BRPI0613908A2 - microemulsions - Google Patents

Abstract

MICROEMULSOES. The present invention relates to microemulsions or concentrates thereof comprising a) fipronil and optionally one or more insecticidally active ingredients in addition to fipronil, b) one or more non-alcoholic organic solvents, c) one or more anionic surfactants, and d) one or more non-ionic surfactants. Microemulsions or concentrates are suitable in the field of crop protection.

Description

Patent Descriptive Report for "MICROEMULSIONS".

The present invention relates to the field of crop protection formulations. In particular, the invention relates to liquid formulations in the form of microemulsions or concentrates thereof comprising agrochemical active ingredients.

Active ingredients for crop protection generally not employed in their pure form. 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 formulation of the active ingredient.

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, GB2 267 825 A, WO 94/23578, EP-A 0 330 904, EP-A 0 533 057, DE-A 36 24910, 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 protection formulation with superior chemical and physical stability and agrochemical activity.

Surprisingly, it has now been found that this objective is achieved by specific or concentrated microemulsions (ME) thereof of the present invention.

Therefore, the present invention relates to microemulsions and concentrates thereof comprising

a) Fipronyl {5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4 - [(trifluoromethyl) sulfinyl] -1H-pyrazol-3-carbonitrile (CAS-RN 120068- 37-3)} and optionally one or more insecticidally active ingredients in addition to fipronil,

b) etonal,

c) one or more anionic surfactants, and

d) one or more nonionic surfactants.

In addition, microemulsions and concentrates thereof according to the invention may, if appropriate, additionally comprise conventional adjuvants and additives as other components.

The term microemulsion concentrate (MC) is a composition which forms microemulsions upon dilution with water, for example oil-in-water or oil-in-water microemulsions. By microemulsion is meant an emulsion that is thermodynamically stable and has an emulsified phase droplet size which generally ranges from 10-400 nm, preferably 50-250 nm.

In general, microemulsion concentrates according to the invention comprise the following amounts of components a), b), c) and d), where "% by weight" herein and throughout the report, unless otherwise defined, refers to relative weight of the component concerned based on the total weight of the formulation:

Component a): 0.001-50 wt%, preferably 0.1-40 wt%, especially preferably 5-40 wt%.

Component b): 0.1-5 wt%, preferably 0.5-2 wt%, especially preferably 1-2 wt%.

Component c): 0.1-25% by weight, preferably 1-20% by weight, especially preferably 2-15% by weight.

Component d): 0.1-40 wt%, preferably 1-30 wt%, especially preferably 2-15 wt%.

Suitable insecticidally active ingredients (a) which may be used in addition to fipronil are, for example, compounds selected from the group consisting of

