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WO2007017040A2 - Microemulsions and concentrates comprising fipronil - Google Patents

Microemulsions and concentrates comprising fipronil Download PDF

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Publication number
WO2007017040A2
WO2007017040A2 PCT/EP2006/006904 EP2006006904W WO2007017040A2 WO 2007017040 A2 WO2007017040 A2 WO 2007017040A2 EP 2006006904 W EP2006006904 W EP 2006006904W WO 2007017040 A2 WO2007017040 A2 WO 2007017040A2
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WO
WIPO (PCT)
Prior art keywords
spp
microemulsions
concentrates
fipronil
agrochemical composition
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Application number
PCT/EP2006/006904
Other languages
French (fr)
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WO2007017040A3 (en
Inventor
Wang Bing
Ma Jufa
Guo Jingquan
Tong Xianming
Richard Dickmann
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Bayer Cropscience S.A.
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Application filed by Bayer Cropscience S.A. filed Critical Bayer Cropscience S.A.
Priority to MX2008001116A priority Critical patent/MX2008001116A/en
Priority to JP2008523177A priority patent/JP2009502826A/en
Priority to BRPI0613908-6A priority patent/BRPI0613908A2/en
Priority to EP06754725A priority patent/EP1912505A2/en
Publication of WO2007017040A2 publication Critical patent/WO2007017040A2/en
Publication of WO2007017040A3 publication Critical patent/WO2007017040A3/en

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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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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

