CA2787550C - Anhydrous composition comprising a dissolved and a suspended pesticide, alkyl lactate and alcohol - Google Patents

Anhydrous composition comprising a dissolved and a suspended pesticide, alkyl lactate and alcohol Download PDF

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CA2787550C
CA2787550C CA2787550A CA2787550A CA2787550C CA 2787550 C CA2787550 C CA 2787550C CA 2787550 A CA2787550 A CA 2787550A CA 2787550 A CA2787550 A CA 2787550A CA 2787550 C CA2787550 C CA 2787550C
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alcohol
weight
pesticide
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formulation
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CA2787550A1 (en
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Murat Mertoglu
Winfried Mayer
Dieter Strobel
Rainer Berghaus
Siegfried Strathmann
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BASF SE
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, 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
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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

Abstract

The invention relates to an anhydrous formulation comprising: a) a first pesticide in a dissolved form, b) a second pesticide in the form of suspended particles, c) an alkyl lactate, and d) an alcohol. The invention also relates to a method for controlling phytopathogenic fungi and/or unwanted plant growth and/or unwanted insect or acaride infestations, and/or for regulating the growth of plants. Said formulation is left to act on the respective pests, on the habitat thereof, or on the plants to be protected from the respective pests, on the ground and/or on unwanted plants and/or the useful plants and/or the habitat thereof. The invention also relates to the use of the formulation for increasing the resistance to rain of the applied pesticides.

Description

Anhydrous composition comprising a dissolved and a suspended pesticide, alkyl lactate and alcohol The present invention relates to an anhydrous formulation comprising a) a first pesticide in dissolved form, b) a second pesticide in the form of suspended particles, c) an alkyl lactate, and d) an alcohol. It further relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite infestation and/or of regulating the growth of plants, where the specified formulation is allowed to act on the pests in question, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat. Furthermore, the invention relates to the use of the formulation for increasing the rain resistance of the applied pesticides. Combinations of preferred features with other preferred features are comprised by the present invention.
Agrochemical formulations should ideally have both a curative effect and also a preventative effect. Some of the known pesticides are particularly curatively effective whereas other pesticides are particularly preventatively effective. Thus, for example, boscalid has good preventative effectiveness when it is applied as suspended particles in a fine distribution over the leaf surface. Epoxiconazole is, for example, particularly curatively effective when it is applied as emulsion. In principle, it is possible to prepare mixtures of such pesticides as tank mixture directly in the spray tank from the separate formulations, for example from a suspension concentrate of boscalid and an emulsion concentrate of epoxiconazole. However, as experience shows, tank mixtures are disadvantageous because different formulations have to be handled and their mixing ratios have to be adjusted. Often, a third pesticide should also additionally be added, for example to a mixture of curative and preventative fungicides, a herbicide, insecticide or growth regulator should also be added. Here, the compatibility of the three formulations is very difficult to predict.
WO 2000/18227 discloses a nonaqueous suspension concentrate comprising 50 to 400 g/I of a crop protection agent, 50 to 700 g/I of an adjuvant and 75 to 500 g/I of a solvent, such as alkyl lactates. Here, the suspension concentrate can comprise a mixture of active ingredients, where one of the active ingredients is dissolved in the continuous phase.
WO 2005/074685 discloses a composition for crop protection comprising 2-ethylhexyl lactate, agrochemical active ingredients dissolved therein and further formulation auxiliaries such as benzyl alcohol.
WO 2007/028538 discloses the use of alkyl lactates for improving the effect of crop protection agents, such as pyraclostrobin or epoxiconazole.
WO 2003/075657 discloses a liquid pesticide composition comprising one or more
2 pesticides as active ingredient and a lactate ester as crystallization inhibitor. Suitable pesticides are, for example, epoxiconazole or pyraclostrobin.
The formulations according to the prior art have various disadvantages:
suspension .
concentrates and emulsion concentrates have hitherto had to be mixed in the tank by the user himself. The formulations were not storage-stable or crystallized out. The rain resistance of the pesticides formulated in this way was low. The pesticides were only absorbed slowly or in small amounts into the leaf of the treated plant. The pesticides exhibit low effectiveness.
=
It was therefore an object of the present invention to find a formulation comprising at least two pesticides, where both a suspended and also a dissolved active ingredient is combined in a single formulation. The formulation should have high rain resistance. It should be absorbed very readily into the leaf surface. The formulation should also be storage-stable.
The object was achieved by an anhydrous formulation comprising a) a first pesticide in dissolved form b) a second pesticide in the form of suspended particles c) an alkyl lactate, and d) an alcohol.
Anhydrous formulations comprise in most cases at most 5% by weight of water, preferably at most 1% by weight, particularly preferably at most 0.5% by weight and in particular at most 0.1% by weight.
The first pesticide is present in dissolved form. In most cases, at least 90%
by weight of the first pesticide are dissolved, preferably at least 95% by weight and in particular at least 99% by weight. The first pesticide is generally dissolved in a continuous phase of the formulation.
The second pesticide is present in the form of suspended particles. In most cases, at least 90% by weight of the second pesticide are suspended, preferably at least 95% by weight and in particular at least 99% by weight.
The average particle size of the second pesticide can be determined as D10, D20 or 090 (i.e. particle size for which 10%, 20% or 90%, respectively, of the particles are smaller).
Preferably, Dlo is smaller than 8.0 pm, particularly preferably smaller than 4.0 pm. In a further preferred embodiment, D20 is smaller than 8.0 pm, particularly preferably smaller than 4.0 pm. In a further preferred embodiment, Dgo is smaller than 50.0 pm, particularly preferably smaller than 25.0 pm. The average particle size is usually determined in accordance with CIPAC Method MT 187 "PARTICLE SIZE ANALYSIS
3 BY LASER DIFFRACTION".
Suitable alkyl lactates are Ci-C-12 alkyl lactates, where the alkyl radical may be branched or unbranched, saturated or unsaturated. The alkyl radical is preferably branched. The alkyl radical is preferably saturated. The alkyl radical is particularly preferably branched and saturated. Preferred alkyl lactates are C4-C8 alkyl lactates, particularly preferably C6-C8 alkyl lactates, in particular branched or unbranched octyl lactate. Examples of octyl lactates are 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl,
4-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl,
5-methylheptyl, 6-nnethylheptyl, or n-octyl. A preferred octyl lactate is 2-ethylhexyl lactate. The lactate group can be present in different stereoisomers, for example as D-or L-lactate. Preference is given to the L-lactate group. An especially preferred alkyl lactate is L-(2-ethylhexyl) lactate. The formulation can comprise one or more alkyl lactates, it preferably comprising exactly one alkyl lactate.
The formulation generally comprises 5 to 70% by weight of alkyl lactate, preferably 10 to 60% by weight and in particular 15 to 50% by weight.
Suitable alcohols are all organic solvents with an alcohol group. Usually, the melting point of the alcohol is below 100 C, preferably below 40 C, and in particular below 10 C. As functional groups, the alcohol comprises preferably only at least one alcoholic group, which may, for example, be a primary alcohol group or a phenolic alcohol group.
The alcohol preferably comprises an aryl radical, which may comprise up to two heteroatoms, such as phenyl radical or naphthyl radical. Particular preference is given to the alcohol benzyl alcohol or 2-(1-methylpropyl)phenol (also known as "o-sec butylphenol"), in particular benzyl alcohol. The formulation can comprise one or more alcohols, it preferably comprising exactly one alcohol.
The formulation comprises generally 1 to 50% by weight of alcohol, preferably 3 to 30%
by weight and in particular 7 to 18% by weight.
The weight ratio of alkyl lactate to alcohol is in most cases in the range from 20/1 to 1/10, preferably from 8/1 to 1/3 and in particular from 5/1 to 1/1. Usually, the alkyl lactate and the alcohol form a homogeneous, continuous phase in the formulation.
For example, the anhydrous formulation comprises:
a) a first pesticide in dissolved form, b) a second pesticide in the form of suspended particles, c) 5 to 70 (:)/0 by weight of a C4-C8 alkyl lactate, and d) 3 to 30 `Yo by weight of an alcohol, wherein the alcohol comprises, as a functional group, one alcoholic group; and wherein the weight ratio of alkyl lactate to alcohol is in the range from 8/1 to 1/3.

