WO2006002984A1 - Liquid pesticide compositions - Google Patents
Liquid pesticide compositions Download PDFInfo
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- WO2006002984A1 WO2006002984A1 PCT/EP2005/007256 EP2005007256W WO2006002984A1 WO 2006002984 A1 WO2006002984 A1 WO 2006002984A1 EP 2005007256 W EP2005007256 W EP 2005007256W WO 2006002984 A1 WO2006002984 A1 WO 2006002984A1
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present invention relates to liquid pesticide compositions which comprise at least one organic pesticide compound that is sparingly or even insoluble in water and which upon dilution with water form stable aqueous nanoparticulate formulations.
- the invention also relates to aqueous pesticide compositions which are obtained by diluting the non-aqueous pesticide compositions of the invention with water and to their use for plant protection.
- a pesticide compound hereinafter also referred to as active ingredient, is usually applied in the form of a dilute aqueous composition in order to achieve a good interaction with the target organisms, such as plants, fungi and insects.
- active ingredients that are used as pesticides are only sparingly or even insoluble in water, i.e. they usually have a water-solubility of not more than 1 g/l, often not more than 0.5 g/l and particularly not more than 0.1 g/l at 25°C/1013 mbar. Therefore, formulators are often confronted with difficulties in formulating pesticide compounds in stable formulations that can be easily diluted with water and that deliver maximum loading of the active ingredient per unit volume to the end user.
- Pesticides having a low solubility in water are often formulated as aqueous suspension concentrate (SC) which can be diluted with water for use in the field.
- SC aqueous suspension concentrate
- Suspension concentrates are formulations, wherein the active ingredient is present in the form of finely divided solid particles, which are suspended in an aqueous dispersing medium utilizing surface-active compounds, such as wetting agents, dispersants and rheological or suspending aids for stabilising the active ingredient particles in the dispersing medium.
- SCs the particles of the active ingredient usually have particle sizes in the range of 1 to 20 ⁇ m. Even smaller particle sizes, i.e. ⁇ 1 ⁇ m, e.g. 0.5 to ⁇ 1 ⁇ m, can be obtained by elaborate grinding techniques.
- EC emulsifyable concentrates
- EC water-insoluble active ingredients
- EC emulsifyable concentrates
- EC water- immiscible solvent
- surface-active ingredients EC's
- EC's are usually stable solutions that can be diluted with water to form a milky oil-in-water emulsion, containing the active ingredient dissolved in the solvent droplets.
- EC formulations have a considerable drawback in that they contain considerable amounts of volatile organic solvents which are not entirely satisfactory with regard to their ecological and toxicological properties.
- EC's are limited to pesticide compounds which are soluble in water-immiscible solvents. As a result of the large particle size of the solvents droplets, the bioefficacy of the active ingredient is sometimes not satisfactory.
- WO 92/10937 suggests a pesticide concentrate which comprises a solid water- insoluble pesticide compound and a dispersant which is solubilized in a water-miscible solvent in order to overcome the problems associated with SCs and EC's.
- these formulations Upon dilution with water, these formulations form a suspension of finely divided active ingredient particles.
- the active ingredient is often rapidly precipitated as coarse crystals giving both application problems, such as spray filter or nozzle blockage and poor or inconsistent bioefficacy.
- loading of these compositions with an active ingredient is poor and the particle size of the active ingredient after dilution with water is not entirely satisfactory.
- WO 03/037084 describes a similar concentrated pesticidal solution which comprises one or more water-insoluble pesticide compounds and lignin dissolved in a water- miscible, polar solvent. Depending on the active ingredients choice, it may be rapidly precipitated giving coarse crystalline particles. Thus the active ingredients have inconsistent bioefficacy and application problems are likely to occur.
- WO 02/45507 describes a concentrate composition of a hydrophobic pesticide compound, wherein the active ingredient and at least one surfactant are dissolved in a solvent system comprising hydrophobic, water insoluble alkylalkanoates as a first solvent and polyhydric alcohols or condensates of polyhydric alcohols as a second solvent.
- the compositions require a hydrophobic, water insoluble solvent which is undesirable.
- the formulation Upon dilution with water, the formulation should form a stable aqueous composition of the active ingredient, wherein the average particle size of the dispersed material should not exceed 0.5 ⁇ m, preferably 300 nm and in particular 200 nm. Moreover, the formulation should not form coarse material upon dilution with water and the active ingredient should be stable in the liquid concentrate formulation upon prolonged storage or storage at elevated temperatures. Moreover, the aqueous composition which is obtained by dilution of the liquid concentrate composition should be stable against formation and/or separation of coarse material for at least 12 h.
- liquid pesticide concentrate composition which comprises
- At least one organic pesticide compound C having a water solubility of not more than 5 g/l, in particular of not more than 1 g/l at 25°C/1013 mbar
- at least one organic solvent S having a water solubility of at least 10 g/l at
- the weight ratio of the non-ionic blockcopolymer to the organic pesticide compound P:C is from 0.6:1 to 10:1 and wherein the components a), b), c) and optionally d) make up at least 95 % of the composition.
- compositions of the invention are stable against formation of solids upon storage and can be easily diluted with water without the formation of coarse material.
- the formulation can be loaded with active ingredients in amounts up to 60 % by weight.
- chemical degradation of some active ingredients having chemically labile groups such as hydrazones, semicarbazones, urethanes, sulfonyl ureas, amidosulfonylamides, oxime ethers, phosphonic esters, phosphate esters, and the like is decreased in comparison with other solvent based concentrate formulations.
- the compositions of the present invention Upon dilution with water, the compositions of the present invention form a bluish or even clear emulsion or dispersion, indicating that the droplets/solids dispersed therein are of very small size, the average particle diameter not exceeding 300 nm, preferably not exceeding 200 nm.
- the average particle diameter as referred herein, are weight average particle diameters which can be determined by dynamic light scattering. A skilled person is familiar with these methods which are e.g. described in H. Wiese (D. Distler, Ed.), Aqueous Polymer Dispersions (Wassrige Polymerdispersionen), Wiley-VCH 1999, Chapter 4.2.1 , p. 40ff, and the literature cited therein; H. Auweter, D. Horn, J.
