USOO8741324B2

(12) United States Patent (10) Patent No.: US 8,741,324 B2 Finch et al. (45) Date of Patent: Jun. 3, 2014

(54) LIQUID PESTICIDE COMPOSITIONS (56) References Cited (75) Inventors: Charles W. Finch, Garner, NC (US); U.S. PATENT DOCUMENTS Thomas Byrne, Chapel Hill, NC (US); ck Hassan Oloumi-Sadeghi. Raleigh, NC 4,851,217 A 7, 1989 Mente ...... 525/356 gn, 2l, 5,420,165 A 5/1995 Furch et al. (US) 5,543,573 A * 8/1996 Takagi et al...... 514,590 2007/0020304 A1* 1/2007 Tamarkin et al. ... 424/405 (73) Assignee: BASFSE, Ludwigshafen (DE) 2008/0300313 A1* 12/2008 Byrne et al...... 514,611 (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 EP O 209 462 1, 1987 U.S.C. 154(b) by 910 days. EP O 302701 2, 1989 EP O 427 582 5, 1991 JP 6293605 10, 1994 (22) PCT Filed: Jul. 5, 2005 JP T-285803 10, 1995 JP 115O1630 2, 1999 (86). PCT No.: PCT/EP2005/007256 WO WO 88,07326 * 10, 1988 ...... AON 25,04 WO WO 88,09122 12, 1988 S371 (c)(1), WO WO90,03112 4f1990 (2), (4) Date: Jan. 3, 2007 WO WO92, 10937 7, 1992 WO WO96,27290 9, 1996 WO WO88,09122 * 12, 1998 ...... AON 25.30 (87) PCT Pub. No.: WO2006/002984 WO WOO2,45507 6, 2002 PCT Pub. Date: Jan. 12, 2006 WO WOO3,O37084 5, 2003 * cited by examiner (65) Prior Publication Data US 2007/O184983 A1 Aug. 9, 2007 Primary Examiner — Jane C Oswecki (74) Attorney, Agent, or Firm — Brinks Gilson & Lione Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 60/585,073, filed on Jul. 6, The present invention relates to liquid pesticide concentrate 2004. compositions which comprise at least one organic pesticide compound that is sparingly or even insoluble in water and (51) Int. Cl. which upon dilution with water form stable aqueous nano AOIN 25/02 (2006.01) particulate formulations. The liquid pesticide concentrate AOIN 33/26 (2006.01) compositions of the invention comprise: a) at least one AOIN 37/22 (2006.01) organic pesticide compound C having a water solubility of CO7C 233/65 (2006.01) not more than 1 g/l at 25°C/1013 mbar, b) at least one organic CO7C 233/80 (2006.01) solvent S having a water solubility at least 10 g/l at 25° CO7C 237/00 (2006.01) C./1013 mbar, and which is capable of dissolving the pesti CO7C 243/18 (2006.01) cide compound C, or a mixture of at least one organic solvent CO7C 245/04 (2006.01) S with water, provided that the weight ratio of water to solvent CO7C 251/06 (2006.01) S does not exceed 1:2, c) at least one non-ionic blockcopoly CO7C 251/86 (2006.01) mer P comprising at least one polyethyleneoxide moiety PEO CO7C 275/28 (2006.01) and at least one hydrophobic polyether moiety consisting of CO7C 275/30 (2006.01) repeating units selected from C-Co-alkyleneoxides and Sty CO7C 281/10 (2006.01) rene oxide, d) optionally one or more non-polymeric Surfac CO7C 281/14 (2006.01) tants, wherein the weight ratio of the non-ionic blockcopoly (52) U.S. Cl. mer to the organic pesticide compound P:C is from 0.6:1 to USPC ...... 424.495, 504f 100, 504,319, $94,312 10:1 and wherein the components a), b) and optionally d) 504/334: 504/336; 514/613: 514/615; 564/123; make up at least 95% of the composition. The invention also 564/148: 564/149; 564/181 relates to aqueous pesticide compositions which are obtained (58) Field of Classification Search by diluting the concentrate pesticide compositions of the USPC ...... 424/405; 504/310, 312,334, 336; invention with water and to their use for plant protection. 514/613, 615:564/123, 148, 149, 181 See application file for complete search history. 31 Claims, No Drawings US 8,741,324 B2 1. 2 LIQUID PESTICIDE COMPOSITIONS persant which is solubilized in a water-miscible solvent in order to overcome the problems associated with SCs and This application is a National Stage application of Interna ECs. Upon dilution with water, these formulations form a tional Application No. PCT/EP2005/007256 filed Jul. 5, Suspension of finely divided active ingredient particles. How 2005, which claims the benefit of U.S. Provisional Applica 5 ever, the active ingredient is often rapidly precipitated as tion No. 60/585,073, filed Jul. 6, 2004, the entire contents of coarse crystals giving both application problems, such as which is hereby incorporated herein by reference in its spray filter or nozzle blockage and poor or inconsistent bio entirety. efficacy. Moreover, loading of these compositions with an The present invention relates to liquid pesticide composi active ingredient is poor and the particle size of the active tions which comprise at least one organic pesticide com 10 ingredient after dilution with water is not entirely satisfactory. pound that is sparingly or even insoluble in water and which WO 03/037084 describes a similar concentrated pesticidal upon dilution with waterform stable aqueous nanoparticulate Solution which comprises one or more water-insoluble pesti formulations. The invention also relates to aqueous pesticide cide compounds and lignin dissolved in a water-miscible, compositions which are obtained by diluting the non-aqueous polar solvent. Depending on the active ingredients choice, it pesticide compositions of the invention with water and to 15 may be rapidly precipitated giving coarse crystalline par their use for plant protection. ticles. Thus the active ingredients have inconsistent bioeffi A pesticide compound, hereinafter also referred to as cacy and application problems are likely to occur. active ingredient, is usually applied in the form of a dilute WO 02/45507 describes a concentrate composition of a aqueous composition in order to achieve a good interaction hydrophobic pesticide compound, wherein the active ingre with the target organisms, such as plants, fungi and insects. dient and at least one Surfactant are dissolved in a solvent However, most active ingredients that are used as pesticides system comprising hydrophobic, water insoluble alkylal are only sparingly or even insoluble in water, i.e. they usually kanoates as a first solvent and polyhydric alcohols or conden have a water-solubility of not more than 1 g/l, often not more sates of polyhydric alcohols as a second solvent. The compo than 0.5 g/l and particularly not more than 0.1 g/l at 25° sitions require a hydrophobic, water insoluble solvent which C./1013 mbar. Therefore, formulators are often confronted 25 is undesirable. with difficulties informulating pesticide compounds in stable Therefore, it is an object of the present invention to provide formulations that can be easily diluted with water and that a stable concentrate formulation for organic pesticide com deliver maximum loading of the active ingredient per unit pounds having a water-solubility of not more than 5 g/l, in Volume to the end user. particular not more than 1 g/l or even not more than 0.5 g/l at Pesticides having a low solubility in water are often for 30 25°C./1013 mbar. Upon dilution with water, the formulation mulated as aqueous Suspension concentrate (SC) which can should form a stable aqueous composition of the active ingre be diluted with water for use in the field. Suspension concen dient, wherein the average particle size of the dispersed mate trates are formulations, wherein the active ingredient is rial should not exceed 0.5 um, preferably 300 nm and in present in the form offinely divided solid particles, which are particular 200 nm. Moreover, the formulation should not Suspended in an aqueous dispersing medium utilizing Sur 35 form coarse material upon dilution with water and the active face-active compounds, such as wetting agents, dispersants ingredient should be stable in the liquid concentrate formu and rheological or Suspending aids for stabilising the active lation upon prolonged storage or storage at elevated tempera ingredient particles in the dispersing medium. In SC's, the tures. Moreover, the aqueous composition which is obtained particles of the active ingredient usually have particle sizes in by dilution of the liquid concentrate composition should be the range of 1 to 20 Jum. Even Smaller particle sizes, i.e. <1 40 stable against formation and/or separation of coarse material um, e.g. 0.5 to <1 um, can be obtained by elaborate grinding for at least 12 h. techniques. However, problems are often encountered with This object could surprisingly be achieved by a liquid SC's as a result of settling during prolonged storage or storage pesticide concentrate composition which comprises at elevated temperatures, the resistance of settled particles to a) at least one organic pesticide compound Chaving a water re-Suspension and the formation of crystalline material upon 45 solubility of not more than 5 g/l, in particular of not more storage. As a consequence, the formulations are difficult to than 1 g/l at 25°C/1013 mbar, handle and the bioefficacy may be inconsistent. Moreover, b) at least one organic solvent Shaving a water Solubility of at since the particle size of the active ingredient particles is large least 10 g/l at 25°C/1013 mbar, and which is capable of in SC's, it may often result in a lower efficacy. dissolving the pesticide compound C, or a mixture of at An alternative for formulating water-insoluble active 50 least one organic solvent S with water, provided that the ingredients are so-called emulsifyable concentrates (EC). In weight ratio of water to solvent S does not exceed 1:2. an EC the active ingredient is dissolved in a water-immiscible c) at least one non-ionic blockcopolymer P comprising at Solvent (solubility usually <0.1 g/l), such as an aromatic least one polyethyleneoxide moiety PEO and at least one hydrocarbon, together with surface-active ingredients. EC’s hydrophobic polyether moiety consisting of repeating are usually stable solutions that can be diluted with water to 55 units selected from C-Co-alkyleneoxides and styrene form a milky oil-in-water emulsion, containing the active oxide, ingredient dissolved in the solvent droplets. EC formulations d) optionally one ore more non-polymeric Surfactants, have a considerable drawback in that they contain consider wherein the weight ratio of the non-ionic blockcopolymer to able amounts of Volatile organic Solvents which are not the organic pesticide compound P:C is from 0.6:1 to 10:1 and entirely satisfactory with regard to their ecological and toxi 60 wherein the components a), b), c) and optionally d) make up cological properties. Moreover, ECs are limited to pesticide at least 95% of the composition. compounds which are soluble in water-immiscible solvents. The compositions of the invention are stable against for As a result of the large particle size of the solvents droplets, mation of Solids upon storage and can be easily diluted with the bioefficacy of the active ingredient is sometimes not sat water without the formation of coarse material. Moreover, the isfactory. 65 formulation can be loaded with active ingredients in amounts WO92/10937 suggests apesticide concentrate which com up to 60% by weight. Surprisingly chemical degradation of prises a solid water-insoluble pesticide compound and a dis Some active ingredients having chemically labile groups, US 8,741,324 B2 3 4 Such as hydrazones, semicarbazones, urethanes, Sulfonyl The total number of ethyleneoxide repeating units and ureas, amidosulfonylamides, oxime ethers, phosphonic repeating units in the PAO moiety or moieties will usually be esters, phosphate esters, and the like is decreased in compari in the range from 20 to 2,000, preferably 40 to 1,000 and in son with other solvent based concentrate formulations. particular 65 to 450 (number average). Among the non-ionic Upon dilution with water, the compositions of the present 5 blockcopolymers P those are preferred which have a number invention form a bluish or even clear emulsion or dispersion, average molecular weight My ranging from 1,000 to 100,000 indicating that the droplets/solids dispersed therein are of Dalton, preferably from 2,000 to 60,000 Dalton, more pref very small size, the average particle diameter not exceeding erably from 2,500 to 50,000 Dalton and in particular from 300 nm, preferably not exceeding 200 nm. The average par 3,000 to 20,000 Dalton. ticle diameter as referred herein, are weight average particle 10 The weight ratio of PEO moieties and PAO moieties (PEO: diameters which can be determined by dynamic light scatter PAO) in the non-ionic blockcopolymer usually ranges from ing. A skilled person is familiar with these methods which are 1:10 to 10:1, preferably from 1:10 to 2:1, more preferably e.g. described in H. Wiese (D. Distler, Ed.). Aqueous Polymer from 2:8 to 7:3 and in particular from 3:7 to 6:4. Dispersions (Wassrige Polymerdispersionen), Wiley-VCH In general, the PEO moieties and the PAO moieties make 1999, Chapter 4.2.1, p. 40ff, and the literature cited therein; 15 up at least 80% by weight and preferably at least 90% by H. Auweter, D. Horn, J. Colloid Interf. Sci. 105 (1985), p. weight, e.g. 90 to 99.5% by weight of the non-ionic blockco 399; D. Lilge, D. Horn, Colloid Polym. Sci. 269 (1991), p. polymer P. 704; and H. Wiese, D. Horn, J. Chem. Phys. 94 (1991), p. Among the blockcopolymers P those are preferred which 6429. have a HLB-value ranging from 5 to 20 and in particular from Surprisingly the aqueous compositions, that are obtained 7 to 18. by diluting the liquid pesticide compositions with water, have Preferred blockcopolymers for use in the compositions of enhanced physical stability, i.e. the formation of solids during the invention can be described by the following formulae P1 dilution and after 24 h after dilution is not observed. More to P5: over chemical degradation in the diluted compositions of R PEO O PAO R2 P1 labile active ingredients such as Sulfonyl ureas, hydrazones 25 and the like, e.g. by hydrolysis, is decreased. R PAO O. PEO H P2 Surprisingly, the liquid compositions result in an improved biological performance of the active ingredients. R PEO PAO NR PAO' PEO' R P3 The liquid compositions comprise at least one non-ionic blockcopolymer P, which comprises at least one and prefer 30 R PEO PAO (O-A)-O PAO' PEO' R' P4 ably at least two polyethyleneoxide moiety PEO and at least one poly-C-C-alkyleneoxid moiety PAO. R PEO PAO NR-A'-NR PAO' PEO' R P5 The non-ionic blockcopolymers usually make up from 10 wherein n is 0 or 1, to 80% by weight, preferably 15 to 50% by weight and in A, A are a bivalent organic radical which has 2 to 20 carbon particular 20 to 50% by weight of the non-aqueous composi 35 atoms and which may carry 1 or 2 hydroxy groups and/or 1, tion according to the invention. The weight ratio of non-ionic 2, 3 or 4 ether moieties and which may also carry 1 or 2 blockcopolymer P to pesticide compound C is preferably radicals of the formula R PEO PAO PAO, PAO' are from 0.8:1 to 5:1 more preferably from 0.9:1 to 4:1, and in PAO moieties as defined above, in particular poly-C-C- particular from 1:1 to 3:1. alkylenoxide moieties, The PAO moiety in the non-ionic blockcopolymer P usu 40 PEO, PEO' are polyethyleneoxide moieties, ally comprises at least 3, preferably at least 5, in particular 10 R is C-C alkyl or a radical R PEO PAO – to 100 repeating units (number average) which are derived R" is C-Coalkyl or C-Co alkylphenyl, from C-Co alkyleneoxides, such as propyleneoxide, 1.2- R. R. R. are each independently hydrogen, C-Cs alkyl, butyleneoxide, cis- or trans-2,3-butyleneoxide or isobutyle C-Cs alkylcarbonyl, or benzyl, and neoxide, 1.2-pentenoxide, 1.2-hexene oxide, 1,2-decene 45 R", Rare each independently hydrogen, C-Cs alkyl or a oxide or styrene oxide. Thus, the PAO moieties can be radical R PEO PAO – described by the general formula ( O CHR CHR) A skilled person will readily understand that the radicals wherein q is the number of repeating units in the PAO moiety, R", R. RandR in formulae P1 to P5 are linked to the PEO R and Rare independently selected from C-C alkyl and or PAO moiety via an oxygen atom. hydrogen, provided that at least one of the radicals R. R” is 50 R" and R in formulae P1 and P2 are preferably C-Co different from hydrogen and the total number of carbonatoms alkyl and in particular C-C alkyl, such as methyl, ethyl, of R and R' in one repeating unit is from 1 to 8. One of the n-propyl, isopropyl. n-butyl, 2-butyl, n-pentyl, n-hexyl, radicals R or R' may also be a phenyl radical while the other n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, isodecyl, 3-propyl is hydrogen. hexyl and the like. R in formula P1 is preferably hydrogen. Preferably the repeating units in the PAO moiety are 55 RandR informulae P3, P4 and P5are preferably hydrogen. derived from C-C alkyleneoxides. Preferably, the PAO moi R in formula P3 is preferably C-C alkyl, in particular eties comprise at least 50% by weight and more preferably at Ca-Co alkyl. least 80% by weight of repeating units derived from propy Suitable radicals A and A' in formulae P4 and P5 may be leneoxide. If the PAO moiety comprises different repeating aliphatic or cycloaliphatic radicals or aromatic radicals or units, these different repeating units may be arranged statis 60 mixed aromatic/aliphatic or mixed aliphatic/cycloaliphatic tically or preferably blockwise. radicals. Examples for aliphatic radicals A and A are C-Co The PEO moieties of the non-ionic blockcopolymer Pusu alkandiyl, wherein 1, 2, 3 or 4 CH-moieties may be replaced ally comprise at least 3, preferably at least 5, and more pref by oxygen or Sulfur, e.g. ethane-1,2-diyl, propane-1,3-diyl. erably at least 10 repeating units derived from ethyleneoxide butane-1,4-diyl, hexane-1,4-diyl, 3-oxapentane-1,5-diyl. (number average). Thus, the PEO moiety can be described by 65 3-oxahexane-1,6-diyl, 4-oxaheptane-1,7-diyl. 3,6-dioxaoc the general formula (CH2—CH2—O), wherein p is the num tane-1,8-diyl. 3,7-dioxanonane-1,9-diyl and 3.6.9-trioxaun ber of repeating units within the PEO moiety. decan-1,11-diyl. Examples of cycloaliphatic radicals A, A US 8,741,324 B2 5 6 comprise Cs-Cs-cycloalkane-diyl and C7-C bicycloal Solvent S will depend on the organic pesticide compound C to kanediyl, which may carry 1, 2, 3 or 4 C-C-alkyl groups, be formulated in the non-aqueous liquid pesticide composi e.g. methyl groups, such as cyclohexane-1,2-, -1.3-, and -1,4- tion. However, the skilled person can easily select an appro diyl. Aromatic radicals A, A are for example 1.2-phenylene, priate solvent by routine experiments. 1.3-phenylene, 1,4-phenylene. Mixed aliphatic/aromatic The liquid compositions of the invention may also com radicals A, A are those which comprise one or more prise a mixture of at least one organic solvent S with water, alkanediyl units and at least one aromatic unit Such as a provided that the weight ratio of water to solvent S does not phenyl ring. Examples for mixed aliphatic/aromatic radicals exceed 1:2 and in particular 1:3 is equal or below, e.g. 1:3 to A. A comprise diphenylmethane-4,4'-diyl. 4,4'-2.2-bis(phe 1:100 or from 1:5 to 1:50. In another embodiment, the com nyl)propanediyl and the like. Mixed aliphatic/cycloaliphatic 10 radicals A, A are those which comprise one or more positions do not contain water, i.e. the weight ratio of solvent alkanediyl units and at least one cycloaliphatic unit Such as a to water is below 1:50, in particular below 1:100. In this case, cyclohexane ring. Examples for mixed aliphatic/cy the solvent S is preferably completely miscible with water. cloaliphatic radicals A, A comprise methylcyclohexane-1,7- Preferably, the amount of water does not exceed 20% by diy1, 4,4'-bis(cyclohexyl)methanediyl. 