Definitions

  • the present invention relates to the field of crop protectant formulations.
  • the invention relates to liquid formulations in the form of microemulsions or concentrates thereof which comprise agrochemical active ingredients.
  • Active ingredients for crop protection are generally not employed in their pure fo ⁇ n. Depending on the field and type of application, and on physical, chemical and biological parameters, the active ingredient is employed as a mixture with conventional adjuvants and additives as a solid or liquid active ingredient formulation.
  • Liquid formulations are described, for example, in EP-A 0 261 492, EP-A 0 394 847, WO 2004/054360, WO 95/17822, WO 98/31223, WO 89/03176, EP-A 0 357 149, WO 02/45507, GB 2 267 825 A, WO 94/23578, EP-A 0 330 904, EP-A 0 533 057, DE-A 36 24 910, WO 01/74785, EP-A 0 400 585, and EP-A 0 118 579.
  • the object of the present invention was to provide an improved crop protectant formulation with superior chemical and physical stability and agrochemical activity.
  • the present invention relates to microemulsions and concentrates thereof comprising
  • fipronil ⁇ 5-amino-l-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-4-[(trifluoromethyl)-sulfinyl]-lH- pyrazole-3-carbonitrile (CAS-RN 120068-37-3) ⁇ and optionally one or more insecticidally active ingredient in addition to fipronil, b) ethonal, c) one or more anionic surfactants, and d) one or more nonionic surfactants.
  • microemulsions and concentrates thereof according to the invention may, if appropriate, additionally comprise conventional adjuvants and additives as further components.
  • microemulsion concentrate is understood as meaning a composition wliich forms microemulsions upon dilution with water, for example oil-in-water microemulsions or water-in-oil - - microemulsions.
  • a microemulsion is understood as being an emulsion which is thermodynamically stable and has a droplet size of the emulsified phase which is generally in the range of 10-400 run, preferably 50-250 nm.
  • microemulsion concentrates according to the invention comprise the following amounts of components a), b), c) and d), where "% by weight” here and in all of the description, unless otherwise defined, refers to the relative weight of the component in question based on the total weight of the formulation:
  • Component b) 0.1-5% by weight, preferably 0.5-2% by weight, especially preferably 1-2% by weight.
  • Component c) 0.1-25% by weight, preferably 1-20% by weight, especially preferably 2-15% by weight.
  • Component d) 0.1-40% by weight, preferably 1-30% by weight, especially preferably 2-15% by weight.
  • Suitable insecticidally active ingredients a are, for example, compounds selected from the group consisting of
  • acephate acequinocyl, acetamiprid, acetoprole, acrinathrin, alanycarb, aldicarb, aldoxycarb, allethrin (d- cis-trans, d-trans), allyxycarb, aluminium phosphide, amidoflumet, aminocarb, amitraz, avermectin, aza- dirachtin, azamethiphos, azinphos (-methylAethyl), azocyclotin, benclothiaz, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, bifenazate, bifenthrin, binapacyrl, bioallethrin, bioallethrin-S- cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, bistriflur
  • insecticidally active ingredients a) which may be present in the microemulsions or concentrates thereof in addition to f ⁇ ronil are: cypermethrin, deltamethrin, imidacloprid, amitraz, triazophos, and their salts, for example the sodium salts, further preferred triazophos.
  • the active ingredients listed above are known from, for example, The Pesticide Manual, 13th edition (2003), British Crop Protection Council.
  • Component b) ethonal is a mixture of ethanol and benzene, which is well know to the skilled person.
  • Suitable as anionic surfactants c) are, for example, sulfates, sulfonates, phosphates and ph ' osponates of hydrocarbons which may optionally comprise alkylene oxide units.
  • the sulfates, sulfonates, - - phosphates and phosponates can exist in acid form or as salts.
  • Preferred anionic surfactants c) are those of the formula (I) hereinbelow:
  • the te ⁇ n alkylene oxide units is understood as meaning in particular units of C 2 -Ci O -alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, it being possible for the units within the surfactant to be identical or different from one another and to be arranged as a random mixture or blockwise.
  • R is preferably a Ci-C 2 o-alkyl radical (for example methyl, ethyl, propyl, butyl) or a C 6 -C 24 -aryl radical (for example phenyl, biphenyl, naphthyl) which can optionally have attached to it one or more radicals, for example from the Ci-C 2 o-alkyl group (for example linear or branched Ci-C 2 o-alkyl such as sec-butyl or dodecyl) which can have attached to it one or more radicals such as C 6 -C 2 o-aryl radicals (for example phenyl, biphenyl, naphthyl), and C 6 -C 2 o-aryl (for example phenyl, biphenyl or naphthyl) which can optionally have attached to it one or more radicals such as Ci-Cjo-alkyl (for example methyl, ethyl, propyl, butyl), or
  • R is a radical R 2 O-(AO) W , where w is an integer from 1 to 100 and AO is an alkylene oxide unit, for example (EO) x (PO) x (BO) 2 , where EO is an ethylene oxide unit, PO a propylene oxide unit, BO a butylene oxide unit, x an integer from 0-100, y an integer from 0- 100, z an integer from 0 to 100 and the total x+y+z is at least 1, and the alkylene oxide unit, for example (EO) x (PO) y (BO) z , can be arranged randomly or blockwise, and
  • R 2 is H, a Ci-C 2 o-alkyl radical (for example methyl, ethyl, propyl, butyl) or a C 6 -C 24 -aryl radical (for example phenyl, biphenyl, naphthyl), which can optionally have attached to it one or more radicals, for example from the Ci-C 2 o-alkyl group (for example linear or branched Ci-C 2 o-alkyl such as sec- butyl or dodecyl) which can have attached to it one or more radicals such as Ce-C 2O - aryl radicals (for example phenyl, biphenyl, naphthyl), and C 6 -C 2 o-aryl (for example phenyl, biphenyl or naphthyl) which can optionally have attached to it one or more radicals such as Q-Cio-alkyl (for example methyl, ethyl, propyl, butyl), or R 2
  • alkylarylsulfonates such as dodecylbenzenesulfonates, for example alkaline earth metal dodecylbenzenesulfonates such as calcium dodecylbenzenesulfonates (for example Phenylsulfonat® CaIOO by Clariant), alkylarylpolyglycol ether sulfates and sulfonates, in particular arylalkylaryl polyglycol ether sulfates such as tristyrylphenyl polyglycol ether sulfates, in particular the alkali metal or ammonium or triethanolamine salts (for example Soprophore® series by Rhodia), alkyl ether sulfates and their salts (for example such as Genapol® LRO by Clariant), alkyl sulfates and alkylsulfonates (for example such as the Hostapur® series by Clariant), alkylarylsulfonates, for example al
  • Suitable nonionic surfactants d) are, for example, alkoxylates, for example ethoxylates, propoxylates or butoxylates and their combinations.
  • alkoxylates is understood as meaning compounds comprising alkylene oxide units, in particular units of C 2 -Ci 0 -alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, it being possible for the units within the surfactant to be identical or different from one another and arranged randomly or blockwise.
  • alkoxylates d) are compounds of the formula (II) hereinbelow: R'-(AO) W -R 2 ( ⁇ ) in which R 1 is selected from the group H, HO, Ci-C 3 o-alkyl, which can be linear or branched (for example methyl, ethyl, propyl, butyl, pentyl, hexyl), CpQo-alkoxy, preferably Q-Cio-alkoxy, which can be linear or branched (for example methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), C 6 -C 24 -aryl (for example phenyl), which can optionally have attached to it one or more radicals such as Ci-C 3 o-arylalkyl (for example styrylphenyl) or Ci-C 30 -alkyl, in which the alkyl groups can be linear or branched (for example butyl or dodecyl), C 6
  • R 1 is a sorbitan ester residue, a glycerol ester residue or Ci-C 3 o-alkyl-NR 4 , preferably Ci O -C 2 o-alkyl- NR 4 , in which the Ci-C 2 o-alkyl group can be linear or branched (for example dodecyl, hexadecyl, octadecyl) and in which R 4 equals H or C r Cio-alkyl (for example methyl, ethyl, propyl, butyl), R 2 equals H or CpC ⁇ -alkyl which can be linear or branched (for example methyl, ethyl, propyl, butyl, pentyl or hexyl), and
  • w is an integer from 1 to 100, •
  • AO is an alkylene oxide unit, for example (EO) x (PO) y (BO) z , where EO is an ethylene oxide unit, PO a propylene oxide unit, BO a butylene oxide unit, x an integer from 0-100, y an integer from 0-100, z an integer from 0 to 100 and the total x+y+z is at least 1, and the alkylene oxide unit, for example (EO) x (PO) y (BO) z , has a random or blockwise structure.
  • alkylaryl polyalkoxylates for example the ethoxylates, propoxylates and/or butoxylates, arylalkylaryl polyalkoxylates such as tristyrylphenyl polyalkoxylates (for example Soprophor® series by Rhodia) and alkylphenyl polyalkoxylates such as tributylphenyl polyalkoxlates (for example Sopagenat® series by Clariant), alkylene oxide block copolymers such as ethylene oxide (EO)/propylene oxide (PO) block copolymers or ethylene oxide (EOybutylene oxide (BO) block copolymers (for example Pluronic® series by BASF), polyalkylene oxides such as polyethyene oxides, polypropylene oxides or polybutylene oxides, optionally substituted at one of the two terminal oxygen atoms by Ci-C 22 -hydrocarbon radicals, preferably Cio-
  • carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio, and the corresponding unsaturated and/or substituted radicals
  • their carbon skeleton can be straight-chain or branched in each case.
  • these radicals generally have 1 to 30 carbon atoms, the lower carbon skeletons, for example those having 1 to 6 carbon atoms, or, in the case of unsaturated groups, 2 to 6 carbon atoms, being preferred.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or sec-butyl, pentyls, hexyls, such as n-hexyl, i- hexyl and 1, 3- dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1,4- dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals which correspond to the alkyl radicals; for example, alkenyl is allyl, l-methylprop-2-en-l-yl, 2-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-l-yl, l-methylbut-3-en-l-yl and l-methylbut
  • Alkenyl in the form (C 3 -C 4 )alkenyl, (C 3 -C 5 )alkenyl, (C 3 -C 6 )alkenyl, (C 3 -Cg)alkenyl or (C 3 -C] 2 )- alkenyl is preferably an alkenyl radical having 3 to 4, 3 to 5, 3 to 6, 3 to 8 or 3 to 12 carbon atoms in which the double bond is not located at the carbon atom which is linked to the remaining moiety of the compound of the formula (I) ("yl" position).
  • This also applies analogously to (C 3 -C 4 )alkynyl and -the like, (C 3 -C 4 ) alkenyloxy and the like and (C 3 -C 4 )alkynyloxy and the like.
  • a hydrocarbon radical means a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl.
  • a hydrocarbon radical preferably has 1 to 40 carbon atoms, with preference 1 to 30 carbon atoms; a hydrocarbon radical is especially preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
  • Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydro- naphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.
  • a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more hetero atoms in the ring, preferably from the group consisting of N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 hetero atoms.
  • the heterocyclic radical can be for example a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more hetero atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or it is a partially or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetrahydro- furyl.
  • heteroaryl such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more hetero atoms, for example pyri
  • Suitable substituents for a substituted heterocyclic radical are the substituents mentioned further below, and additionally also oxo.
  • the oxo group can also be present at those hetero ring atoms which may exist at various levels of oxidation, for example in the case of N and S.
  • Halogen is, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl which is partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCl 3 , CHCl 2 , CH 2 CH 2 Cl;