- the aqueous compositions that are obtained by diluting the liquid pesticide compositions with water, have enhanced physical stability, i.e. the formation of solids during dilution and after 24 h after dilution is not observed. Moreover chemical degradation in the diluted compositions of labile active ingredients such as sulfonyl ureas, hydrazones and the like, e.g. by hydrolysis, is decreased.
- liquid compositions result in an improved biological performance of the active ingredients.
- the liquid compositions comprise at least one non-ionic blockcopolymer P, which comprises at least one and preferably at least two polyethyleneoxide moiety PEO and at least one poly-C 3 -C 4 -alkyleneoxid moiety PAO.
- the non-ionic blockcopolymers usually make up from 10 to 80 % by weight, preferably 15 to 50 % by weight and in particular 20 to 50 % by weight of the non-aqueous composition according to the invention.
- the weight ratio of non-ionic blockcopolymer P to pesticide compound C is preferably from 0.8:1 to 5:1 more preferably from 0.9:1 to 4:1 , and in particular from 1 :1 to 3:1.
- the PAO moiety in the non-ionic blockcopolymer P usually comprises at least 3, preferably at least 5, in particular 10 to 100 repeating units (number average) which are derived from C 3 -C 10 alkyleneoxides, such as propyleneoxide, 1 ,2-butyleneoxide, cis- or trans-2,3-butyleneoxide or isobutyleneoxide, 1 ,2-pentenoxide, 1 ,2-hexene oxide, 1 ,2-decene oxide or styrene oxide.
- C 3 -C 10 alkyleneoxides such as propyleneoxide, 1 ,2-butyleneoxide, cis- or trans-2,3-butyleneoxide or isobutyleneoxide, 1 ,2-pentenoxide, 1 ,2-hexene oxide, 1 ,2-decene oxide or styrene oxide.
- the PAO moieties can be described by the general formula (-O-CHR x -CHR y ) q , wherein q is the number of repeating units in the PAO moiety, R x and R y are independently selected from C 1 -C 8 alkyl and hydrogen, provided that at least one of the radicals R x , R y is different from hydrogen and the total number of carbon atoms of R x and R y in one repeating unit is from 1 to 8.
- One of the radicals R x or R y may also be a phenyl radical while the other is hydrogen.
- the repeating units in the PAO moiety are derived from C 3 -C 4 alkyleneoxides.
- the PAO moieties comprise at least 50 % by weight and more preferably at least 80 % by weight of repeating units derived from propyleneoxide. If the PAO moiety comprises different repeating units, these different repeating units may be arranged statistically or preferably blockwise.
- the PEO moieties of the non-ionic blockcopolymer P usually comprise at least 3, preferably at least 5, and more preferably at least 10 repeating units derived from ethyleneoxide (number average).
- the PEO moiety can be described by the general formula (CH 2 -CH 2 -O) P , wherein p is the number of repeating units within the PEO moiety.
- the total number of ethyleneoxide repeating units and repeating units in the PAO moiety or moieties will usually be in the range from 20 to 2,000, preferably 40 to 1 ,000 and in particular 65 to 450 (number average).
- the non-ionic blockcopolymers P those are preferred which have a number average molecular weight MN ranging from 1 ,000 to 100,000 Dalton, preferably from 2,000 to 60,000 Dalton, more preferably from 2,500 to 50,000 Dalton and in particular from 3,000 to 20,000 Dalton.
- the weight ratio of PEO moieties and PAO moieties (PEO: PAO) in the non-ionic blockcopolymer usually ranges from 1 : 10 to 10:1 , preferably from 1 : 10 to 2:1 , more preferably from 2:8 to 7:3 and in particular from 3:7 to 6:4.
- blockcopolymers P those are preferred which have a HLB-value ranging from 5 to 20 and in particular from 7 to 18.
- Preferred blockcopolymers for use in the compositions of the invention can be described by the following formulae P1 to P5:
- PAO 1 PAO' are PAO moieties as defined above, in particular poly-C 3 -C 4 -alkylenoxide moieties,
- R is C 1 -C 20 alkyl or a radical R 2 -PEO-PAO-
- R a , R b are each independently hydrogen, C 1 -C 8 alkyl or a radical R 2 -PEO-PAO-.
- R 1 and R 2 in formulae P1 and P2 are preferably C 1 -C 2O alkyl and in particular C 1 -C 8 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, isodecyl, 3-propylhexyl and the like.
- R 2 in formula P1 is preferably hydrogen.
- R 3 and R 4 in formulae P3, P4 and P5 are preferably hydrogen.
- R in formula P3 is preferably C 1 -C 20 alkyl, in particular C 4 -C 20 alkyl.
- C 2 -C 20 alkandiyl wherein 1 , 2, 3 or 4 CH 2 -moieties may be replaced by oxygen or sulfur, e.g. ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, hexane-1 ,4-diyl, 3-oxapentane-1 ,5-diyl, 3-oxahexane-1 ,6-diyl, 4-oxaheptane-1 ,7-diyl, 3,6-dioxaoctane-1 ,8-diyl, 3,7-dioxanonane-1 ,9-diyl and 3,6,9-trioxaundecan-1 ,11-diyl.
- cycloaliphatic radicals A, A' comprise C 5 -C 8 -cycloalkane-diyl and
- Examples for mixed aliphatic/cycloaliphatic radicals A, A' comprise methylcyclohexane- 1 ,7-diyl, 4,4'-[bis(cyclohexyl)methane]diyl, 4,4'-[2,2-bis(cyclohexyl)propane]diyl and the like.
- Preferred radicals A 1 A' are selected from C 2 -C 20 alkandiyl, wherein 1 , 2, 3 or 4 CH 2 -moieties may be replaced by oxygen.
- non-ionic blockcopolymers of formulae P1 to P5 those of formulae P2 and P4 are especially preferred.
- non-ionic blockcopolymer P a single type of non-ionic blockcopolymer P or different types of blockcopolymers P may be used.
- the non-aqueous liquid pesticide composition comprises at least 2, e.g. 2, 3 or 4 different types of non- ionic blockcopolymers P.