3a The term pesticides refers to at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators.
Preferred pesticides are epoxiconazole, pyraclostrobin, or metconazole..
Particularly preferred pesticides are growth regulators. Mixtures of pesticides of two or more of the aforementioned classes can also be used. The person skilled in the art is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 14th Ed.
(2006), The British Crop Protection Council, London. Suitable pesticides are:

A) strobilurins:
azoxystrobin, dimoxystrobin, coumoxystrobin, coumethoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxystrobin, methyl 242-(2,5-dimethylphenyloxymethyl)pheny1]-3-methoxyacrylate, 2-(2-(3-(2,6-di-chloropheny1)-1-methylallylideneaminooxymethyl)pheny1)-2-methoxyimino-N-methylacetamide;
B) carboxamides:
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, fluxapyroxad, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penflufen penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methylthiazole-5-carboxanilide, N-(4'-trifluoromethylthiobipheny1-2-y1)-3-difluoromethy1-1-methy1-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethylbuty1)-pheny1)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide;
- carboxylic acid morpholides: dimethomorph, flumorph, pyrimorph;
- benzamides: flumetover, fluopicolide, fluopyram, zoxamid;
- other carboxamides: carpropamid, diclocymet, mandipropamid, oxytetracyclin, silthiofam, N-(6-methoxypyridin-3-yl)cyclopropanecarboxamide;
C) azoles:
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, nnyclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;
- imidazoles: cyazofamid, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole;
- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole, 2-(4-chloropheny1)-N14-(3,4-dimethoxy-phenyl)isoxazol-5-y1]-2-prop-2-ynyloxyacetamide;
D) nitrogenous heterocyclyl compounds - pyridines: fluazinam, pyrifenox, 345-(4-chloropheny1)-2,3-dimethylisoxazolidin-3-y1]-pyridine, 345-(4-methylpheny1)-2,3-dimethylisoxazolidin-3-yllpyridine;
- pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil;
- piperazines: triforine;
- pyrroles: fludioxonil, fenpiclonil;
- morpholines: aldinnorph, dodemorph, dodemorph acetate, fenpropimorph, tridennorph;
- piperidines: fenpropidin;