acefate, acequinocil, acetamipride, acetoprol, acrinatrine, alanicarb, aldicarb, aldoxycarb, alethrin (d-cis-trans, d-trans), allixicarb, aluminum phosphide, ami-doflumet, aminraz, avermectin, azadiractin, aamhiphip -zinphos (-methyl / ethyl), azocyclothine, benclothiaz, bendiocarb, benfuracarb, bensultap, benzoxime, beta-cyfluthrin, bifenazate, bifenthrin, bi-oalethrin, bioallethrin-S-cyclopentol isomer, bioethanethretrine, bioresmethrin, bistrifluron, bromfenvinphos (-methyl), bromophosethyl, bromopropylate, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, cadusaphos, camfeclor, carbaryl, carbofuran, carbofuran, carbofenazon, carbofuran chlordane, clordime-form, chloridexiphos, chlorphenapyr, chlorfenvinphos, chlormephos, chlorobenzylate, chloro-picrine, chlorpyrifos (methyl / ethyl), clovaportrin, chromafenozide, cis-cypermethrin, cis-permethine, cis-resetrin, clocetrine, clociter, ntezine, clotianidine, clothiazoben, codlemone, coumaphos, cryolite, cyanophenophones, cyanophos, cycloprene, cycloprotrin, cyflumetophen, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin (alpha-, beta-, theta- cyzothine, zymetine, , DDT, deltamethrin, demeton-s-methyl, demeton-s-methylsulfon, diafentiuron, dialiphos, diazinon, diclofention, dichlorvos / DDVP, dicofol, dicrotophos, dicyclan-zurone, dimethoate, dimethylvinf dinap, dimethyl dinap, dimethyl dinap, dimethane dinoc, -no, diophenolane, dioxabenzophos, disulfoton, DNOC, emamectin, emamecin-benzoate, empenthrin (1R isomer), endosulfan, EPN, epofenonan, esfenvalerat, ethiofencarb, etion, etiprol, etoprofos, etofenprofur, etofenfurate, fenamiphos, fenazaquine, fenbutatin oxide, fenflutrin, fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyritrin, fenpiroximate, fensulfotion, fention, fentrifanil, fenvalerate, floni-camid, fluacrubimidine, ocitrinate, flucicloxuron, flucitrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flu-pyrazophos, flutenzine, fluvalinate, phonophos, formetanate, formotion, fosmetilan, fostiazate, fubfenprox, furatiocarb, gamma-cihalotrin, HHHCRH heptachlor, heptenopos, hexaflumuron, hexitiazox, hydramethylnone, hydramethylnone, hydroprene, imidacloprid, imiprotrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isophocarb, O-salicylate, isopathinate, isophenyl, isophenyl, isophenyl cymbhalothrin, lindane, lufenuron, malation, mecarbam, metamododium, methacrophs, metamidophos, metidation, metiocarb, methomyl, methoprene, methoxychlor, methoxyphenzide, methyl bromide, metofluthrin, metolcarzone, metholcarzone, metolcarbone naled, nicotine, nitenpiram, nitiazine, novaluron, noviflumuron, ometoate, oxamyl, oxidemeton-methyl, paration (-methyl / ethyl), penfluron, permethrin (eis-, trans-), petroleum, phenothrin (R-trans isomer1), phentate, phorate, fosalone, fosmet, phosphamidon, phosphocarb, foxim, piperonyl butoxide, pirimicarb, (-methyl / ethyl) pyrimiphos, pralethrin, profenofos, profluthrin, propechos, propargite, prope-buffers, propoxur, protiofos, protoate, protrifenbute, pimetrozine, piraclofos, pirafluprol, pyresmethrin, pyrethrum (pyrethrum), pyridaben, pyridalyl, pyridafen-thion, pyridation, pyrimidifen, pyriprol, quipriprine, pyriprine, pyriprole , RU 15525, tallow, silafluofen, spinosad, spirodiclofen, spiromesifen, spirotetramat (CAS-reg.-NQ: 203313-25-1), 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo ethyl carbonate -1-azaspiro [4.5] dec-3-en-4-yl (alias: 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-ester Carbonic acid ethyl 4-yl, CAS-reg.-Ne: 382608-10-8), sulfluramid, sulfotep, sulfuri-la fluoride, sulprofos, tau-fluvalinate, tebufenozide, tebufenpirad, tebupirimfos, teflu-benzuron, tefluthrin, temephos, teralethrin , terbufos, tetrachlorvinphos, tetradifon, tetramethrin (1R isomer), tetrassul, tiacloprid, thiamethoxam, thiocyclam acid oxalate, thiodicarb, thiophonox, thiometultapodium sodium, tolfenpyradine, transflutretrin trietriazole -ron, trimetacarb, triprene, vamidotion, vaniliprol, verbutin, XMC, xylylcarb, ZXI8901. Other preferred ingredients among the insecticidatively active ingredients a) which may be present in the microemulsions or concentrates thereof besides fipronil are: cypermethrin, deltamethrin, imidacloprid, amitraz, triazophos, and their salts, for example sodium salts, and more preferred triazophos.

The active ingredients listed above are known, for example, from The Pesticide Manual, 13th edition (2003), British Crop

Protection Council.

The b) etonal component is a mixture of ethanol and benzene, which is well known to one skilled in the art. Suitable as anionic surfactants c) are, for example, hydrocarbon sulfates, sulfonates, phosphates and phosphates which may optionally comprise alkylene oxide units. Sulfates, sulfonates, phosphates and phosphonates may exist in the form of acid or as salts. Preferred anionic surfactants c) are those of formula (I) below:

<formula> formula see original document page 5 </formula>

where Q is -O-SO3M1 -SO3M, -O-PO3HM or -PO3HM, where M is H or a cation, in particular a metal cation such as an alkali metal ion or an alkaline earth metal ion, or a ammonium,

R is an unsubstituted or substituted C1 -C30 hydrocarbon radical which may be optionally attached via alkylene oxide units, or R is an alkylene oxide unit.

The term alkylene oxide units in particular means units of C 2 -C 10 alkylene oxides, such as ethylene oxide, depropylene oxide or butylene oxide, the units on the surface being possible to be the same or different from each other and are arranged as a random or block mixture.