4,4'-2.2-bis(cyclo 15 weight, in particular 10% by weight of the liquid pesticide hexyl)propanediyl and the like. Preferred radicals A, A are concentrate. If wateris present, the amount is preferably from selected from C-C alkandiyl, wherein 1, 2, 3 or 4 CH 0.1 to 20% by weight, in particular from 0.2 to 10% by weight moieties may be replaced by oxygen. of the liquid pesticide concentrate. Amongst the non-ionic blockcopolymers of formulae P1 to In general, Suitable organic solvents are: P5 those of formulae P2 and P4 are especially preferred. C-Cs alkanols and Cs-Cs cycloalkanols, such as metha According to the invention, a single type of non-ionic nol, ethanol, n-propanol, isopropanol, n-butanol, isobu blockcopolymer P or different types of blockcopolymers P tanol, 2-butanol, tert-butanol, pentanol, isoamyl alco may be used. In a preferred embodiment the non-aqueous hol, n-hexanol. 1-methylpentanol. 1-ethylbutanol, liquid pesticide composition comprises at least 2, e.g. 2, 3 or n-octanol, 2-ethylhexanol, cyclopentanol, cyclohexanol 4 different types of non-ionic blockcopolymers P. Different 25 and the like; types means that the blockcopolymers are distinct with regard polyhydric alcohols, such as ethylene glycol, 1,2-pro to at least one of the following features: molecular weight, panediol. 1,3-propanediol, 1,4-butanediol, neopentyl weight ratio of PEO to PAO, the HLB-value or the molecular glycol, pinacol, pentanediols, hexane diols, glycerol, architecture. Preferably at least one of the blockcopolymers sorbitol and the like; combines at least two of the preferred features. In such mix 30 alkylene glycol monomethyl ethers, monoethyl ethers and tures the blockcopolymer P that combines at least two of the dimethyl ethers, such as ethylene glycol monomethyl preferred features makes up at least 20% by weight, prefer ether, ethylene glycol dimethyl ether, propylene glycol ably at least 30% by weight, e.g. 20 to 90% by weight, in monomethyl ether, ethylene glycol monoethyl ether, and particular 30 to 80% by weight of the total amount of block technical mixtures such as Carbitols, Cellosolves, Dow copolymer P in the composition. 35 anols, Jefferols, Ektasolves, and the like; Non-ionic blockcopolymers P are known in the art and cyclic ethers which may contain an OH group Such as commercially available under the trade names Pluronic R, tetrahydrofuran, pyran, dioxan, tetrahydrofurfurol; such as Pluronic(R) P 65, P84, P 103, P 105, P 123 and Plu di- and tri-C-C-alkylene glycols and their monomethyl, ronic. R L 31, L 43, L 62, L. 62 LF, L 64, L 81, L.92 and L 121, monoethyl- and dimethyl ethers, such as diethylene gly PlurafloR such as PlurafloR L 860, L1030 and L 40 col monomethyl ether, diethylene glycol dimethyl ether, 1060Tetronic(R), such as Tetronic R 704, 709, 1104, 1304, dipropylene glycol and dipropylene glycol monomethyl 702, 1102, 1302, 701,901, 1101, 1301 (BASF Aktiengesell ether; schaft), Agrilan RAEC 167 and Agrilan RAEC 178 (Akcros ketones, having from 3 to 8 C-atoms and optionally a Chemicals), Antarox(R) B/848 (Rhodia), Berol.R. 370 and hydroxyl group, Such as acetone, methylethyl ketone, Berol.R. 374 (Akzo Nobel Surface Chemistry), Dowfax(R) 50 45 methylpropyl ketone, methyl-4-hydroxybutyl ketone, C15, 63 N10, 63 N30, 64 N40 and 81 N10 (Dow Europe), cyclopentanone, cyclohexanone, diaceton alcohol, Genapolr PF (Clariant), Monolan R, such as Monolan RPB, mesityloxide; Monolan RPC, Monolan RPK (Akcros Chemicals), PanoxR) lactones, having from 3 to 8 C-atoms, such as B-propiolac PE (Pan Asian Chemical Corporation), Symperonic R, such tone, Y-butyrolactone, as Symperonic R. PE/L, Symperonic R. PE/F. Symperonic R. 50 carbonates, in particular dimethylcarbonat, diethylcar PE/P. Symperonic(R) PE/T (ICI Surfactants), Tergitol(R) XD, bonat and 2-Oxa-1,3-dioxolan (ethylene carbonate) and Tergitol(R) XH and Tergitol(R) XJ (Union Carbide), Triton(R) 2-oxa-1,3-dioxan (propylene carbonate); CF-32 (Union Carbide), Teric PE Series (Huntsman) and organic acids having from 1 to 8 carbon atoms, preferably Witconol R, such as WitconolRAPEB, WitconolR NS500K 1 to 3 carbon atoms, such as acetic acid, propionic acid, and the like. 55 butyric acid, hexanoic acid, caprylic acid; The non-aqueous liquid pesticide composition usually amines, in particular alkylamines, dialkylamines and tri contains at least one, e.g. 1, 2, 3 or 4 organic solvents Swhich alkylamines having from 1 to 8 carbonatoms, preferably have a water-solubility of at least 10 g/, preferably at least 50 from 2 to 6 carbon atoms, such as methylamine, ethy g/l, in particular at least 100 g/l at 25°C/1013 mbar. In a lamine, diisopropylamine, n-butylamine, isobuty preferred embodiment the solvent S is completely miscible 60 lamine, n-pentylamine, isopentylamine, di-n-propy with water. The solvent S should be capable of dissolving the lamine, isopropylamine, as well as heterocyclic amines, pesticide compound C, i.e. the solubility of the pesticide Such as piperidine, piperazine, morpholine and pyrroli compound C in the mixture of the at least one organic solvent dine, S and the non-ionic blockcopolymer P should be sufficient to amides, n-C-C-alkylamides and N,N-C-C-dialkyla achieve a complete dissolution of the organic pesticide com 65 mides of C-C-aliphatic acids in particular of formic pound C contained in the non-aqueous liquid pesticide com acid or acetic acid, such as formamide, acetamide, dim position of the invention. It is evident that the type of organic ethylformamide, dimethylacetamid, US 8,741,324 B2 7 8 C-C-alkanolamines, C-C-dialkanolamines and C-C- heterocyclic compounds, such as anilazine, benomyl, bos trialkanolamines, such as monoethanolamine, diethano calid, carbendazim, carboxin, oxycarboxin, cyazofa lamine, triethanolamine, 2-methylaminoethanol, 2-dim mid, dazomet, dithianon, famoxadon, fenamidon, fena ethylaminoethanol, isopropanolamine, rimol, fuberidazoles, flutolanil, furametpyr, diisopropanolamine and the like; isoprothiolanes, mepronil, nuarimol, picobeZamid, C-C-alkylesters of formic acid or acetic acid such as probenazoles, produinazid, pyrifenox, pyroquilon, qui methyl formiate, ethyl formiate, methyl acetate, ethyl noxyfen, silthiofam; thiabendazole, thifluzamid, acetate, n-propyl acetate isopropyl acetate and the like; thiophanat-methyl, tiadinil, tricyclazoles, triforine; heterocyclic aromatic or aliphatic amines having prefer nitrophenyl derivatives, such as binapacryl, dinocap, ably from 2 to 6 carbon atoms, 1 or 2 nitrogenatoms and 10 dinobuton, nitrophthal-isopropyl; optionally 1 or 2 further heteroatoms selected from O phenylpyrroles, such as fenpiclonil and fludioxonil; and S. Such as pyrrole, pyridine, picoline, morpholine, non-classified fungicides, such as acibenzolar-S-methyl, piperidine, piperazine, benthiavalicarb, carpropamid, chlorothalonil, cyflufe heterocyclic aldehydes such as furfural; and namid, cymoxanil, diclomezin, diclocymet, diethofen lactames, having preferably from 3 to 6 carbon atoms and 15 carb, edifenphos, ethaboxam, fenhexamid, fentin-ac their N-methyl and N-ethyl derivatives, such as pyrroli etat, fenoxanil, ferimZones, fluaZinam, fosetyl, fosetyl din-2-one, N-methylpyrrolidin-2-one, N-ethylpyrroli aluminum, iprovalicarb, hexachlorobenzol, metrafenon, din-2-one, etc. pencycuron, propamocarb, phthalides, toloclofoS-me The amount of Solvent S in the non-aqueous pesticide thyl, quintoZenes, Zoxamid; composition of the invention usually ranges from 10 to 80% strobilurines, e.g. the compounds disclosed in WO by weight, preferably from 20 to 70% by weight and in 03/075663 by the general formula I, such as azox particular 30 to 60% by weight. In case the liquid pesticide yStrobin, dimoxystrobin, fluoxastrobin, kresoxim-me composition contains water the total amount of solvent S +wa thyl, metominostrobin, orysastrobin, picoxystrobin, ter preferably ranges from 20 to 70% by weight and in par pyraclostrobin and trifloxystrobin; ticular 30 to 60% by weight 25 Sulfenic acid derivatives, such as captafol, captan, dichlo The compositions of the invention also comprise at least fluanid, folpet, tolylfluanid; one organic pesticide compound C which is sparingly soluble cinnamic acid amides and analoga, Such as dimethomorph, or insoluble in water. Preferably the solubility is below 0.5 g/1 flumetover, flumorp; and in particular below 0.1 g/1 at 25° C. and 1013 mbar. 6-aryl-1,2,4-triazolo 1.5-alpyrimidines, e.g. those dis The pesticide compound C can be selected from each 30 closed in WO 98/46608, WO 99,41255 or WO group of active ingredients which are used to protect plants/ 03/004465 by the general formula I; crops from attack or infestation by harmful organisms, i.e. the amido fungicides, such as cyclofenamid and (Z)-N-O- pesticide compound can be selected from acaricides, algi (cyclopropylmethoxyimino)-2,3-difluoro-6-(difluo cides, antecedents, aricides, bactericides, bird repellents, romethoxy)benzyl)-2-phenylacetamid. chemosterilans, fungicides, herbicides, herbicide Safeners, 35 Examples of pesticides compounds C which act as herbi insect attractants, insect repellents, insecticides, mammal cides or herbicide Safeners comprise repellents, mating disrupters, molluscicides, nematicides, 1,3,4-thiadiazoles, such as buthidazoles und cyprazoles; plant activators, plant growth regulators, rhodenticides, Syn amides, such as allidochlor, benzoylpropethyl, bro ergists, Virucides and other compounds with exert an action mobutide, chlorthiamid, dimepiperate, dimethenamid, on the plants to be protected and/or against the harmful organ 40 diphenamid, etobenzanid, flampropmethyl, fosamin, 1S. isoxaben, metaZachlor, monalide, naptalame, pronamid, Examples of Suitable pesticide compounds C which act as propanil; fungicides are for example: aminophosphoric acids, such as bilanafos, buminafos, glu acylalanine, such as benalaxyl, metalaxyl, ofurace, oxa fosinateammonium, glyphosates, Sulfosates; dixyl: 45 aminotriazoles, such as amitrol, anilide, anilofos, mefen amine derivatives, such as aldimorph, dodine, dodemorph, acet, fenpropimorph, fempropidin, guazatline, iminoctadine, aryloxyalkanoic acids, Such as 2,4-D, 2,4-DB, clomeprop, spiroxamin, tridemorph; dichlorprop, dichlorprop-P, dichlorprop-P, fenoprop, anilinopyrimidine, such as pyrimethanil, mepanipyrim or fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, cyrodinyl: 50 napropamides, napro-panilides, triclopyr, and the antibiotics, such as cycloheximid, griseofulvin, kasugamy C-Cs-alkyl esters, e.g. the ethyl or butyl esters, the cin, natamycin, polyoxin und streptomycin; C-C-alkoxy-C-C-alkyl esters, e.g. the 2-ethoxyethyl aZoles, such as bitertanol, bromoconazol, cyproconazole, esters or 2-butoxyethyl esters, and the mono-, di- and difenoconazol, dinitroconazol, epoxiconazol, fen tri-C-C-alkyl ammonium salts, in particular the tri buconazol, fluquiconazol, flusilaZol, flutriafol, hexa 55 ethyl ammonium salts of aryloxyalkanoic acids; conazol, imazalil, ipconazol, metconazol, myclobutanil, benzoic acids, Such as chloramben, dicamba and the penconazol, propiconazol, prochloraz, prothioconazol, C-Cs-alkyl esters, e.g. the ethyl or butyl esters, the tebuconazol, tetraconazol, triadimefon, triadimenol, tri C-C-alkoxy-C-C-alkyl esters, e.g. the 2-ethoxyethyl flumizol, triticonazol; esters or 2-butoxyethyl esters, and the mono-, di- and 2-methoxybenzophenones, e.g. those disclosed in EP-A 60 tri-C-C-alkyl ammonium salts, in particular the tri 897.904 by the general formula I, e.g. metrafenon; ethyl ammonium salts of benzoic acids; dichlorophenyl dicarboximides, such as chloZolinate, benzothiadiazinones, such as bentazon: dichloZoline, isovaledione, iprodion, mycloZolin, pro bleachers, such as clomaZone, diflufenican, fluorochlori cymidon, VincloZolin; dones, flupoxam, fluridone, pyrazolates, Sulcotrione; dithiocarbamates, such as ferbam, nabam, maneb, manco 65 carbamates, such as carbetamid, chlorbufam, chlorpro Zeb, metam, metiram, propineb, polycarbamat, thiram, pham, desmedipham, phenmedipham, Vernolate; Ziram, Zineb; quinolinic acids, such as quinclorac, quinmerac, US 8,741,324 B2 10 dichloropropionic acids. Such as dalapon; dim, sethoxydim and tralkoxydim. Most preferred her dihydrobenzofuranes, such as ethofumesates; bicidal active ingredients type cyclohexenone are: dihydrofuran-3-ones, such as flurtamone; tepraloxydim (see AGROW, no. 243, Mar. 11, 1995, dinitroanilines, such as benefin, butralin, dinitramin, page 21, caloxydim) and 2-(1-2-4- ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, Chlorphenoxypropyl-oxyiminobutyl)-3-hydroxy-5- pendimethalin, prodiamines, profluralin, trifluralin, (2H-tetrahydro-thiopyran-3-yl)-2-cyclohexen-1-on and dinitrophenoles, such as bromofenoxim, dinoseb, type sulfonyl urea: N-(((4-methoxy-6-trifluorimethyl dinoseb-acetate, dinoterb, DNOC, minoterb-acetate; 1,3,5-triazin-2-yl)amino)carbonyl)-2-(trifluorimethyl)- diphenylether, Such as acifluorfen-Sodium, aclonifen, benzolsulfonamid. bifenox, chlornitrofen, difenoxuron, ethoxyfen, fluo 10 rodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, Examples for pesticide compounds C which are useful as lactofen, nitrofen, nitrofluorfen, oxyfluorfen: insecticides, acaricides, nematicides and/or miticides com imidazoles, such as isocarbamid; prise: imidazolinones, such as imazamethapyr, imazapyr, imaza organophosphates, such as acephates, azinphos-methyl, quin, imazethabenzmethyl, imazethapyr, imazapic, 15 chlorpyrifos, chlorfenvinphos, diazinon, dichlorvos, imaZamox; dimethylvinphos, dioxabenzofos, dicrotophos, oxadiazoles, such as methazole, oxadiargyl, oxadiazon: oxiranes, such as tridiphane; dimethoate, disulfoton, ethion, EPN, fenitrothion, phenoles, such as bromoxynil, ioxynil; fenthion, isoxathion, malathion, methamidophos, phenoxyphenoxypropionic acid esters, such as clodinafop, methidathion, methyl-parathion, mevinphos, monocro cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, tophos, OXydemeton-methyl, paraoxon, parathion, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, phenthoates, phosalones, phosmet, phosphamidon, fluazifop-p-butyl, haloxyfop-ethoxy-ethyl, haloxyfop phorates, phoxim, pirimiphos-methyl, profenofos, pro methyl, haloxyfop-p-methyl, isoxapyrifop, pro thiofos, primiphos-ethyl, pyraclofos, pyridaphenthion, paquizafop, quizalofop-ethyl, quizalofop-p-ethyl, 25 Sulprophos, triaZophos, trichlorfon, tetrachlorvinphos, quizalofop-tefuryl; vamidothion; phenylacetic acids and their esters, such as chlorfenac; carbamates, such as alanycarb, benfuracarb, bendiocarb, phenylpropionic acids and theiresters. Such as chlorophen carbaryl, carbofuran, carbosulfan, fenoxycarb, furathio prop-methyl; carb, indoxacarb, methiocarb, methomyl, oxamyl, pir ppi-active ingredients, such as benzofenap, flumiclorac 30 imicarb, propoXur, thiodicarb, triazamate; pentyl, flumioxazin, flumipropyn, flupropacil, pyra Zoxyfen, sulfentraZone, thidiazimin: pyrethroides, such as bifenthrin, cyfluthrin, cycloprothrin, pyrazoles, such as nipyraclofen; cypermethrin, deltamethrin, esfenvalerate, ethofenprox. pyridazines, such as chloridazon, maleic hydrazide, nor fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalo flurazon, pyridate; 35 thrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, pyridincarbonic acids, such as clopyralid, dithiopyr, piclo tralomethrin, alpha-cypermethrin, Zeta-cypermethrin, ram, thiazopyr; permethrin; pyrimidylethers, such as pyrithiobac acid, pyrithiobac-So arthropodic growth regulators: a) chitinsynthesis inhibi dium, KIH-2023, KIH-6127: tors, e.g. benzoyl ureas, such as chlorfluaZuron, Sulfonamides, such as flumetSulam, metoSulam; 40 diflubenzuron, flucycloxuron, flufenoxuron, hexaflu triazolcarboxamides, such as triazofenamid; muron, lufenuron, novaluron, teflubenZuron, triflumu uraciles, such as bromacil, lenacil, terbacil; ron; buprofezin, diofenolan, hexythiaZOX, etoxazole, furtherbenazolin, benfuresate, bensulide, benzofluor, ben clofentazine; b) ecdysone antagonists, such as tazon, butamifos, cafenstroles, chlorthal-dimethyl, cin halofenozide, methoxyfenozide, tebufenozide; c) methylin, dichlobenil, endothall, fluorbentranil, meflui 45 dide, perfluidones, piperophos, toprameZone and juvenoides, such as pyriproxy fen, methoprenes, fenoxy prohexandion-calcium; carb; d) lipid biosynthesis inhibitors, such as spirodi urea herbicides, such as benzthiaZuron, cumyluron, cyclu clofen; ron, dichloralylurea, diflufenZopyr, isononuron, isou neonicotinoides, such as flonicamid, clothianidin, dinote ron, methabenzthiazuron, monisuron, noruron; 50 furan, imidacloprid, thiamethoxam, nitenpyram, nithi phenylurea herbicides, such as anisuron, buturon, chlor azin, acetamiprid, thiacloprid; bromuron, chloreturon, chlorotoluron, choroXuron, further non-classified insecticids are abamectin, ace daimuron, difenoXuron, dimefuron, diuron, fenuron, quinocyl, acetamiprid, amitraz, azadirachtin, benSultap, fluometuron, fluothiuron, isoproturon, linuron, methi bifenazate, cartap, chlorfenapyr, chlordimeform, cyro uron, methyldymron, metobenzuron, metobromuron, 55 metoxuron, monolinuron, monuron, neburon, paraflu mazines, diafenthiuron, dinetofuran, diofenolan, ema ron, phenobenzuron, Siduron, tetrafluoron; mectin, endosulfan, ethiprole, fenazaquin, fipronil, Sulfonyl ureas, such as amidosulfuron, azim Sulfuron, ben formetanate, formetanate hydrochlorid, gamma-HCH, sulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, hydramethylnon, imidacloprid, indoxacarb, isoprocarb, cinosulfuron, cyclosulfamuron, ethametSulfuron-me 60 metolcarb, pyridaben, pymetrozine, spinosad, tebufen thyl, flaZaSulfuron, halosulfuron-methyl, imaZosulfu pyrad, thiamethoxam, thiocyclam, nitenpyram, pipero ron, metSulfuron-methyl, nicosulfuron, primisulfuron, nylbutoxid, thiacloprid, pyridalyl, flonicamid, fluacypy prosulfuron, pyrazosulfuronethyl, rimsulfuron, Sulfo rim, milbemectin, spiromesifen, Spirodiclofen, meturon-methyl, thifensulfuron-methyl, triasulfuron, flupyrazofos, NC 512, tolfenpyrad, flubendiamide, fis tribenuron-methyl, triflusulfuron-methyl, tritosulfuron; 65 trifluron, benclothiaz, pyrafluprole, pyriprole, amidoflu plant protection active ingredients, type cyclohexanone, met, flufenerim, cyflumetofen, acequinocyl, lepimectin, Such as alloxydim, clethodim, cloproxydim, cycloxy profluthrin, dimefluthrin, XMC and xylylcarb, US 8,741,324 B2 11 12 N-phenylsemicarbazones as described in EP-A 462456 by compounds of the following formula as described in WO the general formula I, in particular compounds of the 98/05638 general formula A CH