- dicarboximides: fluorimid, iprodione, procymidone, vinclozolin;
- nonaromatic 5-membered heterocyclic rings: famoxadon, fenamidon, flutianil, octhilinone, probenazole, S-allyl 5-amino-2-isopropyl-3-oxo-4-orthotoly1-2,3-dihydro-pyrazole-1-thiocarboxylate;
5 - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat methylsulfate, fenoxanil, folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-chloro-1-(4,6-dimethoxypyrimidin-2-yI)-2-methyl-1H-benzimidazole, 5-chloro-7-(4-methylpiperidin-1-y1)-6-(2,4,6-trifluoropheny1)41,2,41triazolo[1,5-a]pyrimidine, 5-ethyl-
6-octy141,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
E) carbamates and dithiocarbamates - thio- and dithiocarbannates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;
- carbamates: diethofencarb, benthiavalicarb, iprovalicarb, propamocarb, propamocarb hydrochloride, valiphenal, (4-fluorophenyl) N-(1-(1-(4-cyanophenyl)ethanesulfonyI)-but-2-yl)carbamate;
F) other fungicides - guanidines: dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxins, streptomycin, validamycin A;
- nitrophenyl derivatives: binapacryl, dicloran, dinobuton, dinocap, nitrothal-isopropyl, tecnazene;
- organometallic compounds: fentin salts such as, for example, fentin acetate, fentin chloride, fentin hydroxide;
- sulfurous heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
- organochlorine compounds: chlorthalonil, dichlofluanid, dichlorphen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorophenol and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitrophenyI)-N-ethyl-4-methylbenzenesulfonannide;
- inorganic active substances: phosphorous acid and its salts, Bordeaux mixture, copper salts such as, for example, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- biological products for controlling fungi, plant strengthening products:
Bacillus subtilis strain NRRL No. B-21661 (for example the products RHAPSODY , SERENADE
MAX and SERENADE ASO from AgraQuest, Inc., USA.), Bacillus pumllus strain NRRL No. B-30087 (for example SONATA and BALLAD Plus from AgraQuest, Inc., USA), Ulocladium oudemansii(for example BOTRY-ZEN from BotriZen Ltd., New Zealand), chitosan (for example ARMOUR-ZEN from BotriZen Ltd., New Zealand).
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine, metrafenon, mildiomycin, oxine-copper, prohexadione-calcium, spiroxamin, tolylfluanid, N-(cyclo-propylmethoxyimino-(6-difluoromethoxy-2,3-difluorophenypmethyl)-2-phenyl-acetannide, N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylpheny1)-N-ethyl-N-methylformamidine, N'-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethylphenyI)-N-ethyl-N-methylformamidine, N'-(2-methy1-5-trifluoromethy1-4-(3-trimethylsilanyl-propoxy)pheny1)-N-ethyl-N-methylformamidine, N'-(5-difluoromethy1-2-methy1-4-(3-tri-methylsilanylpropoxy)pheny1)-N-ethyl-N-methylformamidine, N-methyl-(1,2,3,4-tetra-hydronaphthalen-1-y1)-2-{142-(5-methy1-3-trifluoromethylpyrazol-1-ypacetylipiperidin-4-y1}thiazole-4-carboxylate, N-methyl-(R)-1,2,3,4-tetrahydronaphthalen-1-y12-{142-(5-methy1-3-trifluoromethylpyrazol-1-ypacetylipiperidin-4-yllthiazole-4-carboxylate, 6-tert-buty1-8-fluoro-2,3-dimethylquinolin-4-ylacetate, 6-tert-butyl-8-fluoro-2,3-dimethylquinolin-4-y1 methoxyacetate, N-methy1-2-{112-(5-methy1-3-trifluoromethy1-1H-pyrazol-1-ypacetyl]piperidin-4-yll-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-y1]-4-thiazolecarboxamide;
G) growth regulators abscisic acid, amidochlor, ancymidole, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilid, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfid, indole-3-acetic acid, maleic hydrazide, mefluidid, mepiquat (mepiquat chloride), metconazole, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazole, prohexadione (prohexadione-calcium), prohydrojasmone, thidiazuron, triapenthenol, tributylphosphorotrithioate, 2,3,5-triiodo-benzoic acid, trinexapac-ethyl and uniconazole;
H) herbicides - acetamide: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamid, naproanilid, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid analogs: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- bipyridyls: diquat, paraquat;
- carbamates and thiocarbamates: asulam, butylate, carbetamide, desmedipham, dimepiperat, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen,
7 lactofen, oyfluorfen;
- hydroxybenzonitriles: bromoxynil, dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
- phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-0), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
- sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, fluceto-sulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, pro-sulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, tria-sulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfony1)-3-(4,6-dimethoxypyrimidin-2-y1)urea;
- triazines: ametryne, atrazine, cyanazine, dimethametryne, ethiozine, hexazinone, metamitron, metribuzine, prometryne, simazine, terbuthylazine, terbutryne, triaziflam;
- ureas: chlortoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenz-thiazuron, tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulann, florasulam, flucarbazone, flumetsulam, metosulam, orthosulfamuron, penoxsu lam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalide, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfon, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamid, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, fluorochloridon, flurtamon, indanofan, isoxaben, isoxaflutol, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methylarsenic acid, naptalam, oxadiargyl, oxadiazone, oxaziclomefon, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxyfen, pyrazolynate, quinoclamin, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-312-(2-methoxyethoxymethyl)-6-trifluoromethylpyridin-3-carbonyl]bicyclo[3.2.1]oct-3-en-2-one, ethyl (342-chloro-4-fluoro-5-(3-methy1-2,6-dioxo-4-trifluoromethy1-3,6-dihydro-pyrimidin-1-y1)phenoxy]pyridin-2-yloxy)acetate, methyl 6-amino-5-chloro-2-cyclo-propylpyrimidine-4-carboxylate, 6-chloro-3-(2-cyclopropy1-6-methylphenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chlorophenyI)-5-fluoropyridin-2-carboxylic acid, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-carboxylate
8 and methyl 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluorophenyOpyridin-carboxylate;
I) insecticides - organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoat, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalo-thrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin, - insect growth inhibitors: a) chitin synthesis inhibitors: benzoylureas:
chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazin; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb;
d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramate;
- nicotine receptor agonists/antagonists: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chlorothiazol-5-ylmethyl)-2-nitrimino-3,5-dimethy141,3,51triazinane;
- GABA antagonists: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, N-5-am ino-1-(2,6-dichloro-4-methylpheny1)-4-sulfinamoy1-1H-pyrazole-3-thiocarbox-amide;
- macrocyclic lactones: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
- mitochondrial electron transport chain inhibitor (METI) I acaricides:
fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
- METI II and III substances: acequinocyl, fluacyprim, hydramethylnone;
- decouplers: chlorfenapyr;
- inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
- insect ecdysis inhibitors: cryomazin;
- 'mixed function oxidase' inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizon;
9 - others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozin, sulfur, thiocyclam, flubendiamid, chlorantraniliprole, cyazypyr (HGW86); cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron and pyrifluquinazone.