R is preferably a C1 -C20 alkyl radical (e.g. methyl, ethyl, propyl, butyl) or a C6 -C24 aryl radical (e.g. phenyl, biphenyl, naphthyl) which may optionally have one or more radicals attached thereto, for example. example of the C 1 -C 20 alkyl group (e.g. straight or branched C 1 -C 20 alkyl such as sec-butyl or dodecyl) which may have one or more radicals attached thereto such as C 6 -C 20 -aryl radicals (e.g. phenyl, biphenyl, naphthyl) and C6 -C20 -aryl (e.g. phenyl, biphenyl or naphthyl) which may optionally have one or more radicals attached thereto such as C1 -C10 alkyl (e.g. 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) y (BO) z where EO is an ethylene oxide unit , PO a propylene oxide unit, B a butylene oxide unit, χ an integer from O - 100, y an integer from O - 100, ζ an integer from O 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, may be arranged randomly or in blocks, and

R 2 is H, a C 1 -C 20 alkyl radical (e.g. methyl, ethyl, propyl, butyl) or a C 6 -C 24 aryl radical (e.g. phenyl, biphenyl, naphthyl) which may optionally have one or more radicals attached to it, for example from the C 1 -C 20 alkyl group (for example straight or branched C 1 -C 20 alkyl such as sec-butyl or dodecyl) which may have one or more radicals attached thereto such as C 6 -C 20 radicals aryl (e.g. phenyl, biphenyl, naphthyl), and C 6 -C 20 -aryl (e.g. phenyl, biphenyl or naphthyl) which may optionally have one or more radicals attached thereto such as C1-C10-alkyl (e.g. methyl, ethyl, propyl, butyl), or R2 is -O-SO3M, -SO3M, -O-PO3HM or -PO3HM, preferably -PO3HM, where M is H or a cation, in particular a metal cation such as a alkali metal ion or an alkaline earth metal ion, or an ammonium ion.

Especially preferred anionic surfactants c) are alkylaryl sulfonates such as dodecylbenzenesulfonates, for example alkaline earth metal dodecylbenzenesulfonates such as dodecylbenzenesulfonates of calcium (e.g. Phenylsulfonat® CaIOO from Clariant), sulfolates of sulfolates, particularly sulfylates arylalkylaryl polyglycol ether such as triestyrylphenyl polyglycol ether sulphates, in particular alkali metal or ammonium or triethanolamine bones (e.g. Rhodia's Soprophore® series), alkyl ether sulphates and salts thereof (for example such as Genapol® LRO alkyl sulfates and alkyl sulfonates (for example such as Clariant's Hostapur® series), alkyl polyglycol ether phosphates, in particular alkali metal salts (e.g. Rhodia's Rhodafac® series) alkylaryl polyglycol ether phosphates, in particular in the form of alkali metal salts. In general, the salts are preferably metallic such as alkali metal 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 combinations thereof. By the term "alkoxylates" is meant compounds comprising alkylene oxide units, in particular C 2 -C 10 alkylene oxide units, such as ethylene oxide, propylene oxide or butylene oxide, wherein the units in the surfactant may be the same or each other and are arranged randomly or in blocks. Examples of alkoxylates d) are compounds of formula (II) below:

R1- (AO) v2 R2 (II)

where R1 is selected from the group H1 HO, C1 -C3 alkyl which may be straight or branched (e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl), C1 -C30 alkoxy, preferably C1 -C10 alkoxy which may be Branched or branched (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), C6 -C24 -aryl (e.g. phenyl), which may optionally have one or more radicals attached thereto such as C1-C30-arylalkyl (e.g. styrylphenyl) or C 1 -C 30 alkyl, wherein the alkyl groups may be straight or branched (for example butyl or dodecyl), C 6 -C 24 aryloxy (e.g. phenoxy), which may optionally have one or more radicals attached thereto such as C 1 -C 30 -arylalkyl (e.g. styrylphenyl), or C 1 -C 30 -alkyl, wherein the alkyl groups may be straight or branched (e.g. butyl or dodecyl), or

R 1 is a sorbitan ester residue, a glycerol or C 1 -C 30 alkyl-NR 4 ester residue, preferably C 1 -C 2 C 1 -C 11 alkyl-NR 4, wherein C 1 -C 20 alkyl may be straight or branched (e.g. dodecyl, hexadecyl, α-tadecyl) and wherein R4 is H or C1 -C10 alkyl (e.g. methyl, ethyl, propyl, butyl),

R 2 is H or C 1 -C 6 alkyl which may be straight or branched (e.g. 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, χ an integer of Ο 00, y an integer from 0-100,, an integer from 0 to 100 and the total of x + y + z is at least 1, and the alkylene oxide unit, for example (EO) x (PO) y ( BO) z, has a random or block structure.