  • haloalkoxyl is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 Cl; this also applies analogously to haloalkenyl and other halogen-substituted radicals.
  • Hydrocarbon radicals for example alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or heterocyclyl or heteroaryl can be substituted, the substituents meaning, for example, one or more, preferably 1 , 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkyl- -aminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl and unsaturated
  • substituents are, as a rule, those from the group consisting of halogen, for example fluorine and chlorine, (C r C 4 )alkyl, preferably methyl or ethyl, (C r C 4 )haloalkyl, preferably trifluoromethyl, (Ci-C 4 )alkoxy, preferably methoxy or ethoxy, (Ci-C 4 )haloalkoxy, nitro and cyano.
  • substituents methyl, methoxy and chlorine.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubsti- tuted, preferably up to trisubstituted, by identical or different radicals from the group consisting of halogen, (Ci-C 4 )alkyl, (C)-C 4 )alkoxy, (Ci-C 4 )halogenoalkyl, (C r C 4 )halogenoalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4- chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2, 5- and 2,3-dichlorophenyl, o-, m- and p- methoxyphenyl.
  • An acyl radical means the radical of an organic acid which is formed formally by eliminating an OH group from the organic acid, for example a carboxylic acid radical and radicals of acids derived from it such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids and phosphinic acids.
  • An acyl radical is preferably fo ⁇ nyl or aliphatic acyl from the group consisting of CO-R X , CS-R X , CO-OR", CS-OR", CS-SR", SOR Y or SO 2 R Y , where R" and R ⁇ in each case denotes a C 1 -C 30 - hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the two last-mentioned radicals being unsubstituted, N-monosubstituted or N,N-disubstituted.
  • Acyl is, for example, formyl, halogenoalkylcarbonyl, alkylcarbonyl such as (Ci-C 4 )alkylcarbonyl, phenylcarbonyl, it being possible for the phenyl ring to be substituted, for example as stated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N- alkyl- 1-iminoalkyl and other radicals of organic acids.
  • the formula (I) and the other compounds mentioned in the present description also encompass all of the stereoisomers and their mixtures.
  • Such compounds contain one or more asymmetric carbon atoms or else double bonds which are not mentioned specifically in the general formula.
  • the possible stereoisomers which are defined by their specific spatial shape, such as enantiomers, diastereomers, Z- and E-isomers, are all encompassed by the respective formulae and can be obtained from mixtures of the stereoisomers by customary methods or else be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
  • microemulsion concentrates according to the invention can be prepared by customary methods, for example mixing by dissolving or emulsifying the individual components, preferably at room temperature. If further auxiliaries and additives are present, they are likewise preferably introduced at room temperature. In general, the individual components can be added in any desired sequence.
  • the formulation auxiliaries such as inert materials and further additives, are likewise known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed.,
  • agrochemical active ingredients other than component a such as herbicides, fungicides, insecticides, safeners, fertilizers and/or growth regulators, for example in the form of a ready mix or a tank mix.
  • microemulsion concentrates according to the invention can be diluted with water to give micro- emulsions which are likewise subject matter of the present invention.
  • the weight ratio microemulsion concentrate:water can be, for example, 1 :0.1 to 1 :100, preferably 1 : 1 to 1 :100, which gives concentrated microemulsions which, per se, are storage stable.
  • they can be diluted further with water to give spray mixtures which are generally present in the form of emulsions such as microemulsions, aqueous solutions, suspensions or suspoemulsions.
  • microemulsion concentrates and microemulsions according to the invention may be present together in a ready mix which can then be applied in the customary manner, for example in the form of a spray mixture.
  • microemulsion concentrates and microemulsions according to the invention including the spray mixtures which can be obtained from them
  • auxiliaries such as anti-drift agents, humectants, fertilizers such as ammonium sulfate, urea or compound fertilizers, for example on a phosphorus, potassium and nitrogen basis, such as P,K,N fertilizers, or commercially available surfactants other than components c) and d), such as betainic or polymeric surfactants, stabilizers such as pH stabilizers, biocides, UV stabilizers, antifoams, synthetic or natural polymers, solvents, for example polar solvents such as water or unpolar solvents such as saturated or unsaturated aliphatic solvents which can be branched or unbranched, or aromatic solvents such as Solvesso®100, Solvesso®150 or Solvesso®) 200 or xylene.
  • formulation auxiliaries such as anti-drift agents, humectants, fertilizers such as ammonium sulfate, urea or compound fertilizers, for example on a phosphorus, potassium and nitrogen basis, such
  • wetters such as Genapol® LRO (0-20% by weight), dispersants such as Tamol® (0-15% by weight) or further surfactants (nonionic, cationic, anionic, polymeric surfactants) (0-30% by weight);
  • inorganic salts such as NaCl, Na 2 SC ⁇ , MgCl 2 (0-50% by weight), (oligo-, poly-) phosphates; carbonates such as potassium carbonate;
  • fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus- and potassium- containing components, if appropriate further trace elements (0-60% by weight);
  • antifoams such as Fluowet® PP (0-2% by weight);
  • binders such as suitable natural or synthetic substances such as polyamino acids, polyvinyl alcohols, polyvinylpyrrolidone, polyacrylic acid derivatives, (0-15% by weight); or
  • the agrochemical compositions according to the invention can be employed for example by application to the harmful organisms or the locations where they occur, for example by spraying.
  • the agrochemical compositions according to the invention are applied in the form of a spray mixture which comprises the components a), b), c) and d) in effective amounts and, if appropriate, further customary auxiliaries and additives, for example for formulation or use.
  • the spray mixture is prepared on the basis of water, it being possible to add customary auxiliaries and additives, for example oils, such as vegetable oils, or high-boiling hydrocarbons, such as kerosene or paraffin.
  • the concentration of agrochemical active ingredient a) is generally 10 "6 to 10% by weight, preferably 10 "5 to 4% by weight in the applied composition, for example the spray mixture, at an application rate of 1 to 5 000 1/ha, preferably 50 to 1 000 1/ha.
  • concentrated formulations which are present in commercially available form are, if appropriate, diluted in the customary manner, for example by means of water. It may be advantageous to add further amounts of components b), c) and d) and/or other conventional auxiliaries and additives for use, in particular self-emulsifying oils or paraffin oils, to the spray mixtures. Additional components a) or other agrochemical active ingredients other than component a) may also be added.
  • the application rate required of the agrochemical active ingredients a) can vary with the external condi- tions such as temperature, humidity, type of herbicide used. It can vary within wide limits, for example between 0. 001 and 10 kg/ha or more active substance; it is preferably between 0.005 and 5 kg/ha.
  • the agrochemical compositions according to the invention are preferably insecticidal compositions. They have an outstanding insecticidal activity against a broad spectrum of economically important insects.
  • the active compounds are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids and nematodes, which are encountered in agriculture, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector, and have good plant tolerance and favourable toxicity to warm-blooded animals and are tolerated well by the environment.
  • animal pests in particular insects, arachnids and nematodes, which are encountered in agriculture, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector, and have good plant tolerance and favourable toxicity to warm-blooded animals and are tolerated well by the environment.
  • They may be preferably employed as plant protection agents. They are active against normally sensitive and resistance species and against all or some stages of development.
  • the abovementioned pests include: - -
  • Anoplura e.g. Damalinia spp., Haematopi ⁇ us spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • Arachnida e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotar- sonemus la
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • Ancylostoma duodenale From the order of the Helminths e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus
  • Isopoda e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
  • Isoptera e.g. Reticulite ⁇ nes spp.
  • Odontotermes spp From the order of the Lepidoptera e.g.
  • Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • compositions according to the invention in economically important transgenic crops of useful plants and ornamentals, such as of Gramineae crops such as wheat, barley, rye, oats, sorghum and millet, rice and maize or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, pea and other vegetables is also possible.
  • the compositions according to the invention may preferably be employed as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or which have been rendered resistant to the phytotoxic effects of the herbicides by recombinant means.
  • the crops of plants can also have been genetically modified or obtained by the selection of mutants.
  • agrochemical compositions in particular insecticidal compositions, according to the invention may, if appropriate, be present in the fo ⁇ n of mixed formulations together with further agrochemical active ingredients and customary auxiliaries and additives, and these mixed formulations are then applied in the customary manner as a dilution with water, or else be prepared in the form of what are known as tank mixes by jointly diluting the separately formulated, or partially separately formulated, components with water.
  • insecticidal compositions according to the invention can be applied in the customary manner, for example with water as carrier in spray mixture rates of approximately 5 to 4 000 liters/ha. Likewise the compositions can be applied by what are known as the low-volume and ultra-low-volume methods (ULV).
  • UUV ultra-low-volume methods
  • insecticidal compositions of the invention may also comprise one, two or more agrochemical active ingredients other than the insecticides a) (for example herbicids, fungicides), usually in minor amounts, in order to complement the property profile.
  • agrochemical active ingredients other than the insecticides a) (for example herbicids, fungicides), usually in minor amounts, in order to complement the property profile.
  • microemulsion concentrates according to the invention give stable microemulsions upon dilution with water without the use of alcoholic solvent.
  • microemulsion concentrates and microemulsions according to the invention show an advantageous physical application behavior.
  • the agrochemical active ingredient remains uniformly distributed in the spray tank, making possible a uniform application to the crop or area under cultivation.
  • Even mixtures formed in the spray tank ,(tank mixes) such as aqueous solutions, suspensions, emulsions or suspoemulsions are stable.
  • the agrochemical compositions according to the invention have an outstanding biological activity and preferably act synergistically. These effects pe ⁇ nit, inter alia, the application rate to be reduced, a broader spectrum of harmful organisms to be controlled, gaps in the control to be overcome, a more rapid and reliable activity, an extended long-term activity, complete control of the harmful organisms with only one or few applications, and the application window to be widened.