The first pesticide is preferably a pesticide which is soluble to at least 95%
by weight in a mixture of 2-ethylhexyl lactate and benzyl alcohol (weight ratio 3:1) at 20 C. The first pesticide is particularly preferably epoxiconazole, pyraclostrobin, or metconazole, specifically epoxiconazole or pyraclostrobin.
Besides the first pesticide, further pesticides may also be present in dissolved form.
Preferred further pesticides which are present in dissolved form are epoxiconazole or pyraclostrobin.
The formulation comprises generally 0.01 to 50% by weight of the first pesticide, preferably 0.5 to 25% by weight and in particular 3 to 15% by weight.
The second pesticide is preferably a pesticide which is soluble to at most 5%
by weight in a mixture of 2-ethylhexyl lactate and benzyl alcohol (weight ratio 3:1) at 20 C. The second pesticide is particularly preferably boscalid, chlorothalonil, or fluxapyroxad, especially boscalid.
Besides the second pesticide, further pesticides may also be present in the form of suspended particles.
The formulation comprises generally 0.01 to 50% by weight of the second pesticide, preferably 1 to 30% by weight and in particular 8 to 20% by weight.
The weight ratio of the first to second pesticide is in most cases in the range from 50/1 to 1/50, preferably from 5/1 to 1/10 and in particular from 2/1 to 1/4.
Furthermore, the formulations according to the invention may also comprise customary auxiliaries for agrochemical formulations, the choice of auxiliaries depending on the specific application form and/or the active ingredient. Examples of suitable auxiliaries are further solvents, solid carriers, surface-active substances (such as surfactants, solubilizers, protective colloids, wetting agent and tackifiers), organic and inorganic thickeners, bactericides, antifreezes, antifoams, optionally dyes and adhesives (e.g. for the treatment of seed material) or customary auxiliaries for bait formulation (e.g.
attractants, feedants, bittering substances).
Besides the alcohol and the alkyl lactate, suitable further solvents are organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, and also coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, alkylated benzenes and derivatives thereof, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, 5 ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N-methylpyrrolidone. In principle, it is also possible to use solvent mixtures, and also mixtures of the aforementioned solvents and water. Preferably, besides the alcohol and the alkyl lactate, the formulation comprises at most 20% by weight, preferably at most
10 5% by weight and in particular at most 1% by weight, of further solvents.
Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers. The formulation preferably comprises no solid carriers.
Suitable surface-active substances (adjuvants, wetting agents, tackifiers, dispersants or emulsifiers) are the alkali metal salts, alkaline earth metal salts, ammonium salts of aromatic sulfonic acids, e.g. of lignosulfonic acid (Borresperse grades, Borregaard, Norway), phenolsulfonic acid, naphthalenesulfonic acid (Morwet grades, Akzo Nobel, USA) and dibutylnaphthalenesulfonic acid (Nekal grades, BASF, Germany), and also of fatty acids, alkyl- and alkylarylsulfonates, alkyl ether, lauryl ether and fatty alcohol sulfates, and also salts of sulfated hexa-, hepta- and octadecanoles, and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite liquors, and also proteins, denatured proteins, polysaccharides (e.g.
methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol grades, Clariant, Switzerland), polycarboxylates (Sokalan grades, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin grades, BASF, Germany), polyethylenimine (Lupasol grades, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.
Suitable surfactants are in particular anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes. Suitable anionic surfactants are alkali metal salts, alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates or carboxylates. Examples of sulfonates are alkylarylsulfonates,
11 diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acid and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters.
Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated. For the alkoxylation, ethylene oxide and/or propylene oxide can be used, preferably ethylene oxide. Examples of N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl polyglucosides.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. The formulation according to the invention comprises preferably up to 5.0% by weight of cationic surfactants, particularly preferably up to 0.5% by weight, and specifically up to 0.05% by weight.
Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid.
Examples of polybases are polyvinylamines or polyethyleneamines.
The formulation according to the invention can comprise 0.1 to 40% by weight, preferably 1 to 30% by weight and in particular 2 to 20% by weight, total amount of surface-active substances and surfactants, based on the total amount of the formulation.
Suitable thickeners are compounds which impart a modified flow behavior to the formulation, i.e. a high viscosity in the resting state and low viscosity in the agitated state. Examples are polysaccharides, proteins (such as casein or gelatin), synthetic polymers, or inorganic layered minerals. Such thickeners are commercially available, for example xanthan gum (Kelzan , CP Kelco, USA), Rhodopol 23 (Rhodia, France)
12 or Veegum (R.T. Vanderbilt, USA) or Attaclay (Engelhard Corp., NJ, USA).
Preferred thickeners are inorganic layered minerals and polysaccharides, in particular inorganic layered minerals.
The content of thickener in the formulation depends on the effectiveness of the thickener. The person skilled in the art will choose a content in order to obtain the desired viscosity of the formulation. The content will in most cases be 0.01 to 10% by weight.
Bactericides may be added for stabilizing the composition. Examples of bactericides are those based on diclorophen and benzyl alcohol hemiformal, and also isothiazolinone derivatives such as alkylisothiazolinones and benzoisothiazolinones (Acticide MBS from Thor Chemie). Examples of suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerol. Examples of antifoams are silicone emulsions (such as e.g. Silikon SRE, Wacker, Germany or Rhodorsil , Rhodia, France), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
The user customarily uses the formulation according to the invention for application in a premetering device, in a rucksack sprayer, in a spray tank or in a spraying aircraft.
Here, the formulation is brought to the desired use concentration with water and/or buffer, optionally with the addition of further auxiliaries, and thus giving the ready-to-use spray mixture (so-called tank mix). Usually, 50 to 500 liters of the ready-to-use spray mixture are applied per hectare of utilizable agricultural area, preferably 100 to 400 liters. The active ingredient concentrations in the ready-to-use preparations may be varied within relatively large ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
Oils of various types, wetting agents, adjuvants, herbicides, bactericides, other fungicides and/or pesticides can be added to the active ingredients or to the compositions comprising these, and optionally to the tank mix, immediately prior to use.
These agents can be admixed to the compositions according to the invention in the weight ratio 1:100 to 100:1, preferably 1:10 to 10:1. Suitable adjuvants within this context are in particular: organically modified polysiloxanes, e.g. Break Thru S 240 ;
alcohol alkoxylates, e.g. Atplus 245, Atplus MBA 1303, Plurafac LF 300 and Lutensol ON 30; EO-PO block polymers, e.g. Pluronic RPE 2035 and Genapol B;