Especially preferred non-ionic surfactants d) are alkylaryl polyalcoxylates, for example ethoxylates, propoxylates and / or butoxylates, arylalkylaryl polyalkoxylates (such as triestyrylphenyl polyalcoxylates (e.g. Rhodia's Soprophor® series) and polyalkylphenylate polyalcoxylates with alkyl tributylphenylates (eg Sopagenat® Clari-ant series), alkylene oxide block copolymers such as ethylene oxide (EO) / propylene oxide (PO) block copolymers or ethylene oxide (EO) / oxide block copolymers butylene (BO) (for example BASF's Pluronic® series), polyalkylene oxides such as polyethylene oxide, polypropylene oxides or polybutylene oxides, optionally substituted on one of two terminal oxygen atoms with CrC22 hydrocarbon radicals. preferably C10 -C22 hydrocarbon radicals such as straight or branched C10 -C22 alkyl radicals (e.g. decyl, dodecyl, tetra decyl, hexadecyl), for example polyglycol ethers which may be substituted with isotridecyl (eg Clariant's Genapol® series), alkoxylated oils such as ethoxylates such as vegetable oils, for example alkoxylated castor oil such as ethoxylate ( the Cla-riant Emulsogen® series), (C10-C22) alkoxylated fatty amines such as ethoxylated (eg Clariant's Genamin® series).

When the present disclosure refers to carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio, and the corresponding unsaturated and / or substituted radicals, their carbon skeleton may be straight or branched chain in each case. . Unless otherwise mentioned, such radicals generally have 1 to 30 carbon atoms, with lower carbon scaffolds being preferred, for example those having 1 to 6 carbon atoms, or, in the case of unsaturated groups, 2 to 6. carbon atoms. Alkyl radicals, also in the meaning compounds such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or sec-butyl, penylthi, 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 possible unsaturated radicals corresponding to alkyl radicals; for example alkenyl is allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.

Alkenyl in the form (C3 -C4) alkenyl, (C3 -C5) alkenyl, (C3 -C6) alkenyl, (C3 -C8) alkenyl or (C3 -C2) alkenyl is preferably an alkenyl radical having 3 to 4 3 to 5, 3 to 6, 3 to 8, or 3 to 12 carbonoon atoms and the double bond is not located on the carbon atom that is attached to the remainder of the compound of formula (I) ("il" position). This also applies analogously to (C 3 -C 4) alkynyl and the like, (C 3 -C 4) alkenyloxy and others and (C 3 -C 4) alkynyloxy and the like.

A hydrocarbon radical means a straight chain, branched or cyclic, aliphatic or aromatic and saturated or unsaturated hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl or aryl.

A hydrocarbon radical preferably has 1 to 40 carbon atoms, preferably 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 atoms in the orphenyl ring.

Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluoro-renyl and the like, preferably phenyl.

A heterocyclyl (heterocyclyl) radical or ring may be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; preferably it contains one or more ring heteroatoms, preferably from the group consisting of N10 OS; preferably it is a heterocyclylaliphatic radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms. The heterocyclic radical may be for example a heteroaromatic (heteroaryl) radical or ring, such as, for example, a mono-, bi- or polycyclic aromatic system wherein at least one ring contains one or more heteroatoms, 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, pipe-razinyl, dioxolyl morpholinyl, tetrahydrofuril. Suitable substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally also oxo. The oxo group may be present in ring heteroatoms that 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 with halogen, preferably with fluorine, chlorine and / or bromine, in particular with fluorine or chlorine, for example CF3, CHF2, CH2F1CF3CF2, CH2FCHCI, CCl 3, CHCl 2, CH 2 CH 2 Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F1 CF3CF2O1 OCH2CF3 and OCH2CH2CI; This also applies analogously to haloalkenyl and other substituted halogen radicals.

Hydrocarbon radicals, for example alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or heterocyclyl or heteroaryl may 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, hydroxy, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, amino substituted 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 corresponding to the abovementioned hydrocarbon-containing saturated radicals, such as alkenyl, alkynyl, alkynyloxy, alkenyloxy and the like. In the case of carbon atom radicals, those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Preferred substituents are, as a rule, those of the group consisting of halogen, for example fluorine and chlorine, (C 1 -C 4) alkyl, preferably methyl or ethyl, (C 1 -C 4) haloalkyl, preferably trifluoromethyl, (C 1 -C 4) alkoxy, preferably methoxy. toxy or ethoxy, (C1 -C4) haloalkoxy, nitro and cyano. Especially preferred in this context are the methyl, methoxy and chlorine substituents.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or monosubstituted or polysubstituted, preferably even substituted, with the same or different radicals as the group consisting of halogen, (C1-C4) alkoxy, (C1-C4) alkoxy, (C1-C4) haloalkyl, (C1-C4) ) haloalkoxy 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 formally formed by the removal of an OH group from the organic acid, for example a carboxylic acid radical and acid radicals thereof, such as thiocarboxylic acid, optionally N-substituted iminecarboxylic acids or carbonic monoester radicals, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids and phosphinic acids.