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Abstract

The present invention relates to microemulsions or concentrates thereof comprising a) fipronil and optionally one or more insecticidally active ingredient in addition to fipronil, b) one or more nonalcoholic organic solvents, c) one or more anionic surfactants, and d) one or more nonionic surfactants. The microemulsions or concentrates thereof are suitable in the field of crop protection.

Description

Microemulsions
The present invention relates to the field of crop protectant formulations. In particular, the invention relates to liquid formulations in the form of microemulsions or concentrates thereof which comprise agrochemical active ingredients.
Active ingredients for crop protection are generally not employed in their pure foπn. Depending on the field and type of application, and on physical, chemical and biological parameters, the active ingredient is employed as a mixture with conventional adjuvants and additives as a solid or liquid active ingredient formulation.
Liquid formulations are described, for example, in EP-A 0 261 492, EP-A 0 394 847, WO 2004/054360, WO 95/17822, WO 98/31223, WO 89/03176, EP-A 0 357 149, WO 02/45507, GB 2 267 825 A, WO 94/23578, EP-A 0 330 904, EP-A 0 533 057, DE-A 36 24 910, WO 01/74785, EP-A 0 400 585, and EP-A 0 118 579.
The object of the present invention was to provide an improved crop protectant formulation with superior chemical and physical stability and agrochemical activity.
Surprisingly, it has now been found that this object is achieved by the specific microemulsions (ME) or concentrates thereof (MC) of the present invention.
Thus, the present invention relates to microemulsions and concentrates thereof comprising
a) fipronil {5-amino-l-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-4-[(trifluoromethyl)-sulfinyl]-lH- pyrazole-3-carbonitrile (CAS-RN 120068-37-3)} and optionally one or more insecticidally active ingredient in addition to fipronil, b) ethonal, c) one or more anionic surfactants, and d) one or more nonionic surfactants.
In addition, the microemulsions and concentrates thereof according to the invention may, if appropriate, additionally comprise conventional adjuvants and additives as further components.
The term microemulsion concentrate (MC) is understood as meaning a composition wliich forms microemulsions upon dilution with water, for example oil-in-water microemulsions or water-in-oil - - microemulsions. A microemulsion is understood as being an emulsion which is thermodynamically stable and has a droplet size of the emulsified phase which is generally in the range of 10-400 run, preferably 50-250 nm.
In general, the microemulsion concentrates according to the invention comprise the following amounts of components a), b), c) and d), where "% by weight" here and in all of the description, unless otherwise defined, refers to the relative weight of the component in question based on the total weight of the formulation:
Component a): 0.001-50% by weight, preferably 0.1-40% by weight, especially preferably 5-40% by weight.
Component b): 0.1-5% by weight, preferably 0.5-2% by weight, especially preferably 1-2% by weight.
Component c): 0.1-25% by weight, preferably 1-20% by weight, especially preferably 2-15% by weight.
Component d): 0.1-40% by weight, preferably 1-30% by weight, especially preferably 2-15% by weight.
Suitable insecticidally active ingredients a), which could be used in addition to fipronil, are, for example, compounds selected from the group consisting of
acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, alanycarb, aldicarb, aldoxycarb, allethrin (d- cis-trans, d-trans), allyxycarb, aluminium phosphide, amidoflumet, aminocarb, amitraz, avermectin, aza- dirachtin, azamethiphos, azinphos (-methylAethyl), azocyclotin, benclothiaz, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, bifenazate, bifenthrin, binapacyrl, bioallethrin, bioallethrin-S- cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, bromfenvinfos (-methyl), bromophos-ethyl, bromopropylate, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butoxycarboxim, cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chinomethionat, chlofluazuron, chlordane, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvin- phos, chlormephos, chlorobenzilate, chloropicrin, chlorpyrifos (-methyl/-ethyl), chlovaporthrin, chroma- fenozide, cis-cypermethrin, cis-permethrin, cis-resmethrin, clocythrin, cloethocarb, clofentezine, clothia- nidin, clothiazoben, codlemone, coumaphos, cryolite, cyanofenphos, cyanophos, cycloprene, cyclopro- thrin, cyflumetofen, cyfluthrin, cyhalothrin, cyhexatin, cypennethrin (alpha-, beta-, theta-, zeta-), cy- phenothrin, cyromazine, DDT, deltamethrin, demeton-s-methyl, demeton-s-methylsulphon, diafenthi- uron, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicofol, dicrotophos, dicyclanil, diflubenz- uron, dimethoate, dimethylvinphos, dimetilan, dinobuton, dinocap, dinotefuran, diofenolan, dioxabenzo- fos, disulfoton, DNOC, emamectin, emamectin-benzoate, empenthrin (lR-isomer), endosulfan, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethiprole, ethoprophos, etofenprox, etoxazόle, etrim- fos, famphur, fenamiphos, fenazaquin, fenbutatin-oxide, fenfluthrin, fenitrothion, fenobucarb, fenothio- carb, fenoxacrim, fenoxycarb, fenpropatlirin, fenpyrithrin, fenpyroximate, fensul.fothion, fenthion, fen- trifanil, fenvalerate, flonicamid, fluacrypyrim, fluazuron, flubendiamide, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin, fluvalinate, fonofos, formetanate, foπnothion, fosmethilan, fosthiazate, fubfenprox, fiirathiocarb, gam- -ma-cyhalothrin, gamma-HCH, gossyplure, halofenozide, HCH, heptachlor, heptenophos, hexaflumuron, hexythiazox, hydramethylnon, hydramethylnone, hydroprene, imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos, isoprocai-b, isopropyl O-salicylate, isoxathion, ivermectin, japonilure, kadethrin, kinoprene, lambda-cyhalothrin, lindane, lufenuron, malatliion, mecarbam, me- tam-sodium, methacrifos, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxy- chlor, methoxyfenozide, methyl bromide, metofluthrin, metolcarb, metoxadiazone, mevinphos, milbe- mycin, monocrotophos, naled, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, parathion (-methylAethyl), penfluron, peπnethrin (cis-, trans-), petroleum, phenothrin (lR-trans isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos (-methyl/-ethyl), potassium oleate, prallethrin, pro- fenofos, profluthrin, promecarb, propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos, pyrafluprole, pyresmethrin, pyrethrins (pyrethrum), pyridaben, pyridalyl, pyridaphenthion, pyridathion, pyrimidifen, pyriprole, pyriproxifen, quinalphos, resmethrin, rotenone, RU 15525, sebufos, silafluofen, spinosad, spirodiclofen, spiromesifen, spirotetramat (CAS- reg.-No.: 203313-25-1), 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (alias: carbonic acid 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl ester, CAS-reg.-No.: 382608-10-8), sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvali- nate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, terallethrin, terbu- fos, tetrachlorvinphos, tetradifon, tetramethrin (lR-isomer), tetrasul, thiacloprid, thiamethoxam, thio- cyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, triarathene, triazamate, triazophos, triclorfon, triflumuron, trimetliacarb, triprene, vamido- thion, vaniliprole, verbutin, XMC, xylylcarb, ZXI 8901. Further preferred among the insecticidally active ingredients a) which may be present in the microemulsions or concentrates thereof in addition to fφronil are: cypermethrin, deltamethrin, imidacloprid, amitraz, triazophos, and their salts, for example the sodium salts, further preferred triazophos.
The active ingredients listed above are known from, for example, The Pesticide Manual, 13th edition (2003), British Crop Protection Council.
Component b) ethonal is a mixture of ethanol and benzene, which is well know to the skilled person. Suitable as anionic surfactants c) are, for example, sulfates, sulfonates, phosphates and ph'osponates of hydrocarbons which may optionally comprise alkylene oxide units. The sulfates, sulfonates, - - phosphates and phosponates can exist in acid form or as salts. Preferred anionic surfactants c) are those of the formula (I) hereinbelow:
R-Q (I) in which Q is -O-SO3M, -SO3M, -O-PO3HM or -PO3HM, where M is H or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion, R is an unsubstituted or substituted Ci-C3o-hydrocarbon radical which can optionally be bonded via alkylene oxide units, or R is an alkylene oxide unit.
The teπn alkylene oxide units is understood as meaning in particular units of C2-CiO-alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, it being possible for the units within the surfactant to be identical or different from one another and to be arranged as a random mixture or blockwise.
R is preferably a Ci-C2o-alkyl radical (for example methyl, ethyl, propyl, butyl) or a C6-C24-aryl radical (for example phenyl, biphenyl, naphthyl) which can optionally have attached to it one or more radicals, for example from the Ci-C2o-alkyl group (for example linear or branched Ci-C2o-alkyl such as sec-butyl or dodecyl) which can have attached to it one or more radicals such as C6-C2o-aryl radicals (for example phenyl, biphenyl, naphthyl), and C6-C2o-aryl (for example phenyl, biphenyl or naphthyl) which can optionally have attached to it one or more radicals such as Ci-Cjo-alkyl (for example methyl, ethyl, propyl, butyl), or
R is a radical R2O-(AO)W, where w is an integer from 1 to 100 and AO is an alkylene oxide unit, for example (EO)x(PO)x(BO)2, where EO is an ethylene oxide unit, PO a propylene oxide unit, BO a butylene oxide unit, x an integer from 0-100, y an integer from 0- 100, z an integer from 0 to 100 and the total x+y+z is at least 1, and the alkylene oxide unit, for example (EO)x(PO)y(BO)z, can be arranged randomly or blockwise, and
R2 is H, a Ci-C2o-alkyl radical (for example methyl, ethyl, propyl, butyl) or a C6-C24-aryl radical (for example phenyl, biphenyl, naphthyl), which can optionally have attached to it one or more radicals, for example from the Ci-C2o-alkyl group (for example linear or branched Ci-C2o-alkyl such as sec- butyl or dodecyl) which can have attached to it one or more radicals such as Ce-C2O- aryl radicals (for example phenyl, biphenyl, naphthyl), and C6-C2o-aryl (for example phenyl, biphenyl or naphthyl) which can optionally have attached to it one or more radicals such as Q-Cio-alkyl (for example methyl, ethyl, propyl, butyl), or R2 is -0-SO3M, -SO3M, -0-PO3HM or -PO3HM, preferably - PO3HM, where M equals H or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion.
Especially preferred anionic surfactants c) are alkylarylsulfonates such as dodecylbenzenesulfonates, for example alkaline earth metal dodecylbenzenesulfonates such as calcium dodecylbenzenesulfonates (for example Phenylsulfonat® CaIOO by Clariant), alkylarylpolyglycol ether sulfates and sulfonates, in particular arylalkylaryl polyglycol ether sulfates such as tristyrylphenyl polyglycol ether sulfates, in particular the alkali metal or ammonium or triethanolamine salts (for example Soprophore® series by Rhodia), alkyl ether sulfates and their salts (for example such as Genapol® LRO by Clariant), alkyl sulfates and alkylsulfonates (for example such as the Hostapur® series by Clariant), alkyl polyglycol ether phosphates, in particular the alkali metal salts (for example the Rhodafac® series Rhodia), alkylaryl polyglycol ether phosphates, in particular in the foπn of the alkali metal salts. In general, the salts are preferably metal salts such as alkali or alkaline earth metal salts or ammonium or trialkylamine salts.
Suitable nonionic surfactants d) are, for example, alkoxylates, for example ethoxylates, propoxylates or butoxylates and their combinations. The term alkoxylates is understood as meaning compounds comprising alkylene oxide units, in particular units of C2-Ci0-alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, it being possible for the units within the surfactant to be identical or different from one another and arranged randomly or blockwise. Examples of alkoxylates d) are compounds of the formula (II) hereinbelow: R'-(AO)W-R2 (π) in which R1 is selected from the group H, HO, Ci-C3o-alkyl, which can be linear or branched (for example methyl, ethyl, propyl, butyl, pentyl, hexyl), CpQo-alkoxy, preferably Q-Cio-alkoxy, which can be linear or branched (for example methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), C6-C24-aryl (for example phenyl), which can optionally have attached to it one or more radicals such as Ci-C3o-arylalkyl (for example styrylphenyl) or Ci-C30-alkyl, in which the alkyl groups can be linear or branched (for example butyl or dodecyl), C6-C24-aryloxy (for example phenoxy), which can optionally have attached to it one or more radicals such as Ci-C3o-arylalkyl (for example styrylphenyl), or Q-Qo-alkyl, in which the alkyl groups can be linear or branched (for example butyl or dodecyl), or
R1 is a sorbitan ester residue, a glycerol ester residue or Ci-C3o-alkyl-NR4, preferably CiO-C2o-alkyl- NR4, in which the Ci-C2o-alkyl group can be linear or branched (for example dodecyl, hexadecyl, octadecyl) and in which R4 equals H or CrCio-alkyl (for example methyl, ethyl, propyl, butyl), R2 equals H or CpCβ-alkyl which can be linear or branched (for example methyl, ethyl, propyl, butyl, pentyl or hexyl), and
w is an integer from 1 to 100, •
AO is an alkylene oxide unit, for example (EO)x(PO)y(BO)z, where EO is an ethylene oxide unit, PO a propylene oxide unit, BO a butylene oxide unit, x an integer from 0-100, y an integer from 0-100, z an integer from 0 to 100 and the total x+y+z is at least 1, and the alkylene oxide unit, for example (EO)x(PO)y(BO)z, has a random or blockwise structure.
Especially preferred nonionic surfactants d) are alkylaryl polyalkoxylates, for example the ethoxylates, propoxylates and/or butoxylates, arylalkylaryl polyalkoxylates such as tristyrylphenyl polyalkoxylates (for example Soprophor® series by Rhodia) and alkylphenyl polyalkoxylates such as tributylphenyl polyalkoxlates (for example Sopagenat® series by Clariant), alkylene oxide block copolymers such as ethylene oxide (EO)/propylene oxide (PO) block copolymers or ethylene oxide (EOybutylene oxide (BO) block copolymers (for example Pluronic® series by BASF), polyalkylene oxides such as polyethyene oxides, polypropylene oxides or polybutylene oxides, optionally substituted at one of the two terminal oxygen atoms by Ci-C22-hydrocarbon radicals, preferably Cio- C22-hydrocarbon radicals such as straight-chain or branched C10-C22-alkyl radicals (for example decyl, dodecyl, tetradecyl, hexadecyl), for example polyglycol ethers which can be substituted by isotridecyl (for example Genapol® series by Clariant), alkoxylated, such as ethoxylated, oils such as vegetable oils, for example alkoxylated, such as ethoxylated, castor oil (Emulsogen® series Clariant), alkoxylated, such as ethoxylated, (CiO-C22)-fatty amines (for example Genamin® series by Clariant).
When the present description mentions carbon-containing radicals, such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio, and the corresponding unsaturated and/or substituted radicals, their carbon skeleton can be straight-chain or branched in each case. Unless mentioned otherwise, these radicals generally have 1 to 30 carbon atoms, the lower carbon skeletons, for example those having 1 to 6 carbon atoms, or, in the case of unsaturated groups, 2 to 6 carbon atoms, being preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or sec-butyl, pentyls, hexyls, such as n-hexyl, i- hexyl and 1, 3- dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1,4- dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals which correspond to the alkyl radicals; for example, alkenyl is allyl, l-methylprop-2-en-l-yl, 2-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-l-yl, l-methylbut-3-en-l-yl and l-methylbut-2-en- 1-yl; alkynyl is, for example, propargyl, but-2-yn-l-yl, but-3-yn-l-yl, 1- methylbut-3-yn-l-yl. Alkenyl in the form (C3-C4)alkenyl, (C3-C5)alkenyl, (C3-C6)alkenyl, (C3-Cg)alkenyl or (C3-C]2)- alkenyl is preferably an alkenyl radical having 3 to 4, 3 to 5, 3 to 6, 3 to 8 or 3 to 12 carbon atoms in which the double bond is not located at the carbon atom which is linked to the remaining moiety of the compound of the formula (I) ("yl" position). This also applies analogously to (C3-C4)alkynyl and -the like, (C3-C4) alkenyloxy and the like and (C3-C4)alkynyloxy and the like.
A hydrocarbon radical means a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl.
A hydrocarbon radical preferably has 1 to 40 carbon atoms, with preference 1 to 30 carbon atoms; a hydrocarbon radical is especially preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydro- naphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.