- Different types means that the blockcopolymers are distinct with regard to at least one of the following features: molecular weight, weight ratio of PEO to PAO, the HLB-value or the molecular architecture.
- at least one of the blockcopolymers combines at least two of the preferred features.
- the blockcopolymer P that combines at least two of the preferred features makes up at least 20 % by weight, preferably at least 30 % by weight, e.g. 20 to 90 % by weight, in particular 30 to 80 % by weight of the total amount of blockcopolymer P in the composition.
- polyhydric alcohols such as ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, neopentyl glycol, pinacol, pentanediols, hexane diols, glycerol, sorbitol and the like;
- alkylene glycol monomethyl ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and technical mixtures such as Carbitols, Cellosolves, Dowanols, Jefferols, Ektasolves, and the like;
- cyclic ethers which may contain an OH group such as tetrahydrofuran, pyran, dioxan, tetrahydrofurfurol;
- lactones having from 3 to 8 C-atoms, such as ⁇ -propiolactone, ⁇ -butyrolactone, • carbonates, in particular dimethylcarbonat, diethylcarbonat and 2-Oxa-1 ,3-dioxolan (ethylene carbonate) and 2-oxa-1 ,3-dioxan (propylene carbonate);
- C 2 -C 4 -alkanolamines, C 2 -C 4 -dialkanolamines and C 2 -C 4 -trialkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-methylaminoethanol,
- -C 4 -alkylesters of formic acid or acetic acid such as methyl formiate, ethyl formiate, methyl acetate, ethyl acetate, n-propyl acetate isopropyl acetate and the like; • heterocyclic aromatic or aliphatic amines having preferably from 2 to 6 carbon atoms, 1 or 2 nitrogen atoms and optionally 1 or 2 further heteroatoms selected from O and S, such as pyrrole, pyridine, picoline, morpholine, piperidine, piperazine,
- heterocyclic aldehydes such as furfural
- lactames having preferably from 3 to 6 carbon atoms and their N-methyl
- N-ethyl derivatives such as pyrrolidin-2-one, N-methylpyrrolidin-2-one, N-ethylpyrrolidin-2-one, etc.
- compositions of the invention also comprise at least one organic pesticide compound C which is sparingly soluble or insoluble in water.
- the solubility is below 0.5 g/l and in particular below 0.1 g/l at 25°C and 1013 mbar.
- the pesticide compound C can be selected from each group of active ingredients which are used to protect plants/crops from attack or infestation by harmful organisms, i.e. the pesticide compound can be selected from acaricides, algicides, antecedents, aricides, bactericides, bird repellents, chemosterilans, fungicides, herbicides, herbicide safeners, insect attractants, insect repellents, insecticides, mammal repellents, mating disrupters, moluscicides, nematicides, plant activators, plant growth regulators, rhodenticides, synergists, virucides and other compounds with exert an action on the plants to be protected and/or against the harmful organism.
- the pesticide compound can be selected from acaricides, algicides, antecedents, aricides, bactericides, bird repellents, chemosterilans, fungicides, herbicides, herbicide safeners, insect attractants, insect repellent
- Suitable pesticide compounds C which act as fungicides are for example:
- acylalanine such as benalaxyl, metalaxyl, ofurace, oxadixyl
- amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph;
- anilinopyrimidine such as pyrimethanil, mepanipyrim or cyrodinyl
- azoles such as bitertanol, bromoconazol, cyproconazole, difenoconazol, dinitroconazol, epoxiconazol, fenbuconazol, fluquiconazol, flusilazol, flutriafol, hexaconazol, imazalil, ipconazol, metconazol, myclobutanil, penconazol, propiconazol, prochloraz, prothioconazol, tebuconazol, tetraconazol, triadimefon, triadimenol, triflumizol, triticonazol;
- dichlorophenyl dicarboximides such as chlozolinate, dichlozoline, isovaledione, iprodion, myclozolin, procymidon, vinclozolin; • dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamat, thiram, ziram, zineb;
- heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fuberidazoles, flutolanil, furametpyr, isoprothiolanes, mepronil, nuarimol, picobezamid, probenazoles, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam; thiabendazole, thifluzamid, thiophanat-methyl, tiadinil, tricyclazoles, triforine;
- nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal- isopropyl
- phenylpyrroles such as fenpiclonil and fludioxonil
- non-classified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin-acetat, fenoxanil, ferimzones, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzol, metrafenon, pencycuron, propamocarb, phthalides, toloclofos-methyl, quintozenes, zoxamid;
- strobilurines e.g. the compounds disclosed in WO 03/075663 by the general formula I, such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;
- sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
- amido fungicides such as cyclofenamid and
- pesticides compounds C which act as herbicides or herbicide safeners comprise
- • 1 ,3,4-thiadiazoles such as buthidazoles und cyprazoles; • amides, such as allidochlor, benzoylpropethyl, bromobutide, chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid, flampropmethyl, fosamin, isoxaben, metazachlor, monalide, naptalame, pronamid, propanil;
- aminophosphoric acids such as bilanafos, buminafos, glufosinateammonium, glyphosates, sulfosates
- aminotriazoles such as amitrol, anilide, anilofos, mefenacet
- aryloxyalkanoic acids such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, dichlorprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamides, napro-panilides, triclopyr, and the CrC 8 -alkyl esters, e.g. the ethyl or butyl esters, the esters, e.g. the 2-ethoxyethyl esters or 2-butoxyethyl esters, and the mono-, di- and M-C 1 -
- C 8 -alkyl ammonium salts in particular the triethyl ammonium salts of aryloxyalkanoic acids
- benzoic acids such as chloramben, dicamba and the CrC 8 -alkyl esters, e.g. the ethyl or butyl esters, the CrC 4 -alkoxy-CrC 4 -alkyl esters, e.g. the 2- ethoxyethyl esters or 2-butoxyethyl esters, and the mono-, di- and tri-CrC 8 -alkyl ammonium salts, in particular the triethyl ammonium salts of benzoic acids;