(A) o-/

HC-O 10 N

15

Aminoisothiazoles of the formula wherein R'' and R'' are each independently hydrogen, halogen, CN, C-C alkyl, C-C alkoxy, C-C, C R haloalkyl or C-C haloalkoxy and R' is C-C alkoxy, C-Chaloalkyl or C-Chaloalkoxy, e.g. the compound IV, wherein R' is 3-CF and R' is 4-CN and R' is 4-OCF (Metaflumizone); NN-S O X-R amidraZone compounds of the general formula B 25 wherein R= -CHO CH or Hand (B) '= CF, CFCF; 30 Anthranilamides of the formula

O Br

35 C N) (?N-N H N wherein O / C W is chlorine or trifluoromethyl; -N le X and Y are each independently chlorine or bromine; 40 H R’ is C1-Co-alkyl, Cs-Co-alkenyl, Cs-Co-alkynyl, or C-C-cycloalkyl which may be substituted with 1 to 3 and compounds of the formulae halogen atoms, or C-C-alkyl which is Substituted by C-C-alkoxy; 45 R’ and Rare C-C-alkyl or may together with the car CF3, or bon atom, to which they are bound, form C-C-cy cloalkyl which may be unsubstituted or substituted by 1 to 3 halogen atoms; 50 O R" is hydrogen or C-C-alkyl, CF including the enantiomers and salts thereof. F In formula B. R is preferably C-C-alkyl, in particular O methyl or ethyl. In formula B. R and R are preferably CF3. 55 C-C-alkyl, in particular methyl, or R'' and R together N with the carbon atom to which they are bound form a cyclo H propyl ring, which may carry 1 or 2 chlorine atoms. R is O preferably C-C-alkyl, in particular methyl. W is preferably I HN 1. trifluoromethyl. X and Y are preferably chlorine. Preferred 60 examples are compounds of the formula B, wherein X and Y are chlorine, W is trifluoromethyl, R, R and R are methyl and R is methyl or ethyl as well as compounds of the formula B, wherein X and Y are chlorine, W is trifluorom Examples of plant growth regulators comprise gibberel ethyl, R and R together with the carbon atom to which 65 lines and oximes, such as {(isopropylidene)aminol they are bound form a 2.2-dichlorocyclopropyl ring R is oxyacetic acid-2-methoxy-2-oxoethyl ester, and also defo methyl and R is methyl or ethyl. liants, such as thidiaZuron, growth inhibitors, such as butralin, US 8,741,324 B2 13 14 flumetralin, fluoridamid, prohydrojasmon, growth retardants, C-C alkenyloxy, C-C halogenalkenyloxy, (exo)- Such as paclobutraZol, uniconazole, growth stimulators. Such C-C-alkylen and oxy-C-C-alkylenoxy: as brassinolide, forchlorfenuron and the like. L is selected from halogen, cyano, C-C alkyl, C-C halo The compositions of the present invention are particularly genalkyl, C-C alkoxy, C-C halogenalkoxy and C-C, useful for formulating pesticide compound C, which are alkoxycarbonyl: selected from fungicides, insecticides, acaricides, nemati L' is halogen, C-C alkyl or C-C halogenalkyl and in par cides and herbicides. ticular fluorine or chloro; In a preferred embodiment of the compositions of the X is halogen, C-C alkyl, cyano, C-C alkoxy or C-C, present invention the pesticide compound C comprises at halogenalkyl and preferably halogen or methyl. least one insecticide compound. 10 Examples for compounds C are: A particularly preferred embodiment relates to pesticide 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophe compositions which comprise a compound of formula A as nyl)-1.2.4 triazolo 1.5-a-pyrimidine, the at least one organic pesticide compound C. 5-chloro-7-(4-methylpiperazin-1-yl)-6-(2,4,6-trifluorophe A further particularly preferred embodiment relates to pes nyl)-1.2.4 triazolo 1.5-a-pyrimidine, ticide compositions which comprise a compound of formula 15 5-chloro-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-1,2, B as the at least one organic pesticide compound C. In another 4triazolo 1.5-alpyrimidine, preferred embodiment of the compositions of the present 5-chloro-7-(piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-1.2.4 invention the pesticide compound C comprises at least one triazolo 1.5-alpyrimidine, fungicide compound. 5-chloro-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-1,2, Another particularly preferred embodiment of the inven 4triazolo 1.5-alpyrimidine, tion relates to a pesticide composition which comprises at 5-chloro-7-(isopropylamino)-6-(2,4,6-trifluorohenyl)-1.2, least one fungicide which is selected from strobilurines, such 4triazolo 1.5-alpyrimidine, as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim 5-chloro-7-(cyclopentylamino)-6-(2,4,6-trifluorohenyl)-1, methyl, metominostrobin, orysastrobin, picoxystrobin, pyra 25 2.4 triazolo 1.5-alpyrimidine clostrobin or trifloxystrobin, azol fungicides, in particular 5-chloro-7-(2.2.2-trifluorethylamino)-6-(2,4,6-trifluorophe conazoles such as epoxyconazole, tebuconazole, triticona nyl)-1.2.4 triazolo 1.5-a-pyrimidine, Zole, fluguinconazole, flutriafol, metconazole, myclobutanil, 5-chloro-7-(1,1,1-trifluoropropan-2-ylamino)-6-(2,4,6-trif cycproconazole, prothioconazole and propiconazole, bos luorophenyl)-1.2.4 triazolo 1.5-alpyrimidine, calid, dichlorophenyl dicarboximides Such as VincloZoline 30 5-chloro-7-(3.3-dimethylbutan-2-ylamino)-6-(2,4,6-trifluo and 6-aryl-1,2,4-triazolo 1.5-alpyrimidines, e.g. those dis rophenyl)-1,2,4-triazolo 1.5-alpyrimidine, closed in WO 98/46608, WO 99/41255 and WO 03/004465, 5-chloro-7-(cyclohexylmethyl)-6-(2,4,6-trifluorophenyl)-1, in particular compounds of the general formula C 2.4 triazolo 1.5-alpyrimidine, 5-chloro-7-(cyclohexyl)-6-(2,4,6-trifluorophenyl)-1.2.4 35 triazolo 1.5-alpyrimidine, (C) 5-chloro-7-(2-methylbutan-3-yl)-6-(2,4,6-trifluorophenyl)- (L). 1.2.4 triazolo 1.5-alpyrimidine, RX 21 5-chloro-7-(3-methylpropan-1-yl)-6-(2,4,6-trifluorophe nyl)-1.2.4 triazolo 1.5-a-pyrimidine, 40 5-chloro-7-(4-methylcyclohexan-1-yl)-6-(2,4,6-trifluo rophenyl)-1,2,4-triazolo 1.5-a-pyrimidine, e Ll 5-chloro-7-(hexan-3-yl)-6-(2,4,6-trifluorophenyl)-1.2.4 ClN % X triazolo 1.5-alpyrimidine, 5-chloro-7-(2-methylbutan-1-yl)-6-(2,4,6-trifluorophenyl)- wherein: 45 1.2.4 triazolo 1.5-alpyrimidine, R’ is a group NR'R' or linear or branched C-Cs alkyl, 5-chloro-7-(3-methylbutan-1-yl)-6-(2,4,6-trifluorophenyl)- which may be unsubstituted or substituted by halogen, OH, 1.2.4 triazolo 1.5-alpyrimidine, C-C alkoxy, phenyl or C-C cycloalkyl, C-C alkenyl, 5-chloro-7-(1-methylpropan-1-yl)-6-(2,4,6-trifluorophe C-C cycloalkyl, C-C cycloalkenyl, phenyl or naphthyl, nyl)-1.2.4 triazolo 1.5-a-pyrimidine, wherein the 4 last-mentioned radicals may be unsubsti 50 5-methyl-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophe tuted or substituted by 1, 2, 3 or 4 radicals, selected from nyl)-1.2.4 triazolo 1.5-a-pyrimidine, halogen, OH, C-C alkyl, C-C halogenalkoxy, C-C 5-methyl-7-(4-methylpiperazin-1-yl)-6-(2,4,6-trifluorophe alkoxy and C-Chalogenalkyl; nyl)-1.2.4 triazolo 1.5-a-pyrimidine, R'', R' are each independently hydrogen, C-C alkyl, 5-methyl-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-1,2, C-Cs halogenalkyl, C-Co cycloalkyl, C-Chalogen 55 4triazolo 1.5-alpyrimidine, cycloalkyl, C-C alkenyl, Ca-Co alkadienyl, C-Cs 5-methyl-7-(piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-1.2, halogenalkenyl, C-C cycloalkenyl, C-Cs halogency 4triazolo 1.5-alpyrimidine, cloalkenyl, C-Cs alkinyl, C-Cs halogenalkinyl or 5-methyl-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-1,2, C-C cycloalkinyl, 4triazolo 1.5-alpyrimidine, R'' and R' together with the nitrogen atom to which 60 5-methyl-7-(isopropylamino)-6-(2,4,6-trifluorophenyl)-1, they are bound may also form a 5-, 6-, 7- or 8-mem 2.4 triazolo 1.5-alpyrimidine, bered heterocycle which may contain 1, 2 or 3 addi 5-methyl-7-(cyclopentylamino)-6-(2,4,6-trifluorophenyl)- tional heteroatoms selected from N, O and S, and 1.2.4 triazolo 1.5-alpyrimidine, which may carry one or more (e.g. 1, 2 or 3) radicals 5-methyl-7-(2.2.2-trifluoroethylamino)-6-(2,4,6-trifluo selected from the group consisting of halogen, C-C, 65 rophenyl)-1,2,4-triazolo 1.5-a-pyrimidine, alkyl, C-Chalogenalkyl, C-C alkenyl, C-Chalo 5-methyl-7-(1,1,1-trifluoropropan-2-ylamino)-6-(2,4,6-trif genalkenyl, C-C alkoxy, C-C halogenalkoxy, luorophenyl)-1.2.4 triazolo 1.5-alpyrimidine, US 8,741,324 B2 15 16 5-methyl-7-(3.3-dimethylbutan-2-ylamino)-6-(2,4,6-trifluo Sulfates of ethoxylated alkanoles, such as Sulfates of rophenyl)-1.2.4 triazolo 1.5-a-pyrimidine, ethoxylated lauryl alcohol; 5-methyl-7-(cyclohexylmethyl)-6-(2,4,6-trifluorophenyl)- sulfates of alkoxylated alkylphenols: 1.2.4 triazolo 1.5-alpyrimidine, alkylphosphates, Cs-C alkylphosphates; 5-methyl-7-(cyclohexyl)-6-(2,4,6-trifluorophenyl)-1.2.4 5 dialkylphosphates, Cs-C dialkylphosphates; triazolo 1.5-alpyrimidine, dialkylesters of Sulfo Succinic acid. Such as dioctylsulfo 5-methyl-7-(2-methylbutan-3-yl)-6-(2,4,6-trifluorophenyl)- Succinate, 1.2.4 triazolo 1.5-a-pyrimidine, acylsarcosinates, 5-methyl-7-(3-methylpropan-1-yl)-6-(2,4,6-trifluorophe fatty acids, such as Stearates, 10 acylglutamates, nyl)-1.2.4 triazolo 1.5-a-pyrimidine, ligninsulfonates, 5-methyl-7-(4-methylcyclohexan-1-yl)-6-(2,4,6-trifluo condensates of naphthalinesulfonic acid or phenolsul rophenyl)-1.2.4 triazolo 1.5-a-pyrimidine, fonic acid with formaldehyde; 5-methyl-7-(hexan-3-yl)-6-(2,4,6-trifluorophenyl)-1.2.4 non-ionic Surfactants, selected from the group of triazolo 1.5-alpyrimidine, 15 ethoxylated alkanoles, in particular ethoxylated fatty 5-methyl-7-(2-methylbutan-1-yl)-6-(2,4,6-trifluorophenyl)- alcohols and ethoxylated oxoalcohols, such as 1.2.4 triazolo 1.5-a-pyrimidine, ethoxylated lauryl alcohol, ethoxylated isotridecanol, 5-methyl-7-(3-methylbutan-1-yl)-6-(2,4,6-trifluorophenyl)- ethoxylated cetyl alcohol, ethoxylated stearyl alco 1.2.4 triazolo 1.5-alpyrimidine and hol, and esters thereof. Such as acetates 5-methyl-7-(1-methylpropan-1-yl)-6-(2,4,6-trifluorophe ethoxylated alkylphenols, such as ethoxylated non nyl)-1.2.4 triazolo 1.5-a-pyrimidine. ylphenyl, ethoxylated dodecylphenyl, ethoxylated The amount of active ingredient in the liquid compositions isotridecylphenol and the esters thereof, e.g. the is usually at least 1% by weight, preferably at least 5% by acetates weight, particularly at least 8% by weight and more prefer alkylglucosides and alkyl polyglucosides, ably at least 10% by weight. The amount of active ingredient 25 ethoxylated alkylglucosides, will in general not exceed 60% by weight and is preferably up ethoxylated fatty amines, to 50% by weight and in particular up to 40% by weight, ethoxylated fatty acids, based on the total weight of the composition. partial esters, such as mono-, di- and triesters of fatty The liquid compositions of the invention may also com acids with glycerine or Sorbitan, Such as glycerine prise a non-polymeric Surfactant (component d). This addi 30 monostearate, Sorbitanmonooleat, Sorbitantristearat tional surfactant serves to further stabilize the active ingredi ethoxylated esters offatty acids with glycerine or sorbi ent particles in the aqueous composition which is obtained tan, such as ethoxylated glycerine monostearate upon dilution of the liquid composition according to the ethoxylates of vegetable oils or animal fats, such as corn invention. In a preferred embodiment of the invention, the oil ethoxylate, castor oil ethoxylate, tallow oil ethoxy liquid composition comprises the at least one non-polymeric 35 late, surfactant in an amount from 0.1 to 10% by weight, prefer ethoxylates offatty amines, fatty amides or of fatty acid ably from 0.5 to 5% by weight, based on the total weight of the diethanolamides composition. cationic Surfactants, selected from the group of In another preferred embodiment of the invention, the liq quaternary ammonium compounds, in particular alkyl uid composition contains no or less than 0.1% by weight, 40 trimethylammonium salts and dialkyldimethylam based on the total weight of the composition, of a non-poly monium salts, e.g. the halides, sulfates and alkylsul meric Surfactant. fates In contrast to the blockcopolymers P, the non-polymeric Pyridinium salts, in particular alkylpyridinium salts e.g. surfactant usually has a molecular weight below 1,000 dalton, the halides, Sulfates and C-C-alkylsulfates and in particular below 800 dalton. The non-polymeric surfactant 45 Imidazolinium salts in particular N,N'-dialkylimidazo may be non-ionic, anionic, cationic or Zwitterionic. Suitable linium salts, e.g. the halides, Sulfates or methox non-polymeric Surfactants which may be used in the liquid ulfates. compositions of the invention are disclosed, e.g. in As regards the non-polymeric Surfactants, the term “alkyl “McCutcheon's Detergents and Emulsifiers Annual, MC as used herein and if not defined otherwise is a linear or Publishing Corp., Ridgewood, N.J., USA 1981; H. Stache, 50 branched alkyl group having from 4 to 30, preferably from 6 “Tensid-Taschenbuch", 2" ed., C. Hanser, Munich, Vienna, to 22 carbon atoms, e.g. n-hexyl, 1-methylpentyl, n-heptyl, 1981; M. and J. Ash, “Encyclopedia of Surfactants”, Vol. I-III, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 1-methylnonyl, Chemical Publishing Co., New York, N.Y., USA 1980-1981. 2-propylheptyl, n-dodecyl, 1-methyldodecyl, n-tridecyl. Examples of non-polymeric Surfactants comprise n-tetradecyl. n-pentadecyl, n-hexadecyl, n-heptadecyl, n-oc anionic Surfactants, selected from the salts, in particular the 55 tadecyl. n-nonadecyl. n-eicosyl, and the like. The term Sodium, potassium calcium or ammonium salts of “ethoxylated means that OH-functions have been reacted alkylsulfonates, such as lauryl Sulfonate, isotridecylsul with ethyleneoxide to form a oligoethyleneoxide group. The fonate, degree of ethoxylation (number average of ethyleneoxide alkylsulfates, in particular fatty alcohol Sulfates, such as repeating units) will usually be in the range from 1 to 30 and lauryl sulfate, isotridecylsulfate, cetylsulfate, stearyl 60 in particular from 2 to 20. sulfate The composition of the invention may further contain cus aryl- and alkylarylsulfonates, such as napthylsulfonate, tomary auxiliaries. Such as defoamers, thickeners, preserva dibutylnaphtylsulfonate, dodecyidiphenylether sul tives, colorants, stabilizers, adjuvants, wetting agents, pen fonate, cumylsulfonate, nonylbenzenesulfonate, etrants, coupling agents and the like which are usually dodecylbenzene sulfonate; 65 employed in non-aqueous formulations of pesticides. A Sulfonates of fatty acids and fatty acid esters; skilled person will appreciate that some of the aforemen sulfates of fatty acids and fatty acid esters; tioned components, e.g. Surfactants and solvents, may also US 8,741,324 B2 17 18 work as auxiliaries. In particular, Solvents may work as anti The water used for mixing is usually tap water. However freeze agents or penetrants and the aforementioned Surfac the water may already contain water soluble compounds tants may work as adjuvants or wetting agents. which are used in plant protection, e.g. nutrificants, fertilizers Suitable thickening agents include inorganic thickening or water soluble pesticides. agents. Such as clays, hydrated magnesium silicates and 5 The aqueous pesticide compositions of the invention can organic thickening agents, such as polysaccharide gums, like be used as such for plant protection, i.e. for combating organ Xanthan gum, guar gum, gum arabic and cellulose derivatives. isms that are harmful to plants or for protecting crops from Organic thickening agents are employed in amounts of from attack or infestation by Such an harmful organism. Therefore, 0.5 to 30 g/l and preferably from 1 to 10 g/l while inorganic the present invention also relates to an aqueous pesticide thickening agents are employed in amounts of from 0.5 to 30 10 composition which is obtained by diluting the liquid concen g/l and preferably from 1 to 10 g/l. trate composition of the present invention. The present inven Suitable preservatives to prevent microbial spoiling of the tion also relates to the use of the aqueous pesticide composi compositions of the invention include formaldehyde, alkyl tions for plant protection and in particular to a method of esters of p-hydroxybenzoic acid, Sodium benzoate, 2-bromo combating organisms that are harmful to plants such as 15 weeds, fungi, insects, arachnids or nematodes, which com 2-nitropropane-1,3-diol, o-phenylphenol, thiazolinones, prises contacting said harmful organisms, their habit, breed Such as benzisothiazolinone, 5-chloro-2-methyl-4-isothiaz ing ground, food Supply, plant, seed, soil, area, material or olinone, pentachlorophenol. 