobei die Menge des UV- Absorbers bei 0,5 bis 500 Gew.% bezüglich der Menge des Pestizides liegt. 6. Use according to any one of claims 1 to 5, wherein the amount of the UV absorber is 0.5 to 500 wt.% With respect to the amount of the pesticide.
7. Verwendung nach einem der Ansprüche 1 bis 6, wobei zusätzlich zum UV- Absorber ein Antioxidationsmittel verwendet wird. 7. Use according to any one of claims 1 to 6, wherein in addition to the UV absorber, an antioxidant is used.
8. Verwendung nach Anspruch 7, wobei das Gewichtsverhältnis von UV-Absorber zu Antioxidationsmittel im Bereich von 1 / 10 bis 10 / 1 liegt. 8. Use according to claim 7, wherein the weight ratio of UV absorber to antioxidant in the range of 1/10 to 10/1.
9. Verwendung nach einem der Ansprüche 1 bis 8, wobei mindestens zwei UV- Absorber verwendet werden. 9. Use according to any one of claims 1 to 8, wherein at least two UV absorbers are used.
10. Zusammensetzung umfassend ein E- und/oder ein Z-Isomer eines Pestizids enthaltend eine Doppelbindung und einen UV-Absorber, wobei das E-Isomer oder das Z-Isomer des Pestizides zu mindestens 60 Gew.% vorliegt, bezogen auf die Gesamtmenge der E- und Z-Isomere des Pestizides, und wobei der UV-Absorber eine Löslichkeit in Wasser bei 20 °C von mindestens 5.0 g/L hat. A composition comprising an E and / or a Z-isomer of a pesticide containing a double bond and a UV absorber, wherein the E-isomer or Z-isomer of the pesticide is at least 60% by weight based on the total amount of the pesticide E and Z isomers of the pesticide, and wherein the UV absorber has a solubility in water at 20 ° C of at least 5.0 g / L.
1 1 . Zusammensetzung nach Anspruch 10, wobei der UV-Absorber eine Sulfonsäu- regruppe oder ein Polyalkylenoxidgruppe enthält. 1 1. A composition according to claim 10, wherein the UV absorber contains a sulfonic acid group or a polyalkylene oxide group.
12. Zusammensetzung nach Anspruch 10 oder 1 1 , wobei der UV-Absorber ein Sul- fonsäurederivat von Benzophenonen ist. 12. The composition of claim 10 or 11, wherein the UV absorber is a sulfonic acid derivative of benzophenones.
13. Zusammensetzung nach einem der Ansprüche 10 bis 12, enthaltend einen weiteren UV-Absorber, wobei der weitere UV-Absorber öllöslich ist. 13. The composition according to any one of claims 10 to 12, containing a further UV absorber, wherein the further UV absorber is oil-soluble.
14. Zusammensetzung nach einem der Ansprüche 10 bis 13, wobei das Pestizid Me- taflumizon ist. 14. A composition according to any one of claims 10 to 13, wherein the pesticide is metaflizizone.
15. Zusammensetzung nach Anspruch 14, wobei das E-Isomer von Metaflumizon zu mindestens 60 Gew.% vorliegt, bezogen auf die Gesamtmenge der E- und Z- Isomere des Metaflumizon. A composition according to claim 14 wherein the E isomer of metaflumizone is present at at least 60% by weight based on the total amount of E and Z isomers of the metaflumizone.
16. Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die Zusammensetzung gemäß einem der Ansprüche 10 bis 15 auf die jeweiligen Schädlinge, deren Lebens- räum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. 16. A method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to any one of claims 10 to 15 on the respective pests, their Lebens- or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
EP11714762A 2010-04-15 2011-04-14 Uv absorber for reducing the e/z isomerization of pesticides Withdrawn EP2557917A1 (en)

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CA2727153A1 (en) * 2008-06-20 2009-12-23 Basf Se Agrochemical formulation comprising a pesticide, an organic uv photoprotective filter and coated metal oxide nanoparticles

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JP2013523868A (en) 2013-06-17
KR20130051940A (en) 2013-05-21

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