- bleachers such as clomazone, diflufenican, fluorochloridones, flupoxam, fluridone, pyrazolates, sulcotrione; • carbamates, such as carbetamid, chlorbufam, chlorpro-pham, desmedipham, phenmedipham, vernolate;
- dichloropropionic acids such as dalapon
- dihydrobenzofuranes such as ethofumesates
- dihydrofuran-3-ones such as flurtamone
- dinitroanilines such as benefin, butralin, dinitramin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamines, profluralin, trifluralin, dinitrophenoles, such as bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, DNOC, minoterb-acetate;
- diphenylether such as acifluorfen-sodium, aclonifen, bifenox, chlornitrofen, difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;
- imidazoles such as isocarbamid
- imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazethabenz- methyl, imazethapyr, imazapic, imazamox;
- oxadiazoles such as methazole, oxadiargyl, oxadiazon
- oxiranes such as tridiphane
- phenoles such as bromoxynil, ioxynil
- phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxy-ethyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl; • phenylacetic acids and their esters, such as chlorfenac;
- ppi-active ingredients such as benzofenap, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimin;
- pyrazoles such as nipyraclofen
- pyridazines such as chloridazon, maleic hydrazide, norflurazon, pyridate
- pyridincarbonic acids such as clopyralid, dithiopyr, picloram, thiazopyr;
- pyrimidylethers such as pyrithiobac acid, pyrithiobac-sodium, KlH-2023, KIH-6127;
- sulfonamides such as flumetsulam, metosulam
- triazolcarboxamides such as triazofenamid
- uraciles such as bromacii, lenacil, terbacil
- urea herbicides such as benzthiazuron, cumyluron, cycluron, dichloralylurea, diflufenzopyr, isononuron, isouron, methabenzthiazuron, monisuron, noruron; • phenylurea herbicides, such as anisuron, buturon, chlorbromuron, chloreturon, chlorotoluron, choroxuron, daimuron, difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluothiuron, isoproturon, linuron, methiuron, methyldymron, metobenzuron, metobromuron, metoxuron, monolinuron, monuron, neburon, parafluron, phenobenzuron, siduron, tetrafluoron; • sulfonyl ureas, such as amidosulf
- plant protection active ingredients type cyclohexanone, such as ailoxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim.
- Most preferred herbicidal active ingredients type cyclohexenone are: tepraloxydim (see AGROW, no.
- pesticide compounds C which are useful as insecticides, acaricides, nematicides and/or miticides comprise:
- organophosphates such as acephates, azinphos-methyl, chlorpyrifos, chlorfenvinphos, diazinon, dichlorvos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoate, disulfoton, ethion, EPN, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoates, phosalones, phosmet, phosphamidon, phorates, phoxim, pirimiphos-methyl, profenofos, prothiofos, primiphos-ethyl, pyraclofos, pyridaphenthion, sulprophos, triazophos, trichlorfon;
- carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxarnyl, pirimicarb, propoxur, thiodicarb, triazamate;
- • pyrethroides such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin, permethrin;
- arthropodic growth regulators • arthropodic growth regulators: a) chitinsynthesis inhibitors, e.g. benzoyl ureas, such as chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists, such as halofenozide, methoxyfenozide, tebufenozide; c) juvenoides, such as pyriproxyfen, methoprenes, fenoxycarb; d) lipid biosynthesis inhibitors, such as spirodiclofen;
- chitinsynthesis inhibitors e.g. benzoyl ureas
- neonicotinoides such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nithiazin, acetamiprid, thiacloprid;
- insecticids are abamectin, acequinocyl, acetamiprid, amitraz, azadirachtin, bensultap, bifenazate, cartap, chlorfenapyr, chlordimeform, cyromazines, diafenthiuron, dinetofuran, diofenolan, emamectin, endosulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochlorid, gamma-HCH, hydramethylnon, imidacloprid, indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, nitenpyram, piperonylbutoxid, thiacloprid,
- R 11 and R 12 are each independently hydrogen, halogen, CN, C 1 -C 4 aikyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy and R 13 is C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy, e.g. the compound IV, wherein R 11 is 3-CF 3 and R 12 is 4-CN and R 13 is 4-OCF 3 (Metaflumizone);
- W is chlorine or trifluoromethyl
- X and Y are each independently chlorine or bromine
- R 21 is d-C ⁇ -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, or
- C 3 -C 6 -cycloalkyl which may be substituted with 1 to 3 halogen atoms, or C 2 -C 4 -alkyl which is substituted by C- ⁇ -C 4 -alkoxy;
- R 22 and R 23 are C r C 6 -alkyl or may together with the carbon atom, to which they are bound, form C 3 -C 6 -cycloalkyl which may be unsubstituted or substituted by 1 to 3 halogen atoms;
- R 24 is hydrogen or CrC 6 -alkyl
- R 21 is preferably CrC 4 -alkyl, in particular methyl or ethyl.
- R 22 and R 23 are preferably CrC ⁇ alkyl, in particular methyl, or R 22 and R 23 together with the carbon atom to which they are bound form a cyclopropyl ring, which may carry 1 or 2 chlorine atoms.
- R 24 is preferably C 1 -C 4 - alkyl, in particular methyl.
- W is preferably trifluoromethyl.
- X and Y are preferably chlorine.
- Preferred examples are compounds of the formula B, wherein X and Y are chlorine, W is trifluoromethyl, R 22 , R 23 and R 24 are methyl and R 21 is methyl or ethyl as well as compounds of the formula B, wherein X and Y are chlorine, W is trifluoromethyl, R 22 and R 23 together with the carbon atom to which they are bound form a 2,2-dichlorocyclopropyl ring R 24 is methyl and R 21 is methyl or ethyl.
- R -CH 2 O CH 3 or H
- R -CF 2 CF 2 CF 3 ;
- plant growth regulators comprise gibberellines and oximes, such as ⁇ [(isopropylidene)amino]oxy ⁇ acetic acid-2-methoxy-2-oxoethyl ester, and also defoliants, such as thidiazuron, growth inhibitors, such as butralin, flumetralin, fluoridamid, prohydrojasmon, growth retardants, such as paclobutrazol, uniconazole, growth stimulators, such as brassinolide, forchlorfenuron and the like.