2,4-dichlorobenzyl alcohol and environment in which the harmful organisms are growing or mixtures thereof. In general, the amount of preservatives will may grow, or the materials, plants, seeds, soils, Surfaces or be from 0.1 to 10 g/l. spaces to be protected from attack or infestation by harmful Suitable defoamers include polysiloxanes, such as poly organisms with an effective amount of an aqueous composi dimethyl siloxane. Defoamers are usually employed in tion as described herein. The invention also relates to a amounts of from 0.1 to 5 g/l. method for protecting crops from attack or infestation by Suitable stabilizers comprise e.g. UV-absorbers such as harmful organisms such as weeds, fungi, insects, arachnids or cinnamic esters, 3.3-diphenyl-2-cyano acrylates, hydroxy 25 nematodes, which comprises contacting a crop with an effec and/or alkoxy substituted benzophenones, N-(hydroxyphe tive amount of an aqueous composition as described herein. nyl)-benzotriazoles, hydroxyphenyl-s-triazines, oxalic The compositions of the invention after dilution are applied amides and salicylates, e.g. the UVINUL(R)3000,3008,3040, by usual means which are familiar to a skilled person. 3048, 3049, 3050, 3030, 3035, 3039, 3088, UVINUL(R) MC80 and radical scavengers, e.g. ascorbic acid, sterically 30 If the composition contain a fungicide compound they may hindered amines (HALS-compounds) such as UVINUL(R) be applied against the following harmful fungi. 4049H, 4050H and 5050H, and the like and anti-oxidants Alternaria species on vegetables and fruit and rice, such as vitamin E. In general, the amount of stabilizer will be Bipolaris and Drechslera species on cereals, rice and turf, from 0.01 to 10 g/l of the concentrate composition. Blumeria graminis (powdery mildew) on cereals, These customary auxiliaries may be contained within the 35 Botrytis cinerea (gray mold) on Strawberries, vegetables, composition of the present invention. However, it is also ornamentals and grapevines, possible to add these auxiliaries after dilution with water to the ready-to-use aqueous composition. Erysiphe cichoracearum and Sphaerotheca fitliginea on Upon dilution with water, the liquid compositions of the cucurbits, invention forman aqueous pesticide composition which con 40 Fusarium and Verticillium species on various plants, tains the at least one organic pesticide compound C, the at Mycosphaerella species on cereals, bananas and peanuts, least one organic solvent S, the at least one non-ionic block Phakopsara pachyrhizi and Phakopsara meibomiae on copolymer P and optionally one or more non-polymeric Sur Soybeans factants and water. In these compositions, the at least one Phytophthora infestans on potatoes and tomatoes, organic pesticide compound is present in the form of finely 45 divided particles having a particle size in the nm range, i.e. the Plasmopara viticola on grapevines, average particle size as determined by dynamic light scatter Podosphaera leucotricha on apples, ing (at 25°C. and 1,013 mbar) is below 500 nm, preferably in Pseudocercosporella herpotrichoides on wheat and barley, the range from 100 to 300 nm, in particular in the range from Pseudoperonospora species on hops and cucumbers, 10 to 200 nm and most preferably in the range from 10 to 100 50 Puccinia species on cereals, . In order to obtain these aqueous pesticide compositions, Pyricularia Oryzae, Cochliobolus miyabeanus and Corti the liquid compositions of the invention are usually diluted cium Sasakii (Rhizoctonia Solani), Fusarium semitectum with at least 5 parts of water, preferably at least 10 parts of (and/or moniliforme), Helminth. Spp, Cercospora water, in particular at least 20 parts of water and more pref 55 Oryzae, Cochliobolus miyabeanus, Sarocladium Oryzae, erably at least 50 parts of water, e.g. from 10 to 10,000, in S attenuatum, Entvloma Oryzae, Gibberella filikuroi particular from 20 to 1,000 and more preferably from 50 to (bakanae), Grainstaining complex (various pathogens), 250 parts of water per one part of the liquid composition (all Bipolaris species, Drechslera species, Agarico parts are given in parts by weight). mycetidae Such as Rhizoctonia Solani and/or Pythium on Dilution will be usually achieved by pouring the concen 60 rice, trate compositions of the invention into water. Usually, dilu Rhizoctonia species on cotton, rice and turf. tion is achieved with agitation, e.g. with stirring, to ensure a Septoria tritici and Stagonospora nodorum on wheat, rapid mixing of the concentrate in water. However, agitation Uncinula necator on grapevines, is not necessary. Though the temperature of mixing is not Ustilago species on cereals and Sugar cane, and critical, mixing is usually performed attemperatures ranging 65 from 0 to 100° C., in particular from 10 to 50° C. or at ambient Venturia species (scab) on apples and pears; temperature. Paecilomyces variotii on materials (e.g. wood) US 8,741,324 B2 19 20 If the composition contain a compound, having insecti Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovi cidal, acaricidal or nematicidal activity they may be applied nus, Tipula oleracea and Tipula paludosa, against the following pest: thrips (Thysanoptera), e.g. Frankliniella fisca, Franklin Insects from the order of the iella occidentalis, Frankliniella tritici, Scirtothrips citri, lepidopterans (Lepidoptera), for example Agrotis ypsilon, Thrips Oryzae, Thrips palmi and Thrips tabaci, Agrotis segetum, Alabama argillacea, Anticarsia gemmata hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta lis, Argyresthia conjugella, Autographa gamma, Bupalus cephalotes, Atta sexdens, Atta texana, Hoplocampa piniarius, Cacoecia murinana, Capua reticulana, Chemato minuta, Hoplocampa testudinea, Monomorium phara bia brumata, Choristoneura filmiferana, Choristoneura Occi Onis, Solenopsis geminata and Solenopsis invicta, dentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus 10 heteropterans (Heteroptera), e.g. Acrosteinum hilare, Blis pini, Diaphania initidalis, Diatraea grandiosella, Earias sus leucopterus, Cyrtopeltis notatus, Dysdercus cingu insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, latus, Dysdercus intermedius, Eurygaster integriceps, Evetria bouliana, Feltia subterranea, Galleria mellonella, Euschistus impictiventris, Leptoglossus phyllopus, Grapholitha funebrana, Grapholitha molesta, Heliothis 15 Lygus lineolaris, Lygus pratensis, Nezara viridula, armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Piesma quadrata, Solubea insularis and Thyanta perdi Hibernia defoliaria, Hyphantria cunea, Hyponomeuta tor; malinellus, Keiferia lycopersicella, Lambdina fiscellaria, homopterans (Homoptera), e.g. Acyrthosiphon Onobry Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, chis, Adelges laricis, Aphidula masturti, Aphis fabae, Lithocolletis blancardella, Lobesia botrana, Loxostege stic Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis gros ticalis, Lymantria dispar; Lymantria monacha, Lyonetia cler sulariae, Aphis schneideri, Aphis spiraecola, Aphis Sam kella, Malacosoma neustria, Mamestra brassicae, Orgvia buci, Acyrthosiphon pisum, Aulacorthum Solani, pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectino Brachycaudus Cardui, Brachycaudus helichrysi, phora gossypiella, Peridroma Saucia, Phalera bucephala, Brachycaudus persicae, Brachycaudus prunicola, Phthorimaea operculella, Phyllocnistis citrella, Pieris bras 25 Brevicoryne brassicae, Capitophorus horni, Cerosipha sicae, Plathylpena scabra, Plutella xylostella, Pseudoplusia gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, includens, Rhyacionia frustrana, Scrobipalpula absoluta, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis Sitotroga cerealella, Sparganothis pilleriana, Spodoptera radicola, Dysaulacorthum pseudosolani, Dysaphis frugiperda, Spodoptera littoralis, Spodoptera litura, Thau plantaginea, Dysaphis pyri, Empoasca fabae, Hya matopoea pity'Ocampa, Tortrix viridana, Trichoplusia ni and 30 lopterus pruni, Hyperomyzus lactucae, Macrosiphum Zeiraphera Canadensis, avenae, Macrosiphum euphorbiae, Macrosiphon rosae, beetles (Coleoptera), for example Agrilus sinuatus, Agri Megoura viciae, Melanaphis pyrarius, Metopolophium otes lineatus, Agriotes obscurus, Amphimalus solstitia dirhodium, Myzodes persicae, Myzus ascalonicus, lis, Anisandrus dispar, Anthonomus grandis, Anthono Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, mus pomorum, Atomaria linearis, Blastophagus 35 Nilaparvata lugens, Pemphigus bursarius, Perkinsiella piniperda, Blitophaga undata, Bruchus rufimanus, Bru saccharicida, Phorodon humuli, Psylla mali, Psylla chus pisorum, Bruchus lentis, Byctiscus betulae, piri, Rhopalomyzus ascalonicus, Rhopalosiphum mai Cassida nebulosa, Cerotoma trifiurcata, Ceuthorrhyn dis, Rhopalosiphum padi, Rhopalosiphum insertum, chus assimilis, Ceuthorrhynchus mapi, Chaetocnema Sappaphis mala, Sappaphis mali, Schizaphis graminum, tibialis, Conoderus vespertinus, Crioceris asparagi, 40 Schizoneura lanuginosa, Sitobion avenae, Trialeurodes Diabrotica longicornis, Diabrotica 12-punctata, vaporariorum, Toxoptera aurantiand, and Viteus viti Diabrotica virgifera, Epilachna varivestis, Epitrix hir folii; tipennis, Eutinobothrus brasiliensis, Hylobius abietis, termites (Isoptera), e.g. Calotermes flavicollis, Leucote Hypera brunneipennis, Hypera postica, Ips typogra rmes flavipes, Reticulitermes lucifigus und Termes phus, Lema bilineata, Lema melanopus, Leptinotarsa 45 natalensis, decemlineata, Limonius Californicus, Lissorhoptrus orthopterans (Orthoptera), e.g. Acheta domestica, Blatta Oryzophilus, Melanotus communis, Melligethes aeneus, Orientalis, Blattella germanica, Forficula auricularia, Gryl Melolontha hippocastani, Melolontha melolontha, lotalpa gryllotalpa, Locusta migratoria, Melanoplus bivitta Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn tus, Melanoplus femur-rubrum, Melanoplus mexicanus, Mel chus ovatus, Phaedon cochleariae, Phyllotreta chryso 50 anoplus sanguinipes, Melanoplus spretus, Nomadacris cephala, Phyllophaga sp., Phyllopertha horticola, Phyl Septemfasciata, Periplaneta americana, Schistocerca ameri lotreta memorum, Phyllotreta striolata, Popillia cana, Schistocerca peregrina, Stauronotus maroccanus and japonica, Sitona lineatus and Sitophilus granaria, Tachycines asynamorus, dipterans (Diptera), for example Aedes aegypti, Aedes Arachnoidea, such as arachnids (Acarina), e.g. of the fami vexans, Anastrepha ludens, Anopheles maculipennis, 55 lies Argasidae. Ixodidae and Sarcoptidae. Such as Amblvo Ceratitis capitata, Chrysomya bezziana, Chrysomya mma americanum, Amblyomma variegatum, Argas persicus, hominivorax, Chrysomya macellaria, Contarinia Boophilus annulatus, Boophilus decoloratus, Boophilus Sorghicola, Cordylobia anthropophaga, Culex pipiens, microplus, Dermacentor Silvarum, Hvalomma truncatum, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Ixodes ricinus, Ixodes rubicundus, Omithodorus moubata, Fannia canicularis, Gasterophilus intestinalis, Glossina 60 Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhi morsitans, Haematobia irritans, Haplodiplosis eques picephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes tris, Hvlemyia platura, Hypoderma lineata, Liriomyza scabiei, and Eriophyidae spp. Such as Aculus Schlechtendali, sativae, Liriomyza trifoli, Lucilia Caprina, Lucilia cup Phyllocoptrata oleivOra and Eriophyes Sheldoni; Tarsonemi rina, Lucilia sericata, Lycoria pectoralis, Mayetiola dae spp. Such as Phytonemus pallidus and Polyphagotarson destructor, Musca domestica, Muscina stabulans, 65 emus latus; Tenuipalpidae spp. Such as Brevipalpus phoeni Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phor cis; Tetranychidae spp. Such as Tetranychus cinnabarinus, bia antiqua, Phorbia brassicae, Phorbia coarctata, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus US 8,741,324 B2 21 22 telarius and Tetranychus urticae, Panonychus ulmi, Panony The compositions containing a herbicide can be applied in chus citri, and Oligonychus pratensis, conventional manner, usually as an aqueous composition Nematodes, especially plant parasitic nematodes Such as which is obtained from a composition of the invention by root knot nematodes, Meloidogyne hapla, Meloidogyne diluting with water. incognita, Meloidogyne javanica, and other Meloidogyne 5 The required application rate of the pure active compounds species; cyst-forming nematodes, Globodera rostochiensis without formulation auxiliary, depends on the density of the and other Globodera species; Heterodera avenae, Het undesired vegetation, on the development stage of the plants, erodera glycines, Heterodera Schachtii, Heterodera trifolii, on the climatic conditions of the location where the compo and other Heterodera species; Seed gall nematodes, Anguina sition is used and on the application method. In general, the species; Stem and foliar nematodes, Aphelenchoides species; 10 application rate is from 0.001 to 3 kg/ha, preferably from Sting nematodes, Belonolaimus longicaudatus and other 0.005 to 2 kg/ha and in particular from 0.01 to 1 kg/ha, from Belonolaimus species; Pine nematodes, Bursaphelenchus 0.1 g/ha to 1 kg/ha, from 1 g/ha to 500 g/ha or from 5 g/ha to xylophilus and other Bursaphelenchus species; Ring nema 500 g/ha of active substance. todes, Criconema species, Criconemella species, Cri 15 The diluted compositions are applied to the plants mainly conenoides species, Mesocriconema species; Stem and bulb by spraying, in particular foliar spraying. Application can be nematodes, Dity lenchus destructor, Dity lenchus dipsaci and carried out by customary spraying techniques using, for other Dity lenchus species; Awl nematodes, Dolichodorus example, water as carrier and spray liquor rates of from about species; Spiral nematodes, Heliocotylenchus multicinctus 100 to 1 000 l/ha (for example from 300 to 400 l/ha). Appli and other Helicotylenchus species; Sheath and sheathoid 20 cation of the preparations by the low-volume and the ultra nematodes, Hemicycliophora species and Hemiciri low-volume method is possible, as is their application in the conenoides species; Hirshmanniella species; Lance nema form of microgranules. todes, Hoploaimus species; false rootknot nematodes, In a preferred embodiment of the invention, composition of Nacobbus species; Needle nematodes, Longidorus elongatus active ingredients are applied in a rate which provides control and other Longidorus species: Lesion nematodes, Pratylen- 25 of weeds or crops, in particular post-emergence to the weed or chus neglectus, Pratylenchus penetrans, Pratylenchus curvi crop, but preferably prior to the planting, seeding or emer tatus, Pratylenchus goodevi and other Pratylenchus species; gence of a desired crop. Burrowing nematodes, Radopholus similis and other Radop In another preferred embodiment of the invention, control holus species: Reniform nematodes, Rotylenchus robustus of weeds or crops is provided by an application of the com 30 position of active ingredients before a desired crop is seeded, and other Rotylenchus species; Scutellonema species; Stubby planted or emerged (pre-emergence or pre-plant application), root nematodes, Trichodorus primitivus and other Tri followed by one or more treatments after the crop is emerged chodorus species, Paratrichodorus species; Stunt nematodes, with one or more herbicides which are selective in the crop. Tvlenchorhynchus claytoni, Tilenchorhynchus dubius and Moreover, it may be useful to apply the compositions other Tilenchorhynchus species; Citrus nematodes, Tvlen 35 according to the invention jointly as a mixture with other crop chulus species; Dagger nematodes, Xiphinema species; and protection products, for example with pesticides or agents for other plant parasitic nematode species: controlling phytopathogenic fungi or bacteria. Also of inter If the compositions according to the invention contain an est is the miscibility with mineral salt solutions which are insecticide compound which is active against rice pathogens, employed for treating nutritional and trace element deficien the composition may also be used to combat rice phatogens 40 cies. Non-phytotoxic oils and oil concentrates may also be Such as rice water weevil (Lissorhoptrus Oryzaphilus), rice added. stem borer (Chilo suppresalis), rice leaf roller, rice leaf Inafurther embodiment of the invention, the compositions beetle, rice leaf miner (Agromyca Oryzae), leafhoppers