A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more hetero atoms in the ring, preferably from the group consisting of N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 hetero atoms. The heterocyclic radical can be for example a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more hetero atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or it is a partially or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetrahydro- furyl. Suitable substituents for a substituted heterocyclic radical are the substituents mentioned further below, and additionally also oxo. The oxo group can also be present at those hetero ring atoms which may exist at various levels of oxidation, for example in the case of N and S.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl which is partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxyl is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; this also applies analogously to haloalkenyl and other halogen-substituted radicals. Hydrocarbon radicals, for example alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or heterocyclyl or heteroaryl can be substituted, the substituents meaning, for example, one or more, preferably 1 , 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkyl- -aminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl and unsaturated aliphatic radicals which correspond to the abovementioned saturated hydrocarbon-containing radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy and the like. In the case of radicals with carbon atoms, those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Preferred substituents are, as a rule, those from the group consisting of halogen, for example fluorine and chlorine, (CrC4)alkyl, preferably methyl or ethyl, (CrC4)haloalkyl, preferably trifluoromethyl, (Ci-C4)alkoxy, preferably methoxy or ethoxy, (Ci-C4)haloalkoxy, nitro and cyano. Especially preferred in this context are the substituents methyl, methoxy and chlorine.
Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubsti- tuted, preferably up to trisubstituted, by identical or different radicals from the group consisting of halogen, (Ci-C4)alkyl, (C)-C4)alkoxy, (Ci-C4)halogenoalkyl, (CrC4)halogenoalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4- chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2, 5- and 2,3-dichlorophenyl, o-, m- and p- methoxyphenyl.
An acyl radical means the radical of an organic acid which is formed formally by eliminating an OH group from the organic acid, for example a carboxylic acid radical and radicals of acids derived from it such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids and phosphinic acids.
An acyl radical is preferably foπnyl or aliphatic acyl from the group consisting of CO-RX, CS-RX, CO-OR", CS-OR", CS-SR", SORY or SO2RY, where R" and Rγ in each case denotes a C1-C30- hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the two last-mentioned radicals being unsubstituted, N-monosubstituted or N,N-disubstituted.
Acyl is, for example, formyl, halogenoalkylcarbonyl, alkylcarbonyl such as (Ci-C4)alkylcarbonyl, phenylcarbonyl, it being possible for the phenyl ring to be substituted, for example as stated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N- alkyl- 1-iminoalkyl and other radicals of organic acids. The formula (I) and the other compounds mentioned in the present description also encompass all of the stereoisomers and their mixtures. Such compounds contain one or more asymmetric carbon atoms or else double bonds which are not mentioned specifically in the general formula. The possible stereoisomers, which are defined by their specific spatial shape, such as enantiomers, diastereomers, Z- and E-isomers, are all encompassed by the respective formulae and can be obtained from mixtures of the stereoisomers by customary methods or else be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
The microemulsion concentrates according to the invention can be prepared by customary methods, for example mixing by dissolving or emulsifying the individual components, preferably at room temperature. If further auxiliaries and additives are present, they are likewise preferably introduced at room temperature. In general, the individual components can be added in any desired sequence.
The preparation processes are known in principle and are described, for example, in Winnacker- Kϋichler, "Chemische Technologie" [Chemical Technology], volume 7, C. Hauser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, New York, 1973; K. Martens, "Spray Drying" Handbook, 3 rd Ed. 1979, G. Goodwin Ltd. London; H. Mollet, A. Grubenmann, "Formulierungstechnik" [Formulation Technology], Wiley- VCH, Weinheim 2000.
The formulation auxiliaries, such as inert materials and further additives, are likewise known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed.,
Darland Books, Caldwell NJ., H. v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J.
Wiley & Sons, New York; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, New York 1963;
McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., New York 1964; Schδnfeldt,
"Grenzflachenaktive Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker- Kϋichler, "Chemische Technologie", volume 7, C. Hauser
Verlag Munich, 4th Ed. 1986.
Based on these formulations, it is also possible to prepare combinations with agrochemical active ingredients other than component a), such as herbicides, fungicides, insecticides, safeners, fertilizers and/or growth regulators, for example in the form of a ready mix or a tank mix.
The microemulsion concentrates according to the invention can be diluted with water to give micro- emulsions which are likewise subject matter of the present invention. The weight ratio microemulsion concentrate:water can be, for example, 1 :0.1 to 1 :100, preferably 1 : 1 to 1 :100, which gives concentrated microemulsions which, per se, are storage stable. For application .purposes, they can be diluted further with water to give spray mixtures which are generally present in the form of emulsions such as microemulsions, aqueous solutions, suspensions or suspoemulsions.
-Components a), b), c) and d) of the microemulsion concentrates and microemulsions according to the invention may be present together in a ready mix which can then be applied in the customary manner, for example in the form of a spray mixture.
In addition to components a), b), c) and d), the microemulsion concentrates and microemulsions according to the invention, including the spray mixtures which can be obtained from them
(hereinbelow all referred to as agrochemical compositions according to the invention), may additionally comprise as further component customary auxiliaries and additives, for example formulation auxiliaries such as anti-drift agents, humectants, fertilizers such as ammonium sulfate, urea or compound fertilizers, for example on a phosphorus, potassium and nitrogen basis, such as P,K,N fertilizers, or commercially available surfactants other than components c) and d), such as betainic or polymeric surfactants, stabilizers such as pH stabilizers, biocides, UV stabilizers, antifoams, synthetic or natural polymers, solvents, for example polar solvents such as water or unpolar solvents such as saturated or unsaturated aliphatic solvents which can be branched or unbranched, or aromatic solvents such as Solvesso®100, Solvesso®150 or Solvesso®) 200 or xylene. These agrochemical compositions and their preparation and use are likewise novel and subject matter of the present invention.
Preferred examples of customary auxiliaries and additives are
• wetters such as Genapol® LRO (0-20% by weight), dispersants such as Tamol® (0-15% by weight) or further surfactants (nonionic, cationic, anionic, polymeric surfactants) (0-30% by weight);
• inorganic salts such as NaCl, Na2SC^, MgCl2 (0-50% by weight), (oligo-, poly-) phosphates; carbonates such as potassium carbonate;
• fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus- and potassium- containing components, if appropriate further trace elements (0-60% by weight);
• antifoams such as Fluowet® PP (0-2% by weight);
• binders such as suitable natural or synthetic substances such as polyamino acids, polyvinyl alcohols, polyvinylpyrrolidone, polyacrylic acid derivatives, (0-15% by weight); or