An acyl radical is preferably formyl or aliphatic acyl of the group consisting of CO-Rx, CS-Rx, CO-ORx, CS-ORx, CS-SRx, SORor SO2Ryi where Rx and Ry in each case represent a CrC30-hydroxy radical. carbide which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the last two mentioned radicals being unsubstituted, N-monosubstituted or N, N-disubstituted.

Acyl is, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C1 -C4) alkylcarbonyl, phenylcarbonyl, and phenyl may be substituted, for example as mentioned above for phenyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfonyl, N-alkyl-1-iminoalkyl and other organic acid radicals.

Formula (I) and the other compounds mentioned in this report also cover all stereoisomers and mixtures thereof. Such compounds contain one or more asymmetric carbon atoms or double bonds which are not specifically mentioned in the formula. Possible stereoisomers, which are defined by their specific spatial format, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the respective formulas and may be obtained from mixtures of stereoisomers by standard methods or may still be prepared by stereoselective reactions in combination with. Uses stereochemically pure starting materials.

The microemulsion concentrates according to the invention may be prepared by usual methods, for example by mixing or dissolving the individual components, preferably at ambient temperature. If other auxiliaries and additives are present, they are also preferably introduced at room temperature: In general, individual components may be added in any desired sequence.

Preparation processes are in principle known and are described, for example, in Winnacker-Küichler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed.1986, Wade van Valkenburg "Pesticide Formulations", Mareei Dekker, New York, 1973; K. Martens, Spray Drying "Handbook, 3rd Ed. 1979, G. Good-win Ltd. London; H. Mollet, A. Grubenmann," Formulierungstechnik ", Wiley-VCH, Weinheim 2000.

Formulation aids, such as inert materials and other additives, are also known and are described, for example, in: Wat-kins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., DarlandBooks, 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 EmulsifiersAnnual", MC Publ. Corp., Ridgewood N.J .; Sisley & Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., New York 1964; Schónfeldt, "Grenzflächenaktive Àthylenoxidaddukte" [Tissue Ethylene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küichler, "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, protectors, fertilizers and / or growth regulators, for example in the form of a ready mix or in form of a tank mix.

Microemulsion concentrates according to the invention may be diluted with water to give microemulsions which are also subject matter of the present invention. The weight ratio of microemulsion concentrate to water may range, for example, from 1: 0.1 to 1: 100, preferably 1: 1 to 1: 100, which gives concentrated microemulsions which, per se, are storage stable. . For application, they may be further diluted with water to give spray mixtures that are generally present in the form of emulsions such as microemulsions, aqueous solutions, suspensions or suspoemulsions.

The components a), b), c) and d) of the microemulsion concentrates and microemulsions according to the invention may all be present in a ready mix which can then be applied, for example in the form of a spray mixture. .

In addition to components a), b), c) and d), micro-emulsion concentrates and microemulsions according to the invention, including spray mixtures obtainable therefrom (all hereinafter referred to as agrochemical compositions according to the invention). ) may further comprise as other customary composites and additives, for example formulation aids such as anti-settling agents, wetting agents, fertilizers such as ammonium sulfate, urea or compound fertilizers, for example phosphorus-based, potassium and nitrogen, such as commercially available fertilizers Ρ, Κ, Ν, or surfactants other than components c) and d), such as betaine or polymeric surfactants, stabilizers such as pH stabilizers, biocides, UV stabilizers, defoamers soluble synthetic or natural polymers, for example polar solvents such as water or non-polar solvents such as aliphatic solvents saturated or unsaturated oils which may be branched or unbranched, or aromatic solvents such as Solves-so®100, Solvesso®150 or Solvesso®) 200 or xylene. These agrochemical compositions and their preparation and use are also novel and constitute subject matter of the present invention.