contain a compound, in particular an insecticide compound (Nephotettix spp., especially Smaller brown leafhopper, green which is active against non-crop pests. Therefore the inven rice leafhopper), planthoppers (Delphacidae, especially 45 tion also relates to a method for controlling non-crop pests white backed planthopper, brown rice planthopper), Stink comprising contacting the pests or their food Supply, habitat, bugs. breeding grounds or theirlocus with formulation according to If the compositions according to the invention contain a the invention comprising at least an insecticide. herbicide compound it will be used to control undesired veg The invention further relates to the use of a composition etation. The control of undesired vegetation is understood as 50 according to the invention comprising at least an insecticide meaning the destruction of weeds. Weeds, in the broadest for the protection of non-living organic materials against sense, are understood as meaning all those plants which grow non-crop pests. in locations where they are undesired, for example: Non-crop pests are pests of the classes Chilopoda and Dicotyledonous weeds of the genera: Sinapis, Lepidium, Diplopoda and of the orders Isoptera, Diptera, Blattaria (Blat Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Che- 55 todea), Dermaptera, Hemiptera, Hymenoptera, Orthoptera, nopodium, Urtica, Senecio, Amaranthus, Portulaca, Siphonaptera, Thysanura, Phthiraptera, Araneida, Parasiti Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, formes and Acaridida, for example: Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, centipedes (Chilopoda), e.g. Scutigera coleoptrata, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, millipedes (Diplopoda), e.g. Narceus spp., Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, 60 spiders (Araneida), e.g. Latrodectus mactans, and Ranunculus, Taraxacum. Loxosceles reclusa, Monocotyledonous weeds of the genera: Echinochloa, Scabies (Acaridida): e.g. sarcoptes sp., Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, ticks and parasitic mites (Parasitiformes): ticks (Ixodida), Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes paci Agropyron, Cynodon, Monochoria, Fimbristyslis, Sagittaria, 65 ficus, Rhiphicephalus sanguineus, Dermacentor ander Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, soni, Dermacentor variabilis, Amblyomma ameri Dactyloctenium, Agrostis, Alopecurus, Apera. canum, Ambryomma maculatum, Ornithodorus hermsi, US 8,741,324 B2 23 24 Ornithodorus turicata and parasitic mites (Mesostig nus eurysternus, Haematopinus suis, Linognathus vituli, mata), e.g. Ornithonyssus bacoti and Dermanyssus Bovicola bovis, Menopon gallinae, Menacanthus stra gallinae, mineus and Solenopotes capillatus. termites (Isoptera), e.g. Calotermes flavicollis, Leucote For examples, formulation according to the invention com rmes flavipes, Heterotermes aureus, Reticulitermes fia 5 prising at least an insecticide can be used for the protection of vipes, Reticulitermes virginicus, Reticulitermes lucifit non-living organic materials, including but are not limited to gus, Termes natalensis, and Coptotermes formosanus, house-hold goods such as fats, oils, mono- oligo- or polyor cockroaches (Blattaria-Blattodea), e.g. Blattelia ger ganosaccharides, proteins, or fresh or decaying fruits; cellu manica, Blattella asahinae, Periplaneta americana, lose-containing materials e.g. wooden materials such as Periplaneta japonica, Periplaneta brunnea, Periplaneta 10 houses, trees, board fences, or sleepers and also paper, and filigginosa, Periplaneta australasiae, and Blatta Orien also construction materials, furniture, leathers, animal, plant talis, and synthetic fibers, vinyl articles, electric wires and cables as flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes well as styrene foams. albOpictus, Aedes vexans, Anastrepha ludens, Anoph Furthermore, a formulation according to the invention eles maculipennis, Anopheles crucians, Anopheles albi 15 comprising at least an insecticide can be used for the protec manus, Anopheles gambiae, Anopheles freeborni, tion of non-living organic materials against non-crop pests Anopheles leucosphyrus, Anopheles minimus, Anoph selected from the group consisting of the class Diplopoda and eles quadrimaculatus, Caliphora vicina, Chrysomya of the orders Isoptera, Diptera, Blattaria (Blattodea), Der bezziana, Chrysomya hominivorax, Chrysomya macel maptera, Hemiptera, Hymenoptera, Orthoptera, and Thysa laria, Chrysops discalis, Chrysops silacea, Chrysops la. atlanticus, Cochliomyia hominivorax, Cordylobia The present invention also relates to a method for the anthropophaga, Culicoides furens, Culex pipiens, Culex protection of non-living organic materials against non-crop nigripalpus, Culex quinquefasciatus, Culex tarsalis, pests as mentioned above comprising contacting the pests or Culiseta inomata, Culiseta melanura, Dermatobia their food Supply, habitat, breeding grounds, theirlocus or the hominis, Fannia canicularis, Gasterophilus intestinalis, 25 non-living organic materials themselves with a pesticidally Glossina morsitans, Glossina palpalis, Glossina fisci effective amount of a formulation according to the invention. pes, Glossina tachinoides, Haematobia irritans, Haplo Furthermore, a formulation according to the invention diplosis equestris, Hippelates spp., Hypoderma lineata, comprising at least an insecticide can be used for protecting Leptoconops torrens, Lucilia caprina, Lucilia cuprina, cellulose-containing non-living organic materials, e.g. for Lucilia sericata, Lycoria pectoralis, Mansonia spp., 30 protecting cellulose-containing non-living organic materials Musca domestica, Muscina stabulans, Oestrus ovis, against non-crop pests from the Isoptera, Diptera, Blattaria Phlebotomus argentipes, Psorophora columbiae, Pso (Blattodea), Hymenoptera, and Orthoptera orders, most pref rophora discolor; Prosimulium mixtum, Sarcophaga erably the Isoptera orders. haemorrhoidalis, Sarcophaga sp., Simulium vittatum, The present invention also provides a method for protect Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, 35 ing cellulose-containing non-living organic materials against Tabanus lineola, and Tabanus similis, non-crop pests, preferably from the Isoptera, Diptera, Blat Earwigs (Dermaptera), e.g. forficula auricularia, taria (Blattodea), Hymenoptera, and Orthoptera orders, most true bugs (Hemiptera), e.g. Cimex lectularius, Cimex hemi preferably the Isoptera orders, comprising contacting the pterus, Reduvius senilis, Triatoma spp., Rhodnius pro pests or their food Supply, habitat, breeding grounds, their lixus, and Arilus critatus, 40 locus or the cellulose-containing non-living organic materials ants, bees, wasps, sawflies (Hymenoptera), e.g. Cremato themselves with a a formulation according to the invention gaster spp., Hoplocampa minuta, Hoplocampa comprising at least an insecticide. testudinea, Monomorium pharaonis, Solenopsis gemi Furthermore, a formulation according to the invention nata, Solenopsis invicta, Solenopsis richteri, Solenopsis comprising at least an insecticide can be used for protecting xyloni, Pogonomyrmex barbatus, Pogonomyrmex cali 45 mono- oligo- or polysaccharides and proteins. fornicus, Dasy mutila Occidentalis, Bombus spp. Furthermore, a formulation according to the invention Vespula squamosa, Paravespula vulgaris, Paravespula comprising at least an insecticide can be used for protection of pennsylvanica, Paravespula germanica, Dolicho mono- oligo- or polysaccharides and proteins against non vespula maculata, Vespa crabro, Polistes rubiginosa, crop pests selected from the Dermaptera, Diplopoda, Camponotus floridanus, and Linepithema humile, 50 Isoptera, Diptera, Blattaria (Blattodea), Hymenoptera, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta Orthoptera and Tysanura orders, most preferably the Isoptera, domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Diptera, Blattaria (Blattodea), and Hymenoptra orders. Melanoplus bivittatus, Melanoplus femurrubrum, Mel Furthermore, a composition according to the invention anoplus mexicanus, Melanoplus sanguinipes, Melano comprising at least an insecticide can be used for used for plus spretus, Nomadacris Septemfasciata, Schistocerca 55 protection of animals against non-crop pest of the class americana, Schistocerca gregaria, Dociostaurus Chilopoda, and of the orders Araneida, Hemiptera, Diptera, maroccanus, Tachycines asynamorus, Oedaleus Senega Phthiraptera, Siphonaptera, Parasitiformes and Acaridida by lensis, Zonozerus variegatus, Hieroglyphus daganensis, treatment of the pests in water bodies and/or in and around Kraussaria angulifera, Calliptamus italicus, Chortoice buildings, including but not limited to walls, ground, manure tes terminifera, and Locustana pardalina, 60 piles, turfgrass, pastures, sewers and materials used in the fleas (Siphonaptera), e.g. Ctenocephalides felis, Cteno construction of buildings and also mattresses and bedding, cephalides canis, Xenopsylla cheopis, Pulex irritans, with a formulation according to the present invention. Tunga penetrans, and Nosopsyllus fasciatus, Animals include warm-blooded animals, including silverfish, firebrat (Thysanura), e.g. Lepisma saccharina humans and fish. Thus, a formulation according to the inven and Thermobia domestica, 65 tion comprising at least an insecticide can be used for protec lice (Phthiraptera), e.g. Pediculus humanus capitis, tion of warm-blooded animals such as cattle, sheep, Swine, Pediculus humanus CorpOris, Pthirus pubis, Haematopi camels, deer, horses, poultry, rabbits, goats, dogs and cats. US 8,741,324 B2 25 Furthermore, a formulation according to the invention comprising at least an insecticide can be used for protecting amidraZone I: wooden materials such as trees, board fences, sleepers, etc. C2H5 and buildings such as houses, outhouses, factories, but also C HN1 construction materials, furniture, leathers, fibers, vinyl 2 articles, electric wires and cables etc. from ants and/or ter NN C mites, and for controlling ants and termites from doing harm H3C to crops or human being (e.g. when the pests invade into CF C C houses and public facilities). A formulation according to the 10 amidraZone II: invention comprising at least an insecticide can be are applied CH5 not only to the Surrounding soil Surface or into the under-floor C HN1 soil in order to protect wooden materials but it can also be na CH applied to lumbered articles such as surfaces of the under 15 floor concrete, alcove posts, beams, plywoods, furniture, etc., HC CH3 wooden articles such as particle boards, halfboards, etc. and CF C vinyl articles Such as coated electric wires, vinyl sheets, heat insulating material Such as styrene foams, etc. In case of My is the number average molecular weight application againstants doing harm to crops or human beings, blockcopolymer P': EO/PO triblockoopolymer, OH termi the ant control composition of the present invention is directly nated; My 4960, EO/PO ratio 43:57, HLB-Value 9; applied to the nest of the ants or to its Surrounding or via bait blockoopolymer P': EO/PO triblockcopolymer, OH termi COntact. nated; M3650, EO/PO ratio 25:75, HLB-Value 6: 25 blockcopolymer P: EO/PO triblockcopolymer, OH termi Furthermore, a formulation according to the invention nated: My 2500, EO/PO ratio 25:75, HLB-Value 9; comprising at least an insecticide can be applied preventively blockcopolymer P': EO/PO triblockoopolymer, OH termi to places at which occurrence of the pests is expected. nated; M5750, EO/PO ratio 43:57, HLB-Value 8: If the formulation according to the present invention is blockcopolymer P: EO/PO triblockcopolymer, OH termi intended for seed treatment purposes, the formulation may 30 nated: M. 4500, EO/PO ratio 50:50, HLB-Value 15; optionally comprise also pigments. Suitable pigments or dyes blockcopolymer P: EO/PO triblockcopolymer, OH termi for seed treatment formulations are pigment blue 15:4, pig nated: My 2900, EO/PO ratio 66:34, HLB-Value 15; ment blue 15:3, pigment blue 15:2, pigment blue 15:1, pig blockcopolymer P3: EO/PO triblockcopolymer, OH termi ment blue 80, pigment yellow 1, pigment yellow 13, pigment nated; My 4460, EO/PO ratio 43:57, HLB-Value 9. red 112, pigment red 48:2, pigment red 48:1, pigment red 35 blockcopolymer P': EO/PO triblockcopolymer, My 6000, 57:1, pigment red 53:1, pigment orange 43, pigment orange EO/PO ratio 60:40, 34, pigment orange 5, pigment green 36, pigment green 7. blockcopolymer P': EO/PO triblockcopolymer, My 4290, pigment white 6, pigment brown 25, basic violet 10, basic EO/PO ratio 30:70, HLB-Value 9. violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, blockcopolymer P': EO/PO triblockcopolymer, Mw 7500, 40 EO/PO ratio 60:40, acid yellow 23, basic red 10, basic red 108. blockcopolymer P": EO/PO triblockoopolymer, M4200, The invention furthermore comprises seeds treated with EO/PO ratio 40:60, HLB-Value 12-18. the formulation according to the present invention. II.1 Compositions 1.1-1.7, 2.1-2.8, 3.1-3.2, 4.1-4.9, 5.1-5.12, Suitable seeds are for example various crop seeds, fruit 6, 1-6.10, 7.1-7.9 and 8.1 species, vegetables, spices and ornamental seed, for example 45 General Procedure A: corn/maize (Sweet and field), durum wheat, soybean, wheat, The active ingredient and optionally further additives are barley, oats, rye, triticale, bananas, rice, cotton, Sunflower, stirred in the solvent S at room temperature until complete potatoes, pasture, alfalfa, grasses, turf, Sorghum, rapeseed, dissolution. The thus obtained solution is mixed with block Brassica spp., Sugar beet, eggplants, tomato, lettuce, iceberg copolymer P and optionally further Surfactant until a homog lettuce, pepper, cucumber, squash, melon, bean, dry-beans, 50 enous mixture is obtained. peas, leek, garlic, onion, cabbage, carrot, tuber Such as Sugar General Procedure B: cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, The active ingredient and optionally further additives are grapevines, pepper, fodder beet, oil seed rape, pansy, impa stirred in a mixture of the solvent S and the blockcopolymer tiens, petunia and geranium. Pat room temperature until complete dissolution. 55 The compositions outlined in Tables 1, 3, 4, 5, 6, 7 and 8 The following examples are intended to further illustrate were prepared by the general procedure A. The compositions the present invention. outlined in Table 2 were prepared by the general procedure B. I Analytics: In Tables 1 to 8 the amounts of the ingredients are given in % Particle sizes were determined by dynamic light scattering by weight. with a “Nicomp by Particle Sizing System PSS, Model 60 Upon dilution with water (100 parts per 1 part of compo 370 at 250 C. sition) the compositions of Tables 1 to 8 form bluish clear II. Preparation of the Compositions of the Invention: compositions, wherein the active ingredient particles have an average diameter below 100 nm (as determined by quasi 1. In the Tables 1 to 14, the following abbreviations are used: elastic light scattering). The diluted composition remain semicarbazone: 1-N-(4-Trifluoromethoxyphenyl)semi 65 stable for at least 24 h. A diluted composition is estimated to carbazono-1-(3-cyanophenyl)-2-(4-trifluorometh be stable period of time if the particle size remains below 100 ylphenyl)ethane (Metaflumizone) nm within said time period. US 8,741,324 B2 27 28 TABLE 1. TABLE 5 Compositions containing 1-N-(4-Trifluoromethoxyphenyl)semicarbazono Compositions containing (RS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2- 1-(3-cyanophenyl)-2-(4-trifluoromethylphenyl)ethane (metaflumizone) methoxy-1-methylethyl)acetamide (dimethenamid) compositions 1.1 to 1.7): 5 composition composition S.1 5.2 5.3 5.4 5.5 S.6 1.1 1.2 1.3 1.4 1.5 1.6 1.7 dimethenamid 24.0 36.O 24.O 36.O 24.0 36.O Metaflumizone 13.4 134 134 13.4 134 13.4 13.4 Y-butyrolactone 46.0 34.0 Y-butyrolactone SO.8 - - 49.8 49.8 48.8 10 propan-1,3-diol 46.0 34.0 acetOne - SO.8 56.6 51.8 diisopropanolamine 46.0 34.O blockcopolymer P. — 10.0 — 34.8 diethylene glycol blockcopolymer P' 21.6 21.6 10.O 21.6 21.6 21.6 monomethylether blockcopolymer P. 14.2 14.2 10.0 14.2 14.2 14.2 ethanol Vitamin E 1.0 — 1.O acetOne UV-absorber 1.O 1.O 15 blockcopolymer P' 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O blockcopolymer P' 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O