• solvents such as water or organic solvents (0-15% by weight). The agrochemical compositions according to the invention can be employed for example by application to the harmful organisms or the locations where they occur, for example by spraying. As a rule, the agrochemical compositions according to the invention are applied in the form of a spray mixture which comprises the components a), b), c) and d) in effective amounts and, if appropriate, further customary auxiliaries and additives, for example for formulation or use. In general, the spray mixture is prepared on the basis of water, it being possible to add customary auxiliaries and additives, for example oils, such as vegetable oils, or high-boiling hydrocarbons, such as kerosene or paraffin.
Upon application, the concentration of agrochemical active ingredient a) is generally 10"6 to 10% by weight, preferably 10"5 to 4% by weight in the applied composition, for example the spray mixture, at an application rate of 1 to 5 000 1/ha, preferably 50 to 1 000 1/ha.
For use, concentrated formulations which are present in commercially available form are, if appropriate, diluted in the customary manner, for example by means of water. It may be advantageous to add further amounts of components b), c) and d) and/or other conventional auxiliaries and additives for use, in particular self-emulsifying oils or paraffin oils, to the spray mixtures. Additional components a) or other agrochemical active ingredients other than component a) may also be added.
The application rate required of the agrochemical active ingredients a) can vary with the external condi- tions such as temperature, humidity, type of herbicide used. It can vary within wide limits, for example between 0. 001 and 10 kg/ha or more active substance; it is preferably between 0.005 and 5 kg/ha.
The agrochemical compositions according to the invention are preferably insecticidal compositions. They have an outstanding insecticidal activity against a broad spectrum of economically important insects.
The active compounds are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids and nematodes, which are encountered in agriculture, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector, and have good plant tolerance and favourable toxicity to warm-blooded animals and are tolerated well by the environment. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistance species and against all or some stages of development. The abovementioned pests include: - -
From the order of the Anoplura (Phthiraptera) e.g. Damalinia spp., Haematopiηus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
From the order of the Arachnida e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotar- sonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici. From the order of the Bivalva e.g. Dreissena spp.
From the order of the Chilopoda e.g. Geophilus spp., Scutigera spp.
From the order of the Coleoptera e.g. Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamoφha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp. From the order of the Collembola e.g. Onychiurus armatus. From the order of the Dermaptera e.g. Forficula auricularia. From the order of the Diplopoda e.g. Blaniulus guttulatus.
From the order of the Diptera e.g. Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp. Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp. From the order of the Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp. From the order of the Helminths e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti. Furthermore, protozoa, e.g. Eimeria, may be combated.
From the order of the Heteroptera e.g. Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. From the order of the Homoptera e.g. Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aoni- diella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Meto- polophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Proto- pulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia - - spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii. From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Isopoda e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber. From the order of the Isoptera e.g. Reticuliteπnes spp., Odontotermes spp. From the order of the Lepidoptera e.g. Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoveφa spp., Heliothis spp., Hof- mannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Litho- colletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp. From the order of the Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
From the order of the Siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis. From the order of the Symphyla e.g. Scutigerella immaculata. From the order of the Thysanoptera e.g. Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp. From the order of the Thysanura e.g. Lepisma saccharina.
The use of the insecticidal compositions according to the invention in economically important transgenic crops of useful plants and ornamentals, such as of Gramineae crops such as wheat, barley, rye, oats, sorghum and millet, rice and maize or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, pea and other vegetables is also possible. The compositions according to the invention may preferably be employed as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or which have been rendered resistant to the phytotoxic effects of the herbicides by recombinant means. When the insecticidal compositions according to the invention are used in transgenic crops, effects are frequently observed, in addition to the effects against harmful plants observed in other crops, which are specific for the application in the transgenic crop in question, for example a modified or specifically extended weed spectrum which can be controlled, altered application rates which can be employed for application, preferably good combining properties with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.
The crops of plants can also have been genetically modified or obtained by the selection of mutants.
The agrochemical compositions, in particular insecticidal compositions, according to the invention may, if appropriate, be present in the foπn of mixed formulations together with further agrochemical active ingredients and customary auxiliaries and additives, and these mixed formulations are then applied in the customary manner as a dilution with water, or else be prepared in the form of what are known as tank mixes by jointly diluting the separately formulated, or partially separately formulated, components with water.
The insecticidal compositions according to the invention can be applied in the customary manner, for example with water as carrier in spray mixture rates of approximately 5 to 4 000 liters/ha. Likewise the compositions can be applied by what are known as the low-volume and ultra-low-volume methods (ULV).
In addition, the insecticidal compositions of the invention may also comprise one, two or more agrochemical active ingredients other than the insecticides a) (for example herbicids, fungicides), usually in minor amounts, in order to complement the property profile.
This results in a large number of possibilities for combining a plurality of agrochemical active ingredients with one another and for employing them jointly for controlling harmful organisms such as harmful plants in crops of plants, without deviating from the spirit of the invention.
Surprisingly, the microemulsion concentrates according to the invention give stable microemulsions upon dilution with water without the use of alcoholic solvent.
The microemulsion concentrates and microemulsions according to the invention show an advantageous physical application behavior. During the application, the agrochemical active ingredient remains uniformly distributed in the spray tank, making possible a uniform application to the crop or area under cultivation. Even mixtures formed in the spray tank ,(tank mixes) such as aqueous solutions, suspensions, emulsions or suspoemulsions are stable.
The agrochemical compositions according to the invention have an outstanding biological activity and preferably act synergistically. These effects peπnit, inter alia, the application rate to be reduced, a broader spectrum of harmful organisms to be controlled, gaps in the control to be overcome, a more rapid and reliable activity, an extended long-term activity, complete control of the harmful organisms with only one or few applications, and the application window to be widened.