alcohol ethoxylates, e.g. Lutensol XP 80; and sodium dioctyl sulfosuccinate, e.g.
Leophen RA.
Depending on the nature of the desired effect, the application rates when used in crop protection are between 0.001 and 2.0 kg of active ingredient per ha, preferably between 0.005 and 2 kg per ha, particularly preferably between 0.05 and 0.9 kg per ha,
13 in particular between 0.1 and 0.75 kg per ha.
The present invention further relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite infestation and/or of regulating the growth of plants, where the formulation according to the invention is allowed to act on the pests in question, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat.
The present invention further relates to the use of the formulation according to the invention for increasing the rain resistance of the applied pesticides.
The present invention further relates to the use of the formulation according to the invention for increasing the absorption of the applied pesticides into the plant.
Advantages of the invention are that suspended active ingredients and dissolved active ingredients can now be combined in one formulation meaning that, for example, it is possible to dispense with laborious tank mixing of the individual formulation.
The formulation is storage-stable (even upon repeated cooling below 0 C) and does not crystallize out. The pesticides have a high rain resistance. The pesticides are absorbed very rapidly and in large amounts into the leaf of the treated plant. The pesticides exhibit higher effectiveness compared to conventionally formulated active ingredients.
The yield of the treated plants increases.
The examples below illustrate the invention without limiting it.
Examples Nonionic surfactant A: alkoxylated fatty alcohol, liquid at 25 C; surface tension for 1 g/I
in water at 23 C (DIN 53 914) 28 to 31 mN/m; cloud point according to EN 1890 Method A 21-22 C; setting point according to DIN 51583 ¨10 C
Nonionic surfactant B: polyaromatic ethoxylate, setting point 14 C; surface tension for 0.1% in water at 25 C (DIN 53 914) 40 to 41 mN/m.
Nonionic surfactant C: organomodified siloxane, liquid, pH neutral in water, setting point -10 C.
Nonionic surfactant D: ethoxylate propoxylate of a short-chain fatty alcohol, melting point 30 C, surface tension for 0.1% in water at 25 C (DIN 53 914) 31-32 mN/m Nonionic surfactant E: tristyrylphenol ethoxylate.
Nonionic surfactant F: castor oil, ethoxylated; liquid, water solubility 200 g/I; surface tension 44-45 mN/m (OECD ring method).
Anionic surfactant A: polyetherphosphate, pH in water (100 g/I) at 23 C 2Ø