TABLE 2 Compositions containing methyl N-2-1-(4-chlorophenyl)-1H-pyrazol-3- yloxymethylphenyl-(N-methoxy)carbamate (Pyraclostrobin) composition

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 pyraclostrobin 12.O 24.0 36.O 24.O 24.O 24.O 24.0 24.O Y-butyrolactone 58.0 36.O 24.O S1.O 2-pyrrollidone — 36.0 — N-methyl pyrrollidin-2-one — 36.0 — ethanol — 36.0 — acetOne — 36 blockcopolymer P. 2S.O 2SO 25.O 2S.O 2S.O 2S.O 2S.O 25.0 blockcopolymer P' 1O.O 15.O 15.O 15.O 15.O 15.O 15.O

TABLE 3 TABLE 5-continued Compositions containing methyl N-2-1-(4-chlorophenyl)-1H-pyrazol-3- Compositions containing (RS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2- yloxymethylphenyl-(N-methoxy)carbamate (Pyraclostrobin) and methoxy-1-methylethyl)acetamide (dimethenamid) 2-chloro-N-(4-chlorobiphenyl-2-yl)nicotinamide (Boscalid 40 blockcopolymer P. 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O composition composition 3.1 3.2 5.7 5.8 5.9 S.10 S.11 S.12 boscalid 12.O 12.0 45 pyraclostrobin 12.O 6.O dimethenamid 24.0 36.O 24.O 36.O 24.0 36.O N-methyl pyrrollidin-2-one 46.0 46.0 Y-butyrolactone blockcopolymer P' 2O.O 2O.O propan-1,3-diol blockcopolymer P' 1O.O 16.0 diisopropanolamine diethylene glycol 46.0 34.0

TABLE 4 Compositions containing N-(1-ethylpropyl)-2,6-dinitro-3,4-Xylidine pendimethalin composition

4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 pendimethalin 12.O 24.0 36.0 12.O 24.O 36.0 12.0 24.O 36.0 Y-butyrolactone 58.0 46.0 34.0 diethylene glycol 58.0 46.0 34.0 monomethylether acetOne blockcopolymer P. 1O.O blockcopolymer P' 1O.O blockcopolymer P. 1O.O US 8,741,324 B2 29 30 TABLE 5-continued TABLE 8 Compositions containing (RS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2- Compositions containing 1-4-(2-chloro-C.C.C.-trifluoro-p-tolyloxy)- methoxy-1-methylethyl)acetamide (dimethenamid) 2-fluorophenyl-3-(2,6-difluorobenzoylurea (flufenoxuron monomethylether composition ethanol — 46.0 34.0 8.1 acetOne blockcopolymer P. 1O.O 1.O.O. 10.O flufenoxuron 6.O blockcopolymer P' 1O.O 1.O.O. 10.O N-methyl pyrrollidin-2-one 64.O blockcopolymer P. 1O.O 1.O.O. 10.O blockcopolymer P' 1O.O 10 blockcopolymer P' 1O.O blockcopolymer P. 1O.O

TABLE 6 II.2 Compositions 9.1 to 9.6 Compositions containing ethyl trichloro-2-pyridyloxyacetate Compositions 9.1 to 9.6 were prepared according to (triclopyr-ethyl) 15 method A outlined in I. 1 by dissolving 12.5 parts by weight of composition Metaflumizone in 62.5 parts by weight of Y-butyrolactone and adding thereto 25 parts by weight of blockcopolymer (block 6.1 6.2 6.3 6.4 6.5 6.6 copolymer Pand/or blockcopolymer P as given in Table 9). triclopyr ethyl 24.0 36.O 24.O 36.O 24.0 36.O Each of the compositions was diluted with 100 parts of acetOne 46.0 34.O waterper 1 part of the composition (all parts given are parts by Y-butyrolactone 46.O 34.0 2-pyrrollidinone 46.0 34.0 weight). The obtained compositions were analyzed within 24 diethylene glycol h or 48 h, respectively, with regard to particle size of the monomethylether dispersed active ingredient. ethanol blockcopolymer P. 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O 25 The relative amounts of blockcopolymer P to blockco blockcopolymer p 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O polymer P and the average particle sizes of the dispersed blockcopolymer P. 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O material after dilution with water are given in Table 9. composition TABLE 9 30 6.7 6.8 6.9 6.10 particle size triclopyr ethyl 24.0 36.O 24.0 36.0 Composition PbPc 1) nm. stability ? acetOne Y-butyrolactone 9.1 O:10 48.2 24h 2-pyrrollidinone 9.2 2:8 26.1 48 h. 9.3 4:6 21.7 48 h. diethylene glycol 46.0 34.O 35 monomethylether 9.4 6:4 27.2 48 h. 9.5 8:2 41.9 48 h. ethanol 46.0 34.0 blockcopolymer P. 1O.O 1O.O 1O.O 1O.O 9.6 10:0 59.6 48 h. blockcopolymer P' 1O.O 1O.O 1O.O 1O.O 1) weight ratio of blockcopolymer P to blockcopolymer P. blockcopolymer P. 1O.O 1O.O 1O.O 1O.O 2)A composition is stable in the given time, if the particle size does not exceed 500 nm and no precipitate or crystalline material is observed.

TABLE 7

Compositions containing C-cyano-3-phenoxybenzyl (1S,3S)-3-(2,2- dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (alpha-cypermethrin)

composition

7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 alpha-cypermethrin 24.O 24.O 24.O 24.O 24.O 24.O 24.O 24.O 24.O acetOne 46.0 Y-butyrolactone 46.0 46.0 2-pyrrollidinone — 46.0 — 46.0 diethylene glycol — 46.0 — monomethylether ethanol — 46.0 — cyclohexanone — 46.0 46.0 — blockcopolymer P' 1.O.O. 10.O. 10.O 1 O.O. 10.O. 10.O 3O.O 3O.O 3O.O blockcopolymer P' 1.O.O. 10.O. 10.O 1 O.O. 10.O. 10.0 - blockcopolymer P. 1.O.O. 10.O. 10.O 1 O.O. 10.O. 10.0 - US 8,741,324 B2 31 32 II.3. Composition 10.1 to 10.5 of the Invention, Comparative TABLE 11 Compositions A and B Dilution stability Compositions 10.1 to 10.5 were prepared according to Active ingredient Solvent S after 24h method A outlined in I.1 by dissolving 10 parts by weight of 5 .1 Trichlopyrbutoyl acetone ------Metaflumizone in 70 parts by weight of Y-butyrolactone and .2 Trichlopyr butoyl Y-butyrolactone ------adding thereto 20 parts by weight of blockcopolymeras given .3 dimethenamid P Y-butyrolactone ------in Table 10. 4 dimethenamid P propylene glycol ------.5 dimethenamid P diisopropanolamine ------The type of blockcopolymer and the average particle sizes .6 Trichlopyr TEA’ 2-pyrrollidinone ------of the dispersed material after dilution with water are given in 10 .7 Trichlopyr TEA diethylene glycol ------Table 10. monomethylether .8 Trichlopyr TEA ethanol ------.9 Pyraclostrobin Y-butyrolactone ------TABLE 10 .10 Pendimethaline Y-butyrolactone ------.11 Ronilan Y-butyrolactone ------particle size 15 .12 metaflumizone Y-butyrolactone ------Composition blockcopolymer nm. stability ? .13 Pyraclostrobin 2-pyrrollidinone ------.14 Pendimethaline diethylene glycol ------10.1 Pd 50 24h monomethylether 10.2 Pa 75 24h .15 dimethenamid P diethylene glycol ------10.3 Pe 75 24h monomethylether .16 Pyraclostrobin ethanol ------10.4 Pf 124 48 h. .17 dimethenamid P ethanol ------1O.S Pb 25 24h .18 Trichlopyr TEA Agrosol Ex8 ------.19 Pyraclostrobin acetOne ------2)A composition is stable in the given time, if the particle size does not exceed 500 nm and .20 Pendimethaline acetOne ------no precipitate or crystalline material is observed, .21 dimethenamid P acetOne ------For comparison two conventional non-aqueous composi 25 2-((3,5,6-trichloro-2-pyridinyl)oxylacetic acid 2-butoxyethyl ester ’2-((3,5,6-trichloro-2-pyridinyl)oxylacetic acid triethylammonium salt tions A and B containing 10% by weight of metaflumizone vinclozolin were prepared. 4N octylpyrrollidin-2-one Composition A was a solution of 10 parts by weight of metaflumizone, and 25 parts by weight of an ethoxylated III. Investigation of Chemical Stability: polyarylphenol of the formula CHO(CHCHO), with 30 The following compositions were prepared in order to n=14-18 in 65 parts by weight of a 1:1 mixture of N-meth show the increased stability of compounds which may ylpyrrolidin-2-one and cyclohexanone. undergo chemical degradation in compositions according to Composition B was a solution of 10 parts by weight of the invention. semicarbazone 90 parts by weight of acetone. 35 III.1 Chemical Stability of {(isopropylidene)amino Upon dilution with 100 parts by weight of water per 1 part oxyacetic Acid, 2-methoxy-2-oxoethyl Ester (Oxime Ether) by weight of composition, composition. A formed a suspen The following composition C, D, E and F (comparative), Sion, wherein the initial average particle size of the dispersed 12.1 and 12.2 were prepared by mixing the active ingredients, material was about 0.25um. After 1 h the average particle size Solvents and Surface active compounds given in Table 12a. of the dispersed material was about 0.5um. After 24h, large 40 amounts of crystalline material of 2 mm in size were TABLE 12a observed. Composition