- gibberellines and oximes such as ⁇ [(isopropylidene)amino]oxy ⁇ acetic acid-2-methoxy-2-oxoethyl ester
- defoliants such as thidiazuron
- growth inhibitors such as butralin, flumetralin, fluoridamid, prohydrojasmon
- growth retardants such as paclobutrazol, uniconazole
- growth stimulators such as brassinolide
- compositions of the present invention are particularly useful for formulating pesticide compound C, which are selected from fungicides, insecticides, acaricides, nematicides and herbicides.
- the pesticide compound C comprises at least one insecticide compound.
- a particularly preferred embodiment relates to pesticide compositions which comprise a compound of formula A as the at least one organic pesticide compound C.
- a further particularly preferred embodiment relates to pesticide compositions which comprise a compound of formula B as the at least one organic pesticide compound C.
- the pesticide compound C comprises at least one fungicide compound.
- a pesticide composition which comprises at least one fungicide which is selected from strobilurines, such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, azol fungicides, in particular conazoles such as epoxyconazole, tebuconazole, triticonazole, fluquinconazole, flutriafol, metconazole, myclobutanil, cycproconazole, prothioconazole and propiconazole, boscalid, dichlorophenyl dicarboximides such as vinclozoline and 6- aryl-[1 ,2,4]triazolo[1 ,5-ajpyrimidines, e.g. those disclosed in WO 98/46608, WO 99/41255 and WO 03/
- strobilurines such as
- R x is a group NR 14 R 15 or linear or branched C 1 -C 8 alkyl, which may be unsubstituted or substituted by halogen, OH, CrC 4 alkoxy, phenyl or C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl, phenyl or naphthyl, wherein the 4 last-mentioned radicals may be unsubstituted or substituted by 1 , 2, 3 or 4 radicals, selected from halogen, OH, C r C 4 alkyl, C 1 -C 4 halogenalkoxy, C 1 -C 4 alkoxy and C 1 -C 4 halogenalkyl;
- R 14 , R 15 are each independently hydrogen, C 1 -C 8 alkyl, C 1 -C 8 halogenalkyl,
- R 14 and R 15 together with the nitrogen atom to which they are bound may also form a 5-, 6-, 7- or 8-membered heterocycle which may contain 1 , 2 or 3 additional heteroatoms selected from N, O and S, and which may carry one or more (e.g.
- radicals selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 -C 6 halogenalkyl, C 2 -C 6 alkenyl, C 2 -C 6 halogenalkenyl, C 1 -C 6 alkoxy, C 1 -C 6 halogenalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 halogenalkenyloxy, (exo)- ⁇ -C 6 -alkylen and OXy-C 1 -C 3 -alkylenoxy;
- L is selected from halogen, cyano, C 1 -C 6 alkyl, C 1 -C 4 halogenalkyl, C 1 -C 6 alkoxy, C 1 -C 4 halogenalkoxy and C 1 -C 6 alkoxycarbonyl;
- L 1 is halogen, C 1 -C 6 alkyl or C 1 -C 6 halogenalkyl and in particular fluorine or chloro;
- X is halogen, C 1 -C 4 alkyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 halogenalkyl and preferably halogen or methyl.
- Examples for compounds C are: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]- pyrimidine,
- the liquid composition contains no or less than 0.1 % by weight, based on the total weight of the composition, of a non- polymeric surfactant.
- non-polymeric surfactants comprise
- anionic surfactants selected from the salts, in particular the sodium, potassium calcium or ammonium salts of - alkylsulfonates, such as lauryl sulfonate, isotridecylsulfonate, alkylsulfates, in particular fatty alcohol sulfates, such as lauryl sulfate, isotridecylsulfate, cetylsulfate, stearylsulfate aryl- and alkylarylsulfonates, such as napthylsulfonate, dibutylnaphtylsulfonate, dodecyldiphenylether sulfonate, cumylsulfonate, nonylbenzenesulfonate, dodecylbenzene sulfonate; sulfonates of fatty acids and fatty acid esters; sulfates of fatty acids and fatty acid esters; sulfates
- non-ionic surfactants selected from the group of ethoxylated alkanoles, in particular ethoxylated fatty alcohols and ethoxylated oxoalcohols, such as ethoxylated lauryl alcohol, ethoxylated isotridecanol, ethoxylated cetyl alcohol, ethoxylated stearyl alcohol, and esters thereof, such as acetates ethoxylated alkylphenols, such as ethoxylated nonylphenyl, ethoxylated dodecylphenyl, ethoxylated isotridecylphenol and the esters thereof, e.g.
- ethoxylated alkanoles in particular ethoxylated fatty alcohols and ethoxylated oxoalcohols, such as ethoxylated lauryl alcohol, ethoxylated isotridecanol, ethoxylated cety
- alkylglucosides and alkyl polygucosides - ethoxylated alkylglucosides, ethoxylated fatty amines, ethoxylated fatty acids, partial esters, such as mono-, di- and triesters of fatty acids with glycerine or Sorbitan, such as glycerine monostearate, sorbitanmonooleat, sorbitantristearat ethoxylated esters of fatty acids with glycerine or sorbitan, such as ethoxylated glycerine monostearate ethoxylates of vegetable oils or animal fats, such as corn oil ethoxylate, castor oil ethoxylate, tallow oil ethoxylate, - ethoxylates of fatty amines, fatty amides or of fatty acid diethanolamides
- cationic surfactants selected from the group of quaternary ammonium compounds, in particular alkyltrimethylammonium salts and dialkyldimethylammonium salts, e.g. the halides, sulfates and alkylsulfates
- Pyridinium salts in particular alkylpyridinium salts e.g. the halides, sulfates and C r C 4 -alkylsulfates and
- Imidazolinium salts in particular N,N'-dialkylimidazolinium salts, e.g. the halides, sulfates or methoxulfates.
- alkyl as used herein and if not defined otherwise is a linear or branched alkyl group having from 4 to 30, preferably from 6 to 22 carbon atoms, e.g. n-hexyl, 1-methylpentyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 1-methylnonyl, 2-propylheptyl, n-dodecyl, 1-methyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, and the like.