Preferred examples of usual auxiliaries and additives are

• humectants such as Genapol® LRO (0-20 wt%), dispersant such as Tamol® (0-15 wt%) or other surfactants (nonionic, cationic, anionic, polymeric surfactants) (0-30 wt% );

• inorganic salts such as NaCl, Na 2 SO 4, MgCl 2 (0-50 wt%), (oligo-, poly) phosphates; carbonates such as potassium carbonate;

• fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus and potassium containing components, if appropriate other trace elements (0-60% by weight);

Defoamers 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 may be employed for example by application to harmful organisms or to the places where they occur, for example by spraying. By way of example, the agrochemical compositions according to the invention are applied as a spray mixture comprising components a), b), c) and d) in effective amounts and, if appropriate, other auxiliaries and additives thereof. for example for formulation or for use. In general, the spray mixture is prepared based on water, and auxiliaries and additives may be added, for example oils, such as vegetable oils, or high boiling hydrocarbons, such as kerosene or paraffin.

In application, the concentration of the agrochemical active ingredient (a) generally ranges from 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. l / ha, preferably 50 to 1000 l / ha.

For use, concentrated formulations that are present in commercially available form are, if appropriate, diluted manually by water. It may be advantageous to add other 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 required application rate of agrochemical active ingredients a) may vary with external conditions such as temperature, humidity, type of herbicide used. It may vary within wide limits, for example between 0.001 and 10 kg / ha or more of 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 remarkable insecticide activity against a broad spectrum of economically important insects.

The active compounds are suitable for protecting plant and plant organs, for increasing crop yields, for improving the quality of harvested material, and for controlling animal pests, in particular insects, arachnids and nematodes, which are found in agriculture, in flowers, in gardens and play areas, in the protection of stored products and materials, and in the hygiene sector, and have good plant tolerance and favorable toxicity for warm-blooded and environmentally well-tolerated animals. They may preferably be employed as plant protective agents. They are active against normally sensitive and resistant species and against all or some stages of development. The above mentioned pests include:

From the order of the Anopluros (Phthiraptera) for example Damaliniaspp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectesspp.

From the order of Arachnids for example Acarus siro, Aceria shel-doni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilusspp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssusgallinae, Eotetranychus spp. Epitrimerus pyri, Eutetranychus spp., Erioph-yes spp., Hemitarsonemus spp., Ixodes spp., Latrodeetusmactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp. , Pso-roptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpiomaurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasa-tes lycopersici.

From the order of the Bivalvo for example Dreissena spp.

From the order of the Kilopods for example Geophilus spp., Scutige-ra spp.

From the order of Coleoptera, for example Acanthoscelides obtec-tus, Adoretus spp., Agelastiea alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Apogonia spp., Aogoma spp. ., Bruehidius obtectus, Bruehusspp., Ceuthorhynehus spp., Cleonus mendicus, Conoderus spp., Cosmopoli-tes spp., Costelytra zealandica, Cureulio spp., Cryptorhynehus lapathi. cubae, Gibbium ps-ylloides, Heteronyehus arator, Hylamorpha elegans, Hylotrupes bajulus, Fake Hy-pear, Hypothenemus spp., Laehnosterna consanguinea, Leptinotarsadecemlineata, Lissorhoptrus oryzophilus, Melix spp. Monoehamus spp., Naupac-tus xanthographus, Niptus hololeucus, Oryetes rhinoceros, Oryzaephilus su-rinamensis, Otiorrhynehus sulcatus, Oxieetonia jucunda, Phaedon cochleari-ae, Phyllophaga spp., Popillia japonica spp. , Psylliodes ehry-socephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilusspp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio mo-litor, Tribolium spp., Trogoderma spp., Tyehp sp. ., Za-brus spp.

From the order of the Colemboli for example Onyehiurus armatus.

Of the order of the Dermápteros for example Forfieula auricularia.

From the order of the Diplopods for example Blaniulus guttulatus.

From the order of the Diptera, for example Aedes spp., Anophelesspp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chry-somyia spp., Coehliomyia spp., Cordylobia anthropophaga, Culex spp., Cute-rebra spp., Daeus oleais, Dereob homeais , Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liri-omyza spp. Lueilia spp., Musea spp., Nezara spp., Oestrus spp., Oseinellafrit, Pegomyia hyoscyami, Phorbia spp., Stomoxis spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.

From the order of the Gastropods for example Arion spp., Biomphaliaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oneome-Iania spp., Succinea spp.