Upon dilution with 100 parts by weight of water per 1 part C D 12.1 E F 12.2 by weight of composition, composition B formed a suspen 45 Sion, wherein the initial average particle size of the dispersed Oxime ether 5 5 5 5 5 5 Acetone 85 85 85 68 68 68 material was about 0.5 Lum. Small amounts of crystalline Water 17 17 17 material were observed directly after dilution. After 1 h the Blockcopolymer Ps 10 10 average particle size of the dispersed material was about 1.0 nonylphenol ethoxylate ’ — 7.5 7.5 um. After 24h, large amounts of crystalline material of 2 mm 50 C3-alkyl SulfoSuccinate 2.5 2.55 in size were observed. 1) (isopropylidene)aminoloxyacetic acid, 2-methoxy-2-oxoethyl ester II.3 Composition 11.1 to 11.19 of the Invention, Test on 2) degree of ethoxylation EO = 8 Dilution Stability The samples were stored at 50° C. and removed at weekly 10 parts by weight of pesticide compound are dissolved in 55 intervals for analysis of the degree of degradation (by normal 65 parts by weight of solvent S. Thereto, 25 parts by weight of phase HPLC, UV-detection). The data were fitted to a first blockcopolymer P are added. A clear solution is obtained. order kinetic profile and the time for 10% degradation was The active ingredient and the solvent is given in Table 11. calculated. The results are given in Table 12b. The thus obtained compositions were diluted with 100 parts by weight of water per 1 by weight part of composition. 60 TABLE 12b After 24 h, the diluted compositions were examined by Composition Time for 10% degradation days dynamic light scattering. Each of the diluted compositions C 3.13.1 showed average particle sizes below 100 nm without forma D >SOOO tion of solids. Compositions rated ++++ showed average par 65 11.1 >SOOO ticle sizes below 20 nm while compositions rated +++ had E 1303 average particle sizes between 20 nm and 100 nm. US 8,741,324 B2 34 TABLE 12b-continued triblockcopolymer, sodium-dioctylsulfoSuccinate, ethoxy lated alkanol and ethoxylated alkylphenol. Composition Time for 10% degradation days 15.1 is a liquid concentrate composition according to the F 10.1 invention which contains 12.5% by weight of metaflumizone, 11.2 1169.2 52.8% by weight of butyrolactone and 35% by weight of a blend of blockcopolymers P, P and P. Upon dilution with III.2 Chemical Stability of Diflufenzopyr water the average particle size was about 20 nm. The following composition G and H (comparative), 13.1 Each of the compositions K, L and 15.1 were diluted with water to a concentration of semicarbazone of 3500 ppm for (inventive) were prepared by mixing the active ingredients, 10 100% use rate. Solvents and Surface active compounds given in Table 13. The compositions were applied under field conditions at The samples were stored at 50° C. and removed at weekly different use rates to plantations of several plant species of intervals for analysis of the degree of degradation (by normal leafy and fruiting vegetables, including brassica crops, pota phase HPLC, UV-detection). The data were fitted to a first toes, soybean, tobacco, beets and cotton. The insecticidal order kinetic profile and the time for 10% degradation was 15 activity against the following insect species: calculated. The results are given in Table 13. Heliothis virescens (tobacco budworm) Helicoverpazea (cotton bollworm, tomato fruitworm, corn TABLE 13 earworm) Helicoverpa armigera (old world bollworm) Composition Spodopteraexigua (beet armyworm) G H 13.1 Pseudoplusiaincludens (soybean looper) Spodopteraeridania (Southern armyworm) diflufenzopyr-sodium 5 5 5 Acetone 85 85 85 Spodopteraornithogalli (yellowstriped armyworm) Blockcopolymer Ps 10 Spodopterapraefica (Striped armyworm) nonylphenol ethoxylate 7.5 25 Spodoptera frugiperda (fall armyworm) C3-alkyl SulfoSuccinate 2.5 Mamestrabrassicae (cabbage armyworm) Time for 10% degradation days 4.2 1.1 54.1 Pierisrapae (imported cabbageworm) 1) degree of ethoxylation EO = 8 Hellulaundalis (cabbage webworm) Crocidolomiabinotalis (Asian cabbageworm) III.3 Chemical Stability of Metaflumizone 30 Ostrinianubilalis (European corn borer) The following compositions J (comparative) and 14.1 (in Trichoplusiani (cabbage looper) ventive) were prepared by mixing the active ingredients, sol Plutella xylostella (diamondback moth) vents and Surface active compounds given in Table 14. Keiferiallycopersicella (tomato pinworm) The samples were stored at 25° C. for 1 year. Then the Alabama argillacea (cotton leafworm) content of active ingredient was determined by HPLC-Analy 35 Anticarsia gemmatalis (Velvetbean caterpillar) sis. The results are given in Table 14. Pectinophora gossypiella (pink bollworm) Manduca quinquemaculata (tomato hornworm) TABLE 1.4 Grapholita molesta (oriental fruitmoth) Leptinotarsadecemlineata (Colorado potato beetle) Composition 40 Temnorhinusmendicus (Sugarbeet weevil) Chaetocnema, Phyllotreta & Psylliodes spp. (flea beetles) J 14.1 Aulacophora spp. (pumpkin beetle) semicarbazone 12.5 12.5 Diabrotica spp. (rootworm spp.) Y-Butyrolactone 87.5 57.5 Phaedonbrassicae (leaf beetle) Blockcopolymer Ps 30 45 Recovery after 1 year 9%) 80.0 99.8 Oulema spp. (cereal leaf beetle) was assessed in 100 field trials and for each use rate the 1) 1-N-(4-Trifluoromethoxyphenyl)semicarbazono-1-(3-cyanophenyl)-2-(4-trifluorom average activity against different insect species is categori ethylphenyl)ethane cally rated from 1 to 4. IV Biological Tests: 3 is the standard activity achieved at 100% (standard) use 1. Biological Performance of Compositions Containing 50 rate for the commercial Suspension concentrate K. Rating 4 Metaflumizone: exceeds standard control while 2 is worse than standard con 1.1 Bioefficacy trol and 1 is much worse than standard control. The results are The following compositions K, L, and 15.1 were evaluated given in Table 15. under field conditions: TABLE 1.5 K is a commercial aqueous Suspension concentrate of 55 Average Activity metaflumizone, wherein the average particle size of the active of Composition ingredient after dilution is about 1 lum. K contains 22% by weight of metaflumizone and 10% by weight of surfactant Use Rate (%) K L 15.1 which is a mixture of polyoxypropylene-polyoxyethylene 60 40 n.d. n.d. 2 triblockcopolymer, sodium-dioctylsulfoSuccinate, ethoxy 60 1 1 3 lated alkanol and ethoxylated alkylphenol. 70 2 2 4 85 3 3 4 L is a commercial aqueous Suspension concentrate of 100 3 3 n.d. metaflumizone wherein the average particle size of the active '% use rate of recommended use rate for commercial suspension concentrate K (corre ingredient after dilution is about 1.6 um. L contains 22% by 65 sponds to a concentration of 3500 ppm) weight of metaflumizone and 10% by weight of surfactant 'nd, no data which is a mixture of polyoxypropylene-polyoxyethylene US 8,741,324 B2 35 36 VI. Compositions Containing N-ethyl-2,2-dichloro-1-meth TABLE 16-continued ylcyclo-propanecarboxamide-2-(2,6-dichloro-C.C.C.-tri blockcopolymer P fluoro-p-tolyl)hydrazone (Amidrazone 1) or N-ethyl-2,2-di blockcopolymer P* - 20.O 200 1S.O (methyl)propionamide-2-(2,6-dichloro-C.C.C.-trifluoro-p- blockcopolymer P” 24.O 20.O. 16.O 20.O 20.O 20.O 2O.O tolyl)-hydrazone (Amidrazone II) Compositions VI.1 to Y-butyrolactone VI.52 propylene 40.O 40.0 40.O SO.O SO.O 45.0 SS.O VI. 1 Preparation of Compositions VI.1 to VI.52 carbonate Compositions VI.1 to VI.52 were prepared according to the VI.43 VI.44 VI.45 VI.46 VI.47 VI.48 VI.49 general methods A or Bas described in II.1. The amounts of 10 amidraZone I 1.O.O. 10.O 200 10.0 - active ingredient (either amidraZone I or II), Solvent, and amidraZone II - 10.O. 10.0 1O.O blockcopolymer are given in table 16 in parts by weight. blockcopolymer P' – 30.0 blockcopolymer Pt TABLE 16 blockcopolymer P* 17.5 20.O 200 10.0 - 3O.O blockcopolymer P” 17.5 15.O 20.0 10.0 30.0 VI.1. VI. 2 VI.3 VI.4 VI.5 VI.6 VI.7 15 Y-butyrolactone propylene SS.O SS.O 40.O 70.O 6O.O 6O.O 6O.O amidraZone I 10.7 10.7 - — 11.0 carbonate amidraZone II - 10.7 10.7 10.3 - 11.0 blockcopolymer P' 8.0 — 8.0 — — 10.0 10.0 VI.43 VI.44 VI.45 VI.46 VI.47 VI.48 VI.49 blockcopolymer P 11.5 10.2 11.5 10.2 - 7.0 7.0 blockcopolymer P O.8 0.7 O.8 O.7 3O.O 1.O 1.O amidraZone I blockcopolymer P” 7.1 — 7.1 — amidraZone II 1.O.O. 10.O 100 10.0 10.O. 10.O 1 O.O Y-butyrolactone 69.O 71.3 69.O 71.3 71.O 71 blockcopolymer P' 6.0 15.0 24.0 — — — 6.O propylene — 59.7 — blockcopolymer Pt carbonate blockcopolymer P' 6.O 15.O 24.O 24.O blockcopolymer P” 24.O 15.O 6.O 24.O 15.O 6.O VI.8 VI.9 VI.10 VI.1.1 VI.12 VI.13 VI.14 Y-butyrolactone 25 propylene 6O.O 6O.O 6O.O 6O.O 6O.O 6O.O 6O.O amidraZone I 11.0 - 10.O 1 O.O. 10.O. 10.O 200 carbonate amidraZone II 11.0 blockcopolymer P' 1.O.O. 10.0 - 30.0 - 40.O VI.50 VI.51 VI.52 blockcopolymer P blockcopolymer P 1.0 1.0 30.0 – 40.0 — amidraZone I blockcopolymer P” 7.0 7.0 — 40.O 30 amidraZone II 1O.O 1O.O 1O.O Y-butyrolactone 71.O 71 blockoopolymer P' 1S.O 24.0 propylene - 6O.O 6O.O 6O.O 6O.O 40.O blockoopolymer P carbonate blockoopolymer P 1S.O 6.0 40 blockoopolymer P” VI.1S VI.16 VI.1.7 VI.18 VI.19 VI.20 VI.21 Y-butyrolactone 35 propylene 6O.O 6O.O SO.O amidraZone I 2O.O 100 10.O 20.O 100 10.O 1O.O carbonate amidraZone II biockcopolymer P' 40 3.0 Upon dilution with water (100 parts per 1 part of composition) the compositions of table 16 blookcopolymer P form bluish clear compositions. The diluted composition remain stable for at least 24 h. blookcopolymer P 40.O 3O.O 40.O 2O.O blockoopolymer P” — 20.0 — 27 VI.2 Biological Tests of Compositions VI Y-butyrolaotone 40 1. Adult Insect Vial Contact Assays Against Adult Male Ger propylene 40.O SO.O 6O.O 40.O 70.O 70.O 6O.O man Cockroach, Blattella germanica (Bg), House Fly, Musca carbonate domestica (Md), and Acrobat Ant, Crematogaster sp. (Cre): VI.22 VI.23 VI.24 VI.25 VI.26 VI. 27 VI. 28 Glass vials (20 ml scintillation vials) were treated with a solution, obtained by diluting composition VI.2 or VI.4 with amidraZone I 1.O.O. 10.O. 10.O 1 O.O. 10.O. 10.0 1O.O 45 water. Treatments were made by placing 445 ul of Solution amidraZone II into the bottom of each vial. Each vial was turned on its side blockcopolymer P' 6.O 9.0 12.O 150 18.0 21.0 24.0 blockcopolymer P and placed onto a commercial grade hot dog roller (APW/ blockcopolymer P Wyott HRS-31) without applying any heat. The vials were blockcopolymer P'" 24.O 21.O. 18.O 15.O. 12.O 9.0 6.O allowed to roll (6 rpm), uncapped, for ca. 40-60 minutes to Y-butyrolactone 50 allow treatment to completely coat the vial and allowed for propylene 6O.O 6O.O 6O.O 6O.O 6.O-O 6O.O 6O.O full drying of the water treatment. After drying, a small piece carbonate of cotton dental wick (ca. 5-7 mm wide), lightly moistened VI.29 VI.30 VI.31 VI.32 VI.33 VI.34 VI.35 with 10% sugar water, was placed into the bottom of each vial to supply food and moisture for the insects. Test vials were amidraZone I 1.O.O. 10.O. 10.O 1 O.O. 10.O. 10.O 200 55 held at room temperature (ca. 25° C.) and insects were amidraZone II blockcopolymer P' 27.O. 12.O. 16.O 20.O 24.O 28.0 12.0 observed for incapacitation at 4, 24, and 48 hours after treat blockcopolymer P ment. The results are given in table 17: blockcopolymer P' blockcopolymer P'" 3.0 28.0 24.O 20.0 16.O. 12.O 28.0 TABLE 17 Y-butyrolactone propylene 6O.O SO.O SO.O SO.O SO.O SO.O SO.O 60 Mean Percent Kd? carbonate Hours post Md Cre Bg VI.36 VI.37 VI.38 VI.39 VI.40 VI.41 VI.42 Treatment treatinent 1 ppm 1 ppm 5 ppm amidraZone I 2O.O 20.O 20.O 1 O.O. 10.O 15.O 1O.O VI.4 4 1OO 46.7 100 amidraZone II 65 24 1OO 50 100 blockcopolymer P' 16.O 20.O 24.O 20.0 - 48 1OO 46.7 100 US 8,741,324 B2 37 38 TABLE 17-continued be wet but still loose enough for easy transfer into tubes). The softwood samples (pine) were pre-washed to remove Mean Percent Kd residues of natural defensive chemicals. The softwood Hours post Md Cre Bg material was placed into a Buchner funnel (with filter Treatment treatinent 1 ppm 1 ppm 5 ppm paper) and water was added until sample was covered with VI.2 4 100 1OO 1OO standing water. The sample was allowed to soak for 30 min 24 100 1OO 1OO and then the water was drawn off with vacuum. Additional 48 100 1OO 1OO water as needed for required moisture content was added. Untreated 4 O O O 4. Test soil was prepared by drenching the Soil with a solution, 24 O O O 10 48 3.3 O 13.3 obtained by diluting composition VI.2 or VI.4 with water. The concentration of active ingredient in the soil is given in Test initiated Oct. 27, 2004 (Md, Cre), Oct. 26, 2004 (Bg). table 19. 'Mean is based on 6 insects per vial and 5 reps per treatment, 445 microliters trtvial. 5. The smooth (un-cut) end of each tube was pressed into the 2. Soil Exposure Assays Against Workers of Eastern Subter 15 poured agar to load a 1 cm agar plug into the tube. The plug ranean Termite, Reticulitermes flavipes. was pushed most of the way through the tube (approx.3 cm Test Arenas: from opposite end) with a wood dowel. Approx. 2 cm of Tests were conducted in 60x15 mm plastic Petri dishes. woodflour were loaded into the short end of the tube, a The bottom of each dish was coated with 2 ml agar. rubber stopper was inserted and then the contents were 100 g of Princeton Sandy Loam Soil was incorporated on a firmly packed against the stopper. weight-to-weight ratio of a.i. to Soil in a 100 ml Qorpak jar. 6. A 5 cm length from the top of the agar plug was marked. Incorporation consists of applying 7 ml of composition VI.2 The tube was held upright and loaded with pre-treated test or VI.4 diluted with water to the soil, and shaking the soil by soil to slightly above the 5 cm mark. The tube was lightly hand to mix lightly then rolling the jar on a commercial roller tapped on the counter top to compact the soil. Additional for 30 minutes. After the jar had finished rolling, it was shaken 25 soil was loaded and compacting step was repeated to fill the by hand again and allowed to air dry over night. 2 g of 5 cm length with loosely compacted soil. incorporated soil was added per dish. 15 worker termites were 7. Using a second tube, another agar plug was cut, transferred introduced into each dish, and a piece of filter paper (4x4 into the tube with soil and packed down against the soil to in.) was added to each dish and moistened with a drop of complete the column assembly. distilled water for a food source. Mortality (dead), moribund 8.30 termite workers were collected in a glass vial with 2 or (near death, unable to walk) and intoxicated (obviously 3 short strips of filter paper and transfered all to the top impaired, but able to walk) readings were recorded daily for chamber of the completed soil tube. The tube was capped 9 days. The results are given in table 18: with cork or rubber stopper and stored in upright position in TABLE 1.8 Mean cumulative 90 mortality at days after treatment (DAT 2 Rate ppm a.i. Treatment' (wfw) 1 DAT 2 DAT 4 DAT SDAT 7 DAT 9 DAT VI.2 5 93.3 1OO.O VI.2 10 1OOO VI.4 5 32.O 40.O 64.O 66.7 69.3 80.0 W.4 10 82.7 93.3 1OOO Termidor SC O.S 4.0 813 1OOO Untreated Control O.O 1.3 1.3 2.7 4.0 4.0