- ethoxylated means that OH-f unctions have been reacted with ethyleneoxide to form a oligoethyleneoxide group.
- the degree of ethoxylation (number average of ethyleneoxide repeating units) will usually be in the range from 1 to 30 and in particular from 2 to 20.
- composition of the invention may further contain customary auxiliaries, such as defoamers, thickeners, preservatives, colorants, stabilizers, adjuvants, wetting agents, penetrants, coupling agents and the like which are usually employed in non-aqueous formulations of pesticides.
- auxiliaries such as defoamers, thickeners, preservatives, colorants, stabilizers, adjuvants, wetting agents, penetrants, coupling agents and the like which are usually employed in non-aqueous formulations of pesticides.
- auxiliaries such as defoamers, thickeners, preservatives, colorants, stabilizers, adjuvants, wetting agents, penetrants, coupling agents and the like which are usually employed in non-aqueous formulations of pesticides.
- surfactants and solvents may also work as auxiliaries.
- solvents may work as antifreeze agents or penetrants and the aforementioned surfactants may work as adjuvants or
- Suitable thickening agents include inorganic thickening agents, such as clays, hydrated magnesium silicates and organic thickening agents, such as polysaccharide gums, like xanthan gum, guar gum, gum arabic and cellulose derivatives.
- Organic thickening agents are employed in amounts of from 0.5 to 30 g/l and preferably from 1 to 10 g/l while inorganic thickening agents are employed in amounts of from 0.5 to 30 g/l and preferably from 1 to 10 g/l.
- Suitable preservatives to prevent microbial spoiling of the compositions of the invention include formaldehyde, alkyl esters of p-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1 ,3-diol, o-phenylphenol, thiazolinones, such as benzisothiazolinone, 5-chloro-2-methyl-4-isothiazolinone, pentachlorophenol, 2,4-dichlorobenzyl alcohol and mixtures thereof.
- the amount of preservatives will be from 0.1 to 10 g/l.
- Suitable defoamers include polysiloxanes, such as polydimethyl siloxane. Defoamers are usually employed in amounts of from 0.1 to 5 g/l.
- HALS-compounds such as UVINUL® 4049H, 4050H and 5050H, and the like and anti-oxidants such as vitamin E.
- the amount of stabilizer will be from 0.01 to 10 g/l of the concentrate composition.
- auxiliaries may be contained within the composition of the present invention. However, it is also possible to add these auxiliaries after dilution with water to the ready-to-use aqueous composition.
- the liquid compositions of the invention form an aqueous pesticide composition which contains the at least one organic pesticide compound C, the at least one organic solvent S, the at least one non-ionic blockcopolymer P and optionally one or more non-polymeric surfactants and water.
- the at least one organic pesticide compound is present in the form of finely divided particles having a particle size in the nm range, i.e. the average particle size as determined by dynamic light scattering (at 25 0 C and 1 ,013 mbar) is below 500 nm, preferably in the range from 100 to 300 nm, in particular in the range from 10 to 200 nm and most preferably in the range from 10 to 100 nm.
- the liquid compositions of the invention are usually diluted with at least 5 parts of water, preferably at least 10 parts of water, in particular at least 20 parts of water and more preferably at least 50 parts of water, e.g. from 10 to 10,000, in particular from 20 to 1 ,000 and more preferably from 50 to 250 parts of water per one part of the liquid composition (all parts are given in parts by weight).
- Dilution will be usually achieved by pouring the concentrate compositions of the invention into water. Usually, dilution is achieved with agitation, e.g. with stirring, to ensure a rapid mixing of the concentrate in water. However, agitation is not necessary. Though the temperature of mixing is not critical, mixing is usually performed at temperatures ranging from 0 to 100 0 C, in particular from 10 to 50 0 C or at ambient temperature.
- the water used for mixing is usually tap water. However the water may already contain water soluble compounds which are used in plant protection, e.g. nutrificants, fertilizers or water soluble pesticides.
- compositions contain a fungicide compound they may be applied against the following harmful fungi:
- Botrytis clnerea (gray mold) on strawberries, vegetables, ornamentals and grapevines, - Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
- Cercospora oryzae Cochliobolus miyabeanus, Sarocladium oryzae, S attenuatum, Entyloma oryzae, Gibberella fujikuroi (bakanae), Grainstaining complex (various pathogens), Bipolaris species, Drechslera species, Agaricomycetidae such as Rhizoctonia solani and/or Pythium on rice,
- dipterans for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola,
- Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atta s ⁇ xd ⁇ ns, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
- Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
- homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis
- Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
- Arachnids Acarina
- Argasidae e.g. of the families Argasidae, I
- Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
- compositions according to the invention contain a herbicide compound it will be used to controll undesired vegetation.
- the control of undesired vegetation is understood as meaning the destruction of weeds. Weeds, in the broadest sense, are understood as meaning all those plants which grow in locations where they are undesired, for example:
- the required application rate of the pure active compounds without formulation auxiliary depends on the density of the undesired vegetation, on the development stage of the plants, on the climatic conditions of the location where the composition is used and on the application method.
- the application rate is from 0.001 to 3 kg/ha, preferably from 0.005 to 2 kg/ha and in particular from 0.01 to 1 kg/ha, from 0.1 g/ha to 1 kg/ha, from 1 g/ha to 500 g/ha or from 5 g/ha to 500 g/ha of active substance.
- the diluted compositions are applied to the plants mainly by spraying, in particular foliar spraying.
- Application can be carried out by customary spraying techniques using, for example, water as carrier and spray liquor rates of from about 100 to 1 000 I/ha (for example from 300 to 400 I/ha).
- Application of the preparations by the low-volume and the ultra-low-volume method is possible, as is their application in the form of microgranules.
- composition of active ingredients are applied in a rate which provides control of weeds or crops, in particular post- emergence to the weed or crop, but preferably prior to the planting, seeding or emergence of a desired crop.
- compositions according to the invention may be useful to apply the compositions according to the invention jointly as a mixture with other crop protection products, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria.