= CA 02787550 2012-07-19
14 Anionic surfactant B: alkylbenzenesulfonate 60% by weight dissolved in branched alcohol, setting point -31 C.
Thickener A: organically modified hectorite, finely divided powder.
Thickener B: sheet silicate based on an organically modified smectite, finely divided powder.
Example 1 - Epoxiconazole & boscalid in EHL & benzyl alcohol Epoxiconazole was stirred in a mixture of 200 g of 2-ethylhexyl (S)-lactate (EHL) and 125 g of benzyl alcohol until the active ingredient had dissolved. Then, the other formulation auxiliaries were added (see Table 1) and the mixture was stirred for 10 min.
Finally, boscalid was added, and the mixture was stirred for 5 min and topped up to 1.0 I with 2-ethylhexyl lactate. The resulting suspension was ground using a ball mill.
The particle size was below 4 pm (50%) or below 25 pm (90%).
Stability test: the formulation was subjected to a temperature cycle from -10 C to +10 C for one week. The formulation was stable and no deposition of the suspended particles was found. The viscosity of the formulation was likewise uniformly stable. No crystal growth was found either.
Example 2 - Epoxiconazole & pyraclostrobin & boscalid in EHL & benzyl alcohol Epoxiconazole and pyraclostrobin were stirred in a mixture of 200 g of 2-ethylhexyl lactate and 125 g of benzyl alcohol until the two active ingredients had dissolved. The other formulation auxiliaries were then added (see Table 1) and the mixture was stirred for 10 min. Finally, boscalid was added, and the mixture was stirred for 5 min and topped up to 1.0 I with 2-ethylhexyl lactate. The resulting suspension was ground using a ball mill. The particle size was below 4 pm (50%) or below 25 pm (90%).
The stability test (see Example 1) again exhibited a stable formulation: the formulation was stable and no deposition of the suspended particles was found. The viscosity of the formulation was likewise uniformly stable. No crystal growth was found either.
Example 3 - Epoxiconazole & boscalid in benzyl alcohol (not according to the invention) Epoxiconazole was stirred in a mixture of 300 g of benzyl alcohol until the active ingredient had dissolved. The other formulation auxiliaries were then added (see Table 1) and the mixture was stirred for 10 min. Finally, boscalid was added, and the mixture was stirred for 5 min and topped up to 1.0 I with benzyl alcohol. The resulting suspension was ground using a ball mill. The particle size was below 4 pm (50%) or below 25 pm (90%).
In the stability test (see Example 1), large crystals of boscalid were formed and irreversible phase separation was observed.