Bioassay initiated O3 Now, 2004, *Each mean is based on 75 termites (5 replications/treatment). Commercial Suspension concentrate offipronil

3. Soil Tunneling Assays Against Workers of Eastern Subter 50 test tube racks. When testing with Formosan termites, the ranean Termite, Reticulitermes flavipes. tubes were infested with 30 workers+3 soldiers. To observe the tunneling response of subterranean termites Test Procedure: through treated soil arena tubes containing treated Soil were The completed tubes were stored under standard holding prepared as described below. Termites were placed at one end conditions and observed daily for penetration of tunnels of the tube and the tunneling subsequent mortality effects 55 through the soil columns. Daily progress through the Soil can were evaluated. be marked directly on the tube and measured later (see sample Arena Preparation— data array). Instinctive behavior for termites will be to imme 1. Tests were run in 1.5 cm diameter, transparent tubes (PVC diately start tunneling downward for shelter and termites will tubes) which were cut at one end to a length of 13 to 14 cm. usually penetrate through an untreated soil column in 24 to 48 Any sharp points formed where the tube was cut were 60 hrs. Failure to penetrate into the soil column could be the trimmed. result of repellent treatment in the soil or rapid toxicity. 2.5% agar was prepared and poured into glass Petri dishes to The tubes were examined at 3 and 6 days for number of a depth of 1 cm. surviving termites. The contents of each tube were emptied 3. A quantity of wood flour was prepared for use as an attrac onto a metal tray So that it could be spread out for easier tive food source at the bottom of the tunnel tubes. The 65 location of surviving termites. The survivors were observed hardwood samples will only require addition of enough for symptoms of intoxication or moribundity and recorded on water to thoroughly moisten the woodflour (sample should the data sheet. If the Survivors show no sign of intoxication US 8,741,324 B2 39 40 they were recorded as normal (“norm” on datasheet). Dead tion of the bait material. A water soaked dental wick was termites were usually not found due to rapid deterioration of provided during the starvation period. The water soaked den the bodies in contact with the soil. Any termites not accounted tal wick was removed upon the introduction of the bait solu for through direct observation were considered to be dead. tion. Test dishes were covered with the dish cover to maintain The number dead recorded on datasheet were determined humidity, and maintained in laboratory (22°C.) and observed from the number of termites “not found plus any dead bodies for mortality and intoxicating effects for 5 days. directly observed. The results are given in tables 19a and 19n: Formulation VI.4 resulted in 100% mortality by 3 DAT. Formulation VI.2 resulted in 100% mortality by 5 DAT. TABLE 19 6. Roach Bait No-Choice Assays Against Adult Male German 10 Cockroach, Blattella germanica. Dead intoxicated (Mean 96 Test Arenas: Grease (3 parts petroleum jelly Vaseline}, and 2 parts VI.4 VI.2 Control mineral oil) were placed on the top 3-4 cm of clear plastic 0.5 ppm 0.5 ppm (untreated) Rubbermaid containers measuring 20 LX21 Wx12 H cm to 3 DAT 64 O 71 O O O 15 prevent the insects from escaping. Water was provided with a 6 DAT 96 O 100 O O O 4-dram glass vial with a dental wick half inserted into the vial. The vial was placed on its side to allow easy access for the roaches. The vial was refilled with water every 3-4 days. TABLE 1.9b Bait was prepared using ground catchow and composition VI.2 or VI.4 was incorporated on a weight-to-weight ratio of Tunneling in cm (Mean 90 a.i. to chow. For each treatment, a total of 1 gram of treated VI.4 VI.2 Control chow was prepared using a total Volume of 1 ml of diluted 0.5 ppm 0.5 ppm (untreated) composition to completely wet the chow with each rate of compound. The roaches were placed intest arenas and starved 3 DAT 4.6 4.6 S.O 25 for 24 hours prior to bait introduction, with a water source at 6 DAT S.O S.O S.O all times. Treatments were replicated three times. The amount Termite tunneling was not affected by formulation type; i.e., they were all non-repellent. of treated chow for each arena was weighed out to approxi All formulations resulted in similar mortality at 3 DAT and 6 DAT mately 0.03 grams, and placed in a plastic weigh boat (45 4. Soil Surface Applied Contact Assays Against Argentine mmx45mm). Arenas were placed in the laboratory (22°C.) 30 and covered with blotter paper. Mortality was observed for 3 Ant, Iridomyrmex humilis. days. Test Arenas: Both formulations resulted in 100% mortality by 3 DAT. Tests were conducted in 100x20 mm polystyrene Petri dish. The inner sides of the dishes were painted with Fluon We claim: (Northern Products, Woonsocket, R.I.) to prevent ant escape. 35 1. A liquid pesticide concentrate composition, which com Test arenas were prepared by dispensing a thin layer of 1% prises: agar into the dishes and then spreading 10 g of Princeton a) 1 to 60% by weight, based on the total weight of the Sandy Loam Soil over the agar. composition, of at least one organic pesticide compound Test treatments were applied as Solutions, obtained by Chaving a water solubility of not more than 5 g/l at 25° diluting composition VI.2 or VI.4 with water. The solutions 40 C./1013 mbar, were sprayed (a 1 gal/1000 ft with a DeVilbiss atomizer. b) 10 to 80% by weight, based on the total weight of the Dish covers were used to conserve moisture and additional composition, of at least one organic solvent S having a water added as needed. A Small cotton dental wick was placed water solubility of at least 10 g/l at 25°C/1013 mbar, in each arena soaked with 20% sucrose solution for food and and which is capable of dissolving the pesticide com water source for the duration of test. 15 ants were placed in 45 pound C. each dish, and each treatment was replicated three times. Test c) from 15 to 50% by weight, based on the total weight of dishes were maintained in the laboratory (22° C.) and the composition, of at least one non-ionic blockcopoly observed for mortality daily for 5 to 10 days. mer P comprising at least one polyethyleneoxide moiety All formulations performed equally and VI.4 resulted in PEO and at least one polyether moiety PAO consisting of 100% mortality by 2 DAT while formulation VI.2 resulted in 50 repeating units derived from C-Co-alkyleneoxides 100% mortality at 3 DAT. and/or styrene oxide, wherein the non-ionic blockco 5. Ant Bait No-Choice Assays Against Argentine Ant, Iri polymer P is characterized by an HLB-value ranging domyrmex humilis. from 5 to 20, and wherein the non-ionic blockcopolymer Test Arenas: has a number average molecular weight My ranging Tests were conducted in 100x20 mm Petri dishes. The 55 from 1,000 to 100,000 Dalton; inner sides of the dishes were painted with Fluon (Northern d) optionally from 0.1 to 10% by weight, based on the total Products, Woonsocket, R.I.) to preventant escape. Baits were weight of the composition, of one or more non-poly mixed with a 40% honey/water solution. For honey/water meric Surfactants, incorporation, a stock solution containing 40% by weight of e) wherein the weight ratio of the non-ionic blockcopoly honey in distilled water was prepare. 60 merto the organic pesticide compound P:C is from 0.6:1 For each treatment, compositions VI2. or VI.4 were diluted to 10:1 and wherein the components a), b), c) and option with water and then add to the honey water solution to bring ally d) make up at least 95% of the composition, pro the final solution up to the desired concentration of active vided that if water is present in the composition, the ingredient and 40% honey water. For each test arena, 0.2 ml of weight ratio of water to solvent S does not exceed 1:5. treated honey water Solution was applied to a micro weigh 65 2. The composition as claimed in claim 1, wherein the dish to hold the bait material. 15 ants were introduced into non-ionic blockcopolymer has a number average molecular each test arena dish, starved for 24 hours before the introduc weight My ranging from 2,500 to 50,000 Dalton. US 8,741,324 B2 41 42 3. The composition as claimed in claim 1, wherein the PEO 11. The composition as claimed in claim 8, wherein the and the PAO moieties make up at least 80% by weight of the pesticide compound C is a fungicide compound. non-ionic blockcopolymer P. 12. An aqueous pesticide composition, which is obtained 4. The composition as claimed in claim 1, wherein the by dilution with water of a liquid pesticide concentrate com weight ratio of PEO moieties to PAO moieties in the non position as defined in claim 1, the dilution being at least 10 ionic blockcopolymer ranges from 1:10 to 10:1. parts of water per 1 part of the liquid pesticide concentrate 5. The composition as claimed in claim 1, wherein the composition. non-ionic blockcopolymer is selected from the group of poly 13. The composition as claimed in claim 12, wherein the mers having the following formulae P1 to P5: non-ionic blockcopolymer and the at least one organic pesti 10 R PEO O PAO R2 P1 cide compound C form droplets having an average diameter, determined by dynamic light scattering method, from 10 to R-PAO-O-PEO-H P2 300 nm. 14. A method of combating organisms that are harmful to R PEO PAO NR PAO' PEO' R' P3 15 plants, which comprises contacting said harmful organisms, their habit, breeding ground, food Supply, plant, seed, soil. area, material or environment in which the harmful organisms R PEO PAO (O-A)-O-PAO' PEO' R' P4 are growing or may grow, or the materials, plants, seeds, soils, Surfaces or spaces to be protected from attack or infestation R PEO PAO NR-A'-NR PAO'-PEO' R' P5 by harmful organisms with an effective amount of a compo wherein n is 0 or 1, sition as claimed in claim 12. A., A'area bivalent organic radical which has 2 to 20 carbon 15. A method of combating organisms that are harmful to atoms and which may carry 1 or 2 hydroxy groups and/or plants, which comprises contacting said harmful organisms, 1, 2, 3 or 4 ether moieties and which may also carry 1 or their habit, breeding ground, food Supply, plant, seed, soil. 2 radicals of the formula R PEO PAO – 25 area, material or environment in which the harmful organisms PAO, PAO' are hydrophobic polyether moieties PAO as are growing or may grow, or the materials, plants, seeds, soils, defined in claim 23, Surfaces or spaces to be protected from attack or infestation PEO, PEO' are polyethyleneoxide moieties, by harmful organisms with an effective amount of a compo R is C-C alkyl or a radical R PEO PAO – sition as claimed in claim 13. R" is C-Co alkyl or C-Co alkylphenyl, 30 R. R. Rare each independently hydrogen, C-Cs alkyl, 16. A method for protecting crops from attack or infesta C-C alkylcarbonyl, or benzyl, and tion by harmful organisms which comprises contacting a crop R", Rare each independently hydrogen, C-Cs alkyl or a with an effective amount of a composition as claimed in claim radical R PEO PAO . 12. 6. The composition as claimed in claim 1, containing the 35 17. A method for protecting crops from attack or infesta compound C in an amount from 5 to 50% by weight, based on tion by harmful organisms which comprises contacting a crop the total weight of the composition. with an effective amount of a composition as claimed in claim 7. The composition as claimed in claim 1, comprising at 13. least one non-polymeric Surfactant in an amount from 0.1 to 18. A method for protecting seeds from attack or infesta 10% by weight, based on the total weight of the composition. 40 tion by harmful organisms which comprises contacting a seed 8. The composition as claimed in claim 1, wherein the with an effective amount of a composition as claimed in claim pesticide compound C is selected from fungicides, insecti 12. cides, acaricides, nematicides and herbicides. 19. A method for protecting seeds from attack or infesta 9. The composition as claimed in claim 8, wherein the tion by harmful organisms which comprises contacting a seed pesticide compound C is an insecticide compound. 45 with an effective amount of a composition as claimed in claim 10. The composition as claimed in claim 9, wherein the 13. insecticide compound C is selected from compounds of the 20. A liquid pesticide concentrate composition, compris formula A ing: a) 1 to 60% by weight, based on the total weight of the 50 composition, of at least one organic pesticide compound (A) Chaving a water solubility of not more than 5 g/l at 25° C./1013 mbar, b) 10 to 80% by weight, based on the total weight of the composition, of at least one organic solvent S having a 55 water solubility of at least 50 g/l at 25°C/1013 mbar, and which is capable of dissolving the pesticide com pound C. c) from 15 to 50% by weight, based on the total weight of the composition, of at least one non-ionic blockcopoly 60 mer P comprising at least one polyethyleneoxide moiety PEO and at least one polyether moiety PAO consisting of repeating units derived from C-Co-alkyleneoxides wherein R'' and R'' are each independently hydrogen, and/or styrene oxide, wherein the weight ratio of PEO halogen, CN, moieties to POA moieties in the non-ionic blockcopoly C-C alkyl, C-C alkoxy, C-C haloalkyl or C-C, 65 mer ranges from 3:7 to 7:3, and wherein the non-ionic haloalkoxy and R' is blockcopolymer has a number average molecular C-C alkoxy, C-C haloalkyl or C-Chaloalkoxy. weight My ranging from 2,500 to 100,000 Dalton; and US 8,741,324 B2 43 44 d) optionally from 0.1 to 10% by weight, based on the total c) from 15 to 50% by weight, based on the total weight of weight of the composition, of one or more non-poly the composition, of at least one non-ionic blockcopoly meric surfactants, mer P comprising at least one polyethyleneoxide moiety e) wherein the weight ratio of the non-ionic blockcopoly PEO and at least one polyether moiety PAO consisting of mer to the organic pesticide compound P:C is from 0.6:1 repeating units derived from C-Co-alkyleneoxides to 10:1 and wherein the components a), b), c) and option and/or styrene oxide, wherein the weight ratio of PEO ally d) make up at least 95% of the composition, pro moieties to POA moieties in the non-ionic blockcopoly vided that if water is present in the composition, the mer ranges from 3:7 to 7:3, and wherein the non-ionic weight ratio of water to solvent S does not exceed 1:5. blockcopolymer has a number average molecular 21. The composition as claimed in claim 20, wherein the 10 weight My ranging from 2,500 to 100,000 Dalton; and non-ionic blockcopolymer has a number average molecular d) optionally, comprising less than 0.1% non-polymeric weight My ranging from 2,500 to 50,000 Dalton. Surfactant, based on the total weight of composition, 22. The composition as claimed in claim 20, wherein the e) wherein the weight ratio of the non-ionic blockcopoly PEO and the PAO moieties make up at least 80% by weight of merto the organic pesticide compound P:C is from 0.6:1 the non-ionic blockcopolymer P. 15 23. The composition as claimed in claim 20, wherein the to 10:1 and wherein the components a), b), c) and option pesticide compound C is selected from fungicides, insecti ally d) make up at least 95% of the composition, pro cides, acaricides, nematicides and herbicides. vided that if water is present in the composition, the 24. The composition as claimed in claim 20, wherein the weight ratio of water to solvent S does not exceed 1:5. pesticide compound C is selected from an insecticide com 27. The composition as claimed in claim 26, wherein the pound. non-ionic blockcopolymer has a number average molecular weight My ranging from 2,500 to 50,000 Dalton. 25. The composition as claimed in claim 20, wherein the 28. The composition as claimed in claim 26, wherein the insecticide compound C is selected from compounds of the PEO and the PAO moieties make up at least 80% by weight of formula A the non-ionic blockcopolymer P. 25 29. The composition as claimed in claim 26, wherein the (A) pesticide compound C is selected from fungicides, insecti cides, acaricides, nematicides and herbicides. 30. The composition as claimed in claim 26, wherein the pesticide compound C is selected from an insecticide com 30 pound. 31. The composition as claimed in claim 26, wherein the insecticide compound C is selected from compounds of the formula A

35

(A) wherein R'' and R'' are each independently hydrogen, halogen, CN, C-C alkyl, C-C alkoxy, C-C, 40 haloalkyl or C-C haloalkoxy and R' is C-C alkoxy, C-C haloalkyl or C-Chaloalkoxy. 26. A liquid pesticide concentrate composition, compris 1ng: a) 1 to 60% by weight, based on the total weight of the 45 composition, of at least one organic pesticide compound Chaving a water solubility of not more than 5 g/l at 25° C./1013 mbar, b) 10 to 80% by weight, based on the total weight of the wherein R'' and R'' are each independently hydrogen, composition, of at least one organic solvent S having a 50 halogen, CN, C-C alkyl, C-C alkoxy, C-C, water solubility of at least 50 g/l at 25°C/1013 mbar, haloalkyl or C1-C4 haloalkoxy and R' is C-C alkoxy, and which is capable of dissolving the pesticide com C-C haloalkyl or C-Chaloalkoxy. pound C,