- pesticides or agents for controlling phytopathogenic fungi or bacteria are also of interest.
- mineral salt solutions which are employed for treating nutritional and trace element deficiencies.
- Non-phytotoxic oils and oil concentrates may also be added.
- compositions contain a compound, in particular an insecticide compound which is active against non-crop pests. Therefore the invention also relates to a method for controlling non-crop pests comprising contacting the pests or their food supply, habitat, breeding grounds or their locus with formulation according to the invention comprising at least an insecticide.
- the invention further relates to the use of a composition according to the invention comprising at least an insecticide for the protection of non-living organic materials against non-crop pests.
- Non-crop pests are pests of the classes Chilopoda and Diplopoda and of the orders Isoptera, Diptera, Blattaria (Blattodea), Dermaptera, Hemiptera, Hymenoptera, Orthoptera, Siphonaptera, Thysanura, Phthiraptera, Araneida, Parasitiformes and Acaridida, for example:
- centipedes e.g. Scutigera coleoptrata
- spiders e.g. Latrodectus mactans, and LOXOSC ⁇ I ⁇ S reclusa
- scabies e.g. sarcoptes sp
- ticks and parasitic mites ticks (Ixodida), e.g.
- Ixodes scapularis Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae,
- cockroaches e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
- Psorophora discolor Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
- Earwigs e.g. forficula auricularia
- true bugs Hemiptera
- Cimex lectularius Cimex lectularius
- Cimex hemipterus Reduvius senilis
- Triatoma spp. Rhodnius prolixus
- Arilus critatus
- formulation according to the invention comprising at least an insecticide can be used for the protection of non-living organic materials, including but are not limited to house-hold goods such as fats, oils, mono- oligo- or polyorganosaccharides, proteins, or fresh or decaying fruits; cellulose-containing materials e.g. wooden materials such as houses, trees, board fences, or sleepers and also paper; and also construction materials, furniture, leathers, animal, plant and synthetic fibers, vinyl articles, electric wires and cables as well as styrene foams.
- house-hold goods such as fats, oils, mono- oligo- or polyorganosaccharides, proteins, or fresh or decaying fruits
- cellulose-containing materials e.g. wooden materials such as houses, trees, board fences, or sleepers and also paper
- construction materials furniture, leathers, animal, plant and synthetic fibers, vinyl articles, electric wires and cables as well as styrene foams.
- the present invention also provides a method for protecting cellulose-containing non- living organic materials against non-crop pests, preferably from the Isoptera, Diptera, Blattaria (Blattodea), Hymenoptera, and Orthoptera orders, most preferably the Isoptera orders, comprising contacting the pests or their food supply, habitat, breeding grounds, their locus or the cellulose-containing non-living organic materials themselves with a a formulation according to the invention comprising at least an insecticide.
- a formulation according to the invention comprising at least an insecticide can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
- Suitable seeds are for example various crop seeds, fruit species, vegetables, spices and ornamental seed, for example corn/maize (sweet and field), durum wheat, soybean, wheat, barley, oats, rye, triticale, bananas, rice, cotton, sunflower, potatoes, pasture, alfalfa, grasses, turf, sorghum, rapeseed, Brassica spp., sugar beet, eggplants, tomato, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium.
- corn/maize sweet and field
- durum wheat soybean, wheat, barley, oats, rye, triticale
- bananas rice
- M N is the number average molecular weight
- blockcopolymer P h EO/PO triblockcopolymer, M N 6000, EO/PO ratio 60:40, blockcopolymer P': EO/PO triblockcopolymer, M N 4290, EO/PO ratio 30:70,
- the active ingredient and optionally further additives are stirred in the solvent S at room temperature until complete dissolution.
- the thus obtained solution is mixed with blockcopolymer P and optionally further surfactant until a homogenous mixture is obtained.
- compositions outlined in Tables 1 , 3, 4, 5, 6, 7 and 8 were prepared by the general procedure A.
- compositions outlined in Table 2 were prepared by the general procedure B.
- Tables 1 to 8 the amounts of the ingredients are given in
- compositions of Tables 1 to 8 form bluish clear compositions, wherein the active ingredient particles have an average diameter below 100 nm (as determined by quasi elastic light scattering).
- the diluted composition remain stable for at least 24 h.
- a diluted composition is estimated to be stable period of time if the particle size remains below 100 nm within said time period.
- Table 1 Compositions containing 1-[N-(4-Trifluoromethoxyphenyl)semicarbazono]- 1 -(3-cyanophenyl)-2-(4-trifluoromethylphenyl)ethane (metaflumizone) (compositions 1.1 to 1.7):
- Table 3 Compositions containing methyl /V- ⁇ 2-[1-(4-chlorophenyl)-1 /-/-pyrazol-3- yloxymethyl]phenyl ⁇ (/V-methoxy)carbamate (Pyraclostrobin) and 2-chloro- ⁇ /-(4'-chlorobiphenyl-2-yl)nicotinamide (Boscalid)
- Table 4 Compositions containing ⁇ /-(1 -ethylpropyl)-2,6-dinitro-3,4-xylidine (pendimethalin)
- Table 6 Compositions containing ethyl trichloro-2-pyridyloxyacetate (triclopyr-ethyl)
- Table 7 Compositions containing ⁇ -cyano-3-phenoxybenzyl (1 S,3S)-3-(2,2- dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (alpha-cypermethrin)
- Table 8 Compositions containing 1-[4-(2-chloro- ⁇ , ⁇ , ⁇ -trifluoro-p-tolyloxy)-2- fluorophenyl]-3-(2,6-difluorobenzoyl)urea (flufenoxuron)
- compositions 9.1 to 9.6 were prepared according to method A outlined in 1.1 by dissolving 12.5 parts by weight of Metaflumizone in 62.5 parts by weight of ⁇ - butyrolactone and adding thereto 25 parts by weight of blockcopolymer (blockcopolymer P b and/or blockcopolymer P c as given in Table 9).
- compositions were diluted with 100 parts of water per 1 part of the composition (all parts given are parts by weight).
- the obtained compositions were analyzed within 24 h or 48 h, respectively, with regard to particle size of the dispersed active ingredient.