From the order of the Helminths for example Ancylostoma duodenale,

Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Astra-greases Ascaris spp., Brugia malayi, Brugia timori spp., Chabertia spp., Clonorchis spp., Cooperia spp. latum, Dracunculus medinensis, Echinococ-eus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Facio-la spp., Haemonehus spp., Heterakis spana., Hyymonol-ius spp. Opisthorehisspp., Onehoeerea volvulus, Ostertagia spp., Paragonimus spp., Schistoso-men spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloidesspp., Taenia saginata, Taenia solium -gulus spp., Trichuris trichuria, Wuehereria bancrofti.

In addition, protozoa, for example Eimeria, can be beaten.

From the order of the Heteroptera for example Anasa tristis, Antesti-opsis spp., Blissus spp., Calocoris spp., Campylomma livida, Caveleriusspp., Cimex spp., Creontiades dilutus, Dasynus piperis, Diehelops furcatus, Diconocys duserus spp. spp., Eurygaster spp., Heli-opeltis spp., Horeias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Maeropes excavatus, Miridae, Nezara spp., Oebalus spp., Pen-tomidae, Piesma quadrata, Piezodorus spie. , Psallus seriatus, Pseudaeystapersea, Rhodnius spp., Sahlbergella singularis, Seotinophora spp., Stephani-tis nashi, Tibraea spp., Triatoma spp.

From the order of Homopterans, for example Aeyrthosipon spp., Ae-neolamia spp., Agonoseena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasea cardui, Aonidiella spp., Apha-nostigma piri. Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus heliehrysii Chae-tosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis ju-glandicola, Chrysomphalus ficus, Cieadulina mbila, Coccomytilus halli, Coc-eus spis., Cryptomyzus ribis, Diabuluris spp. Drosieha spp., Dysaphis spp., Dysmicoccusspp., Empoasea spp., Eriosoma spp., Erythroneura spp., Euseelis bilobatus, Geococcus coffeae, stri atellus, Leeanium spp., Lepidosaphes spp., Lipaphis erysimi, Maerosiphum spp., Mahanarva fimbrio-tin, Melanaphis sacchari, MeteaIfieIIa spp. spp., Nilaparvata lugens, Oneometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Pe-regrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodi sph. aspidistrae, Planococcus spp., Protopulvina ria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastro-coccus spp., Rhpalosiph. spp. Seaphoides titanus, Schi-zaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictoeephala festina, Tenalaphara malayensis, Tinoealliscaryaefoliae, Tomaspis spp., Toxoptera spp. loeyba spp., Unaspis spp., Viteus vitifolii.

From the order of the Hymenoptera eg Diprion spp., Hoplo-campa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Isopods for example Armadillidium vulgare, O-niscus asellus, Poreellio scaber.

From the order of the Isoptera for example Retieulitermes spp., Odon-totermes spp.

From the order of the Lepidoptera, for example, Aeronieta major, Aedialeucomelas, Agrotis spp., Alabama argillacea, Antiearsia spp. Clysia ambiguella, Cnaphalocerus spp., Eariasinsulana, Ephestia kuehniella, Euproetis ehrysorrhoea, Euxoa spp., Feltiaspp. Galleria mellonella, Helieoverpa spp., Heliothis spp. , Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Moanda repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectino-phora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella-xylostella = , Pseudaletia spp., Pseudoplusia ineludens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bi sselliel-la, Tortrix viridana, Trichoplusia spp.

From the order of the Orthoptera, for example Aeheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leueophaea maderae, Loeusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.

From the order of the Siphonaptera for example Ceratophyllus spp., Xenopsylla cheopis.

From the order of the symphiles for example Seutigerella immaculata.

From the order of the Tisanoptera eg Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hereinothrips femo-ralis, Kakothrips spp., Rhipiphorothrips cruentatus, Seirtothrips spp., Taenio-thrips cardamoni, Thrips

Of the order of the Thisanuros for example Lepisma saccharina.

The use of the insecticidal compositions according to the invention in economically important transgenic plant crops and useful ornamental plants such as grass crops such as wheat, barley, rye, oats, sorghum and millet, rice and maize or -Trab, cotton, soybean, oilseed rape, potatoes, tomatoes, peas and other vegetables is also possible. The compositions according to the invention may preferably be employed as herbicides in useful plant crops which are resistant to the phytotoxic effects of herbicides or which may be made resistant to the phytotoxic effects of herbicides by recombinant means.

When insecticidal compositions according to the invention are used in transgenic crops, effects are often observed in addition to the effects against harmful plants observed in other crops, which are specific for application to the transgenic plant in question, for example a modified or specifically spectra. weed control weeds, altered application rates that can be employed for application, preferably good combining properties with herbicides to which the transgenic crop is resistant, and an effect on plant growth and yield transgenic culture

Plant crops may also have been genetically modified or obtained by mutant selection.