Example 4 - Epoxiconazole & boscalid in EHL (not according to the invention) Epoxiconazole was stirred in a mixture of 300 g of 2-ethylhexyl lactate, the active ingredient becoming suspended. The other formulation auxiliaries were then added 5 (see Table 1) and the mixture was stirred for 10 min. Finally, boscalid was added, and the mixture was stirred for 5 min and topped up to 1.0 I with 2-ethylhexyl lactate. The resulting suspension was ground using a ball mill. The particle size was below 4 pm (50%) or below 25 pm (90%).
10 In the stability test (see Example 1), epoxiconazole was only partially soluble.
Irreversible phase separation was observed.
Example 5 - Epoxiconazole & boscalid in EHL & benzyl alcohol & water (not according to the invention)
15 Epoxiconazole was stirred in a mixture of 200 g of 2-ethylhexyl lactate and 125 g of benzyl alcohol until the active ingredient had dissolved. The further formulation auxiliaries were then added (see Table 1), and the mixture was stirred for 10 min and then topped up to 1.0 I with 2-ethylhexyl lactate (mixture A).
An aqueous suspension concentrate (280 ml) comprising 500 g/I of boscalid and 1.7%
by weight of phenolsulfonic acid-formaldehyde polycondensate sodium salt was topped up to 1.5 I with water. With slow stirring, mixture A was added and, finally, the mixture was topped up to 3.0 I with water. This gave an aqueous suspoemulsion.
In the stability test (see Example 1), crystals of epoxiconazole were formed.
The suspoemulsion was not stable.
Table 1: Composition of Examples 1 to 5 (all concentrations in g/1) Example No. 1 2 3a) 4a) 5a) 6a) Boscalid 140 140 140 140 140 -Epoxiconazole 50 50 50 50 50 Pyraclostrobin - 60 - - - 60 Nonionic surfactant A 100 100 100 100 100 100 Nonionic surfactant B 18 18 18 18 18 18 Thickener A 8 - 8 8 - -Thickener B - 15 - - - 15 Anionic surfactant A 40 40 40 40 40 40 Nonionic surfactant C - 100 - - - 100 Nonionic surfactant D 18 18 18 18 18 18 Propylene carbonate 2.4 - 2.4 2.4 - , -Nonionic surfactant E 60 60 60 60 60 60 Nonionic surfactant F - 50 - - - 50 Anionic surfactant B 24 24 24 24 24 24
16 Benzyl alcohol 125 125 ad 1 I 125 125 2-Ethylhexyl (S)-lactate ad 1 I ad 1 I ad 1 I ad 1 I ad 1 I
Water ad 3 I
a) not according to the invention Example 6 - Rain resistance Wheat plants (15 plants per pot, in each case 4 pots) were sprayed with the formulations from Example 1 or 2, in each case with an application rate of 2.5 I/ha. For comparison, one experimental series was not sprayed. One hour after spraying, rain was simulated in an amount of 30 mm. For comparison, in each case one experimental series was not subjected to rain. After 36 days, infestation with Septoria was graded.
The results are summarized in Table 2. As comparison (not according to the invention), Bell from BASF SE was used (an aqueous suspension concentrate of 233 g/I
(20.8%
by weight) of boscalid and 67 g/I (6% by weight) of epoxiconazole, 11.2-12.6%
by weight fatty alcohol alkoxylate), using the same application rate. The experiment showed that the rain resistance of the formulations according to the invention is very good.
Table 2: Rain resistance (% infestation with Septoria) Formulation Without rain With rain With rain [/o infestation] [/o infestation] [/0 infestation]
Without treatment 78 85 75 Example 1 0 0 0 Example 2 0 0 0 Bell a) 0 7 6 a) not according to the invention Example 7 ¨ Spreading the spray drop on the leaf surface To determine the spreading behavior of spray drops, spray mixtures were prepared in the customary field concentration in CIPAC water D. In each case, 1 pl drops were placed onto the leaf surface using a Hamilton syringe and the spreading of the spray drop during drying was visually monitored with the help of a stereomicroscope.
The size of the drop immediately after placement (Fo) and the size of the drop after drying (FE) were measured. The experiments were repeated several times and the averages were calculated. Evaluation was carried out in accordance with the following formula:
spreading factor (in percent) = FE:Fo x 100%.
The experiment showed the higher spreading formulation on leaf surfaces.
Table 3: Spreading Spray mixture comprising formulation of Spreading factor Example 1 > 1000%
Example 2 > 1000%
17 Bell a) ¨600%
a) not according to the invention Example 8 - Active ingredient absorption To determine the active ingredient absorption, wheat plants (melon, winter wheat) were grown in a greenhouse to stage 36 BBCH. The corresponding formulations (see Table 4, 5) were applied in a laboratory spray track with the following parameters:
product application rate: corresponding to the field concentration water application rate: 200 I/ha nozzle type: Lechler ID 120 02 (air injector flat-spray nozzle) pressure: 3.33 bar traveling speed: 5 km/h Following application, the wheat plants were further cultivated again for 7 days in the greenhouse. The treated leaves were then cut off and weighed. In a first step, 30-40 g of leaves were cut up small into pieces measuring ca. 5 cm and washed with 200 ml of methanol (50%). A further washing step then took place with 100 ml of methanol (50%). The washing media were separated from the leaves, combined, and analyzed by means of LC-MS-MS (Table 4, 5 "Washable").
The leaves were then treated with 400 ml of extraction medium (70% methanol, 25%
water, 5% 2N HCI) and comminuted using a dispersing rod. One aliquot (ca. 10 ml) of the supernatant was transferred to a centrifuge tube and centrifuged for 5 min at 3000 rpm. 2 ml of the supernatant were placed in a test tube which comprised 2 ml of 0.2N NaOH. 5 ml of cyclohexane were added and the mixture is shaken for 20 min.
1 ml aliquot of the cyclohexane phase was pipetted into a chromatography vial and evaporated to dryness by means of nitrogen. The residue was taken up in 1 ml of methanol (50%), diluted and analyzed like the washing solution by means of LC-MS-MS (Table 4, 5 "Absorption").
The recovery rate of the various active ingredients was determined with untreated plants and active ingredient additions of 1 and 5 mg/kg of leaf mass. For comparison, the commercially available formulations Bell and Diamant0 (suspoemulsion, 114 g/I
of pyraclostrobin, 43 g/I of epoxiconazole, 214 g/I fenpropimorph, 17% by weight of solvent naphtha, 11% by weight of fatty alcohol alkoxylate, 5% by weight of phenolsulfonic acid-formaldehyde polycondensate sodium salt) from BASF SE were used, and also an aqueous suspension concentrate containing 160 g/I of epoxiconazole, 260 g/I of pyraclostrobin ("Comparison A").
The experiments showed that the active ingredients formulated according to the invention are better absorbed into the plants than known formulations of these active ingredients.
18 Table 4: Active ingredient absorption Be110a) Example 1 Washable Absorption Washable Absorption Epoxiconazole 75 25 29 71 Boscalid 94 6 92 8 a) not according to the invention Table 5: Active ingredient absorption Comparison A a) Belle+ Diamant a), b) Example 2 Washable Absorption Washable Absorption Washable Absorption Epoxiconazole 90 10 63 37 21 79 Boscalid 91 9 90 10 Pyraclostrobin 92 8 66 34 52 48 a) not according to the invention; b) weight ratio 1/1.
Example 9 - Biological effectiveness The biological effectiveness against Septoria triticiwas tested on wheat plants in field experiments upon use to BBCH 31-59. 21-42 days after application, the infestation of Septoria was graded and the efficacy was calculated. Whereas in the case of plants treated with Bell , an average efficacy (n = 4) of 72% was found, the formulation from Example 1 exhibited an average effectiveness of 90%.
Example 10- Yield increase The yield of wheat was measured in field experiments in Europe. The untreated fields had on average (n = 13) a yield of 85.1 dt/ha, the fields treated with Bell 97.8 dt/ha and the fields treated with the formulation from Example 1101.6 dt/ha.
Example 11 - Biological effectiveness The biological effectiveness against net blotch was tested on barley plants upon use to BBCH 31-62. 21-42 days after application, the infestation was graded and the efficacy calculated. Whereas in the case of the plants treated with Bell an average effectiveness (n = 8) of 71% was found, the formulation from Example 1 exhibited an average effectiveness of 84%.
Example 12 - Biological effectiveness The biological effectiveness against brown rust was tested on winter wheat upon use to BBCH 32-59. 30-50 days after application, the infestation was graded and the efficacy calculated. Whereas in the case of the plants treated with Bell an average effectiveness (n = 6) of 83% was found, the formulation from Example 1 exhibited an average effectiveness of 88%, and the formulation from Example 2 an average effectiveness of 95%.
19 Example 13 - Biological effectiveness The biological effectiveness against Rhynchosporium was tested on barley upon use to BBCH 31-49. 20-50 days after application, the infestation was graded and the efficacy calculated. Whereas in the case of the plants treated with Bell an average effectiveness (n = 4) of 55% was found, the formulation from Example 1 exhibited an average effectiveness of 65%, and the formulation from Example 2 an average effectiveness of 77%.