Claims

Patent Claims
1. Microemulsions and concentrates thereof comprising a) fipronil and optionally one or more insecticidally active ingredient in addition to fipronil, b) ethonal, c) one or more anionic • surfactants, and d) one or more nonionic surfactants.
2. Microemulsions and concentrates thereof as claimed in claim 1, which comprise, as component a) fipronil only.
3. Microemulsions and concentrates thereof as claimed in claim 1, which comprise, as component a) fipronil in mixture with triazophos.
4. Microemulsions and concentrates thereof as claimed in claim 1, which comprise, as component a) fipronil in mixture with one or more insecticidally active ingredient selected from cypermethrin, deltamethrin, imidacloprid, and amitraz.
5. Microemulsions and concentrates thereof as claimed in claim 1 to 4 , which comprise, as component c), one or more anionic surfactants from the group sulfates, sulfonates, phosphates and phosphonates of hydrocarbons which can optionally be alkoxylated, preferably alkylarylsulfonates, alkylaryl polyglycol ether phosphate sulfates, alkylaryl polyglycol ether phosphate sulfonates, alkyl ether sulfates, alkyl sulfates, alkylsulfonates, alkyl polyglycol ether phosphates and alkylaryl polyglycol ether phosphates.
6. Microemulsions and concentrates thereof as claimed in one or more of claims 1 to 5, which comprise, as component d), one or more nonionic surfactants from the group alkoxylates, preferably alkylaryl polyalkoxylates, alkylene oxide block copolymers, polyalkylene oxides which can be substituted by Ci0-C22-hydrocarbon radicals, alkoxylated oils, alkoxylated C]0- C22-fatty amines.
7. Microemulsions and concentrates thereof as claimed in one or more of claims 1 to 6, which additionally comprise conventional auxiliaries and additives.
8. A method for the preparation of a microemulsion concentrate as claimed in one or more of claims 1 to 7, in which the components are mixed. - -
9. The use of a microemulsion concentrate as claimed in one or more of claims 1 to 8 for the preparation of a microemulsion.
10. An agrochemical composition comprising a) fipronil and optionally one or more • insecticidally active ingredient in addition to fipronil, b) ethonal, c) one or more anionic surfactants, d) one or more nonionic surfactants, and e) water.
11. An agrochemical composition as claimed in claim 10, which additionally comprises conventional auxiliaries and additives.
12. An agrochemical composition as claimed in claim 10 or 11, in the form of a microemulsion or of the spray mixture which can be obtained therefrom.
13. An agrochemical composition which is obtainable by diluting a microemulsion concentrate as claimed in one or more of claims 1 to 7 with water.
14. A process for the preparation of an agrochemical composition as claimed in one or more of claims 10 to 13, in which the components are mixed.
15. A method for controlling harmful organisms, in which an effective amount of an agrochemical composition as claimed in one or more of claims 1 to 7 or 10 to 13 is applied to the harmful organisms or the locations where they occur.
16. A method for controlling undesired vegetation, in which an effective amount of an agrochemical composition as claimed in one or more of claims 1 to 7 or 10 to 13 is applied to the harmful plants, parts of the plants, plant seeds, the area on which the plants grow.
17. The use of an agrochemical composition as claimed in one or more of claims 1 to 7 or 10 to 13 for controlling harmful organisms.
18. The use as claimed in claim 17, wherein the harmful organisms are harmful plants.
PCT/EP2006/006904 2005-07-27 2006-07-14 Microemulsions and concentrates comprising fipronil WO2007017040A2 (en)

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US8367583B2 (en) 2009-05-25 2013-02-05 Sumitomo Chemical Company, Limited Composition and method for controlling pests

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JP2014510100A (en) * 2011-03-23 2014-04-24 マクテシム・ケミカル・ワークス・リミテツド Synergistic agricultural pest control
CN102428913B (en) * 2011-11-11 2014-01-22 山东一览科技有限公司 Microemulsion insecticide and production process thereof
GB201707930D0 (en) * 2017-05-17 2017-06-28 Syngenta Participations Ag Formulation component
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WO2008129060A3 (en) * 2007-04-23 2009-02-19 Basf Se Plant produtivity enhancement by combining chemical agents with transgenic modifications
EP2392662A3 (en) * 2007-04-23 2012-03-14 Basf Se Plant productivity enhancement by combining chemical agents with transgenic modifications
EA017621B1 (en) * 2007-04-23 2013-01-30 Басф Се Plant productivity enhancement by combining chemical agents with transgenic modifications
US20100159400A1 (en) * 2008-12-24 2010-06-24 Samsung Electronics Co., Ltd. Composition for removing a photoresist pattern and method of forming a metal pattern using the composition
US8367583B2 (en) 2009-05-25 2013-02-05 Sumitomo Chemical Company, Limited Composition and method for controlling pests

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BRPI0613908A2 (en) 2011-02-15

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