Agrochemical compositions, in particular insecticidal compositions according to the invention may, if appropriate, be present in the form of mixed formulations together with other customary agrochemical and auxiliary ingredients and additives, and such mixed formulations are then commonly applied as a compound. dilution with water, or may still be prepared in the form of what is known as a mixtures, by diluting together the separately formulated or partially separated formulated components with water.

The insecticidal compositions according to the invention may be applied in a conventional manner, for example with water as a carrier at spray mixture rates of approximately 5 to 4000 liters / ha. Also the compositions may be applied by methods known as low volume methods or ultra low volume (ULV) methods.

In addition, the insecticidal compositions of the invention may also comprise one, two or more agrochemical active ingredients other than insecticides a) (e.g. herbicides, fungicides), usually in small amounts, in order to complement the properties profile.

This results in a large number of possibilities for combining a plurality of agrochemical active ingredients with each other and for employing them together to control harmful organisms such as harmful plants in plant crops, without departing 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.

Microemulsion concentrates and microemulsions according to the invention exhibit advantageous physical application behavior. During application, the agrochemical active ingredient remains uniformly distributed in the spray tank, enabling uniform application to the crop or crop area. 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 a remarkable biological activity and preferably act synergistically. These effects allow, among other things, that the rate of application is reduced, a broader spectrum of harmful organisms to be controlled, control gaps to be overcome, faster and more reliable activity, prolonged long-term activity, complete control of harmful organisms. with only one application or few applications, and the application window is enlarged.

Claims (18)

1. Microemulsions and concentrates thereof comprising a) fipronil and optionally one or more insecticidally active ingredients in addition to fipronil, b) etonal, c) one or more anionic surfactants, and d) one or more nonionic surfactants. 2. Microemulsions and concentrates thereof according to claim 1, which comprise as a component fipronil only. Microemulsions and concentrates thereof according to claim 1, comprising as a) fipronil in admixture with triazophos. Microemulsions and concentrates thereof according to claim 1, comprising as component a) fipronil in admixture with one or more insecticidally active ingredients selected from cypermethrin, deltamethrin, imidacloprid, and amitraz. Microemulsions and concentrates thereof according to claim 1 to 4, comprising as component c) one or more anionic hydrocarbon sulfate, sulfonate, phosphate and phosphonate group which may be optionally alkoxylated, preferably alkylaryl sulfonate, alkylaryl polyglycol ether phosphate, phosphate alkylaryl polyglycol ether sulfonates, alkyl ether sulfates, alkyl sulfates, alkyl sulfonates, alkyl polyglycol ether phosphates and alkylaryl polyglycol ether phosphates. Microemulsions and concentrates thereof according to one or more of claims 1 to 5, which comprise, as component d), one or more alkaryl group non-ionic surfactants, preferably alkylaryl polyalkoxylates, copolymers in alkylene oxide blocks, polyalkylene oxides which may be substituted with C10 -C22 hydrocarbon radicals, alkoxylated oils, C10 -C22 acoxylated fatty amines. Microemulsions and concentrates thereof according to one or more of claims 1 to 6, which further comprises conventional auxiliaries and additives. A method for preparing a microemulsion concentrate as defined in one or more of claims 1 to 7, wherein the components are mixed. Use of a microemulsion concentrate as defined in one or more of claims 1 to 8 for the preparation of a microemulsion. An agrochemical composition comprising a) fipronil and optionally one or more insecticidally active ingredients other than fipronil, b) etonal, c) one or more anionic surfactants, d) one or more nonionic surfactants, and e) water. Agrochemical composition according to claim 10, which further comprises conventional auxiliaries and additives. Agrochemical composition according to claim 10 or 11, in the form of a microemulsion or spray mixture obtainable therefrom. An agrochemical composition which is obtainable by diluting a microemulsion concentrate as defined in one or more of claims 1 to 7 with water. A process for preparing an agrochemical composition as defined in one or more of claims 10 to 13, wherein the components are mixed. A method for controlling weed organisms, wherein an effective amount of an agrochemical composition as defined in one or more of claims 1 to 7 or 10 to 13 is applied to the weed organisms or the locations where they occur. A method for controlling unwanted vegetation, wherein an effective amount of an agrochemical composition as defined in one or more of claims 1 to 7 or 10 to 13 is applied to weeds, plant parts, plant seeds, the area under consideration. that plants grow. Use of an agrochemical composition as defined in one or more of claims 1 to 7 or 10 to 13, for controlling marine organisms. Use according to claim 17, wherein the weeds are weeds.