Claims (14)

Claims
1. An anhydrous formulation comprising a) a first pesticide in dissolved form, b) a second pesticide in the form of suspended particles, c) 5 to 70 % by weight of a C4-C8 alkyl lactate, and d) 3 to 30 % by weight of an alcohol, wherein the alcohol comprises, as a functional group, one alcoholic group; and wherein the weight ratio of alkyl lactate to alcohol is in the range from 8/1 to 1/3.
2. The formulation according to claim 1, where the alkyl lactate is 2-ethylhexyl lactate.
3. The formulation according to claim 1 or 2, where the alcoholic group is a primary alcoholic group or a phenolic alcohol group.
4. The formulation according to any one of claims 1 to 3, where the alcohol is benzyl alcohol or 2-(1-methylpropyl)phenol.
5. The formulation according to any one of claims 1 to 4, where the weight ratio of alkyl lactate to alcohol is in the range from 5/1 to 1/1.
6. The formulation according to any one of claims 1 to 5, comprising 10 to 60% by weight of alkyl lactate.
7. The formulation according to any one of claims 1 to 6, where the first pesticide is soluble to at least 95% by weight in a 3:1 mixture by weight of 2-ethylhexyl lactate and benzyl alcohol at 20°C.
8. The formulation according to any one of claims 1 to 7, where the second pesticide is soluble to at most 5% by weight in a 3:1 mixture by weight of 2-ethylhexyl lactate and benzyl alcohol at 20°C.
9. The formulation according to any one of claims 1 to 8, where the first pesticide is epoxiconazole, pyraclostrobin, or metconazole.
10. The formulation according to any one of claims 1 to 9, where the second pesticide is boscalid, chlorothalonil, or fluxapyroxad.
11. The formulation according to any one of claims 1 to 10, where the average particle size D90 of the second pesticide is less than 50 µm.
12. A method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite infestation and/or of regulating the growth of plants, where the formulation according to any one of claims 1 to 11 is allowed to act on the pests in question, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat.
13. The use of the formulation according to any one of claims 1 to 11 for increasing the rain resistance of the applied pesticides.
14. The use of the formulation according to any one of claims 1 to 11 for increasing the absorption of the applied pesticides into the plant.
CA2787550A 2010-02-12 2011-02-07 Anhydrous composition comprising a dissolved and a suspended pesticide, alkyl lactate and alcohol Active CA2787550C (en)

Applications Claiming Priority (3)

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EP10153451.9 2010-02-12
EP10153451 2010-02-12
PCT/EP2011/051733 WO2011098419A2 (en) 2010-02-12 2011-02-07 Anhydrous composition comprising a dissolved pesticide and a suspended pesticide, alkyl lactate and alcohol

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CA2787550C true CA2787550C (en) 2017-05-09

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AR (1) AR081715A1 (en)
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CA (1) CA2787550C (en)
EA (1) EA021744B1 (en)
HU (1) HUE036088T2 (en)
PL (1) PL2533631T3 (en)
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EP3393237A1 (en) 2015-12-22 2018-10-31 Bayer CropScience Aktiengesellschaft Emulsion concentrates of lipophilic compounds
US9988553B2 (en) * 2016-02-22 2018-06-05 Eastman Chemical Company Thermosetting coating compositions

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EP0024188A1 (en) * 1979-08-14 1981-02-25 Fbc Limited Herbicides that contain difenzoquat
US5059241A (en) * 1983-07-06 1991-10-22 Union Oil Company Of California Plant growth regulation
DK191386D0 (en) * 1986-04-24 1986-04-24 Koege Kemisk Vaerk emulsifier
NZ510741A (en) * 1998-09-25 2003-08-29 Basf Ag Non-aqueous suspension concentrate containing a triazolopyrimidine crop protection active compound, and its use as a pesticide
DE10132459A1 (en) * 2001-07-04 2003-01-23 Cognis Deutschland Gmbh Process for improving the rain resistance of pesticides
US6734141B2 (en) * 2001-11-21 2004-05-11 Goldschmidt Ag Use of non-spreading silicone surfactants in agrochemical compositions
IL148684A (en) * 2002-03-14 2006-12-31 Yoel Sasson Pesticidal composition
KR101196233B1 (en) * 2004-02-06 2012-11-05 메리얼 리미티드 Plant protection compositions and use thereof
EP1931197B1 (en) * 2005-04-18 2015-04-08 Basf Se Preparation containing at least one conazole fungicide a further fungicide and a stabilising copolymer
DE102005042876A1 (en) * 2005-09-09 2007-03-22 Bayer Cropscience Ag Use of lactate esters to improve the effect of pesticides
EP1787516B1 (en) * 2005-11-09 2013-10-23 Agrichem B.V. Sprout inhibiting composition

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HUE036088T2 (en) 2018-06-28
TR201802433T4 (en) 2018-03-21
AR081715A1 (en) 2012-10-17
WO2011098419A3 (en) 2011-12-01
EP2533631B1 (en) 2017-11-22
EP2533631A2 (en) 2012-12-19
UA107694C2 (en) 2015-02-10
EA201201112A1 (en) 2013-03-29
BR112012018072A2 (en) 2015-10-20
KR101869107B1 (en) 2018-06-19
EA021744B1 (en) 2015-08-31
KR20130030250A (en) 2013-03-26
PL2533631T3 (en) 2018-05-30
WO2011098419A2 (en) 2011-08-18
BR112012018072B1 (en) 2018-10-30
CA2787550A1 (en) 2011-08-18

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