- the relative amounts of blockcopolymer P b to blockcopolymer P c and the average particle sizes of the dispersed material after dilution with water are given in Table 9.
- 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.
- composition 10.1 to 10.5 of the invention comparative compositions A and B
- compositions 10.1 to 10.5 were prepared according to method A outlined in 1.1 by dissolving 10 parts by weight of Metaf lumizone in 70 parts by weight of v- butyrolactone and adding thereto 20 parts by weight of blockcopolymer as given in Table 10.
- 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.
- Composition B was a solution of 10 parts by weight of semicarbazone 90 parts by weight of acetone.
- composition A Upon dilution with 100 parts by weight of water per 1 part by weight of composition, composition A formed a suspension, wherein the initial average particle size of the dispersed material was about 0.25 ⁇ m. After 1 h the average particle size of the dispersed material was about 0.5 ⁇ m. After 24 h, large amounts of crystalline material of 2 mm in size were observed.
- composition B Upon dilution with 100 parts by weight of water per 1 part by weight of composition, composition B formed a suspension, wherein the initial average particle size of the dispersed material was about 0.5 ⁇ m. Small amounts of crystalline material were observed directly after dilution. After 1 h the average particle size of the dispersed material was about 1.0 ⁇ m. After 24 h, large amounts of crystalline material of 2 mm in size were observed.
- compositions were diluted with 100 parts by weight of water per 1 by weight part of composition. After 24 h, the diluted compositions were examined by dynamic light scattering. Each of the diluted compositions showed average particle sizes below 100 nm without formation of solids. Compositions rated ++++ showed average particle sizes below 20 nm while compositions rated +++ had average particle sizes between 20 nm and 100 nm. Table 11 :
- compositions were prepared in order to show the increased stability of compounds which may undergo chemical degradation in compositions according to the invention.
- composition C, D, E and F (comparative), 12.1 and 12.2 were prepared by mixing the active ingredients, solvents and surface active compounds given in Table 12a.
- composition G and H were prepared by mixing the active ingredients, solvents and surface active compounds given in Table 13.
- the samples were stored at 50 0 C and removed at weekly intervals for analysis of the degree of degradation (by normal phase HPLC, UV-detection). The data were fitted to a first order kinetic profile and the time for 10 % degradation was calculated. The results are given in Table 13.
- compositions J (comparative) and 14.1 (inventive) were prepared by mixing the active ingredients, solvents and surface active compounds given in Table 14.
- compositions K, L, and 15.1 were evaluated under field conditions:
- K is a commercial aqueous suspension concentrate of metaflumizone, wherein the average particle size of the active ingredient after dilution is about 1 ⁇ m.
- K contains 22 % by weight of metaflumizone and 10 % by weight of surfactant which is a mixture of polyoxypropylene-polyoxyethylene-triblockcopolymer, sodium-dioctylsulfosuccinate, ethoxylated alkanol and ethoxylated alkylphenol.
- L is a commercial aqueous suspension concentrate of metaflumizone wherein the average particle size of the active ingredient after dilution is about 1.6 ⁇ m.
- L contains 22 % by weight of metaflumizone and 10 % by weight of surfactant which is a mixture of polyoxypropylene-polyoxyethylene-thblockcopolymer, sodium-dioctylsulfosuccinate, ethoxylated alkanol and ethoxylated alkylphenol.
- 15.1 is a liquid concentrate composition according to the invention which contains 12.5 % by weight of metaflumizone, 52.8 % by weight of butyrolactone and 35 % by weight of a blend of blockcopolymers P b , P c and P g . Upon dilution with water the average particle size was about 20 nm.
- compositions K, L and 15.1 were diluted with water to a concentration of semicarbazone of 3500 ppm for 100 % use rate.
- compositions were applied under field conditions at different use rates to plantations of several plant species of leafy and fruiting vegetables, including brassica crops, potatoes, soybean, tobacco, beets and cotton.
- leafy and fruiting vegetables including brassica crops, potatoes, soybean, tobacco, beets and cotton.
- Helicoverpazea (cotton bollworm, tomato fruitworm, corn earworm)
- compositions Vl.1 to VI.52 were prepared according to the general methods A or B as described in 11.1.
- the amounts of active ingredient (either amidrazone I or II), solvent, and blockcopolymer are given in table 16 in parts by weight.
- compositions of table 16 Upon dilution with water (100 parts per 1 part of composition) the compositions of table 16 form bluish clear compositions. The diluted composition remain stable for at least 24 h.
- Mean is based on 6 insects per vial and 5 reps per treatment.
- Test Arenas Tests were conducted in 60 X 15 mm plastic Petri dishes. The bottom of each dish was coated with 2 ml agar.
- Arena preparation- 1 Tests were run in 1.5 cm diameter, transparent tubes (PVC tubes) which were cut at one end to a length of 13 to 14 cm. Any sharp points formed where the tube was cut were trimmed.
- a quantity of wood flour was prepared for use as an attractive food source at the bottom of the tunnel tubes.
- the hardwood samples will only require addition of enough water to thoroughly moisten the woodflour (sample should be wet but still loose enough for easy transfer into tubes).
- the softwood samples pine were pre-washed to remove residues of natural defensive chemicals. The softwood material was placed into a Buchner funnel (with filter paper) and water was added until sample was covered with standing water.
- Test soil was prepared by drenching the soil with a solution, obtained by diluting composition Vl .2 or Vl.4 with water. The concentration of active ingredient in the soil is given in table 19.
- each tube was pressed into the poured agar to load 5 a 1 cm agar plug into the tube.
- the plug was pushed most of the way through the tube (approx. 3 cm from opposite end) with a wood dowel. Approx. 2 cm of woodflour were loaded into the short end of the tube, a rubber stopper was inserted and then the contents were firmly packed against the stopper.
- the tube was lightly tapped on the counter top to compact the soil. Additional soil was loaded and compacting step was repeated to fill the 5 cm length with loosely compacted soil.
- the completed tubes were stored under standard holding conditions and observed daily for penetration of tunnels through the soil columns. Daily progress through 5 the soil can be marked directly on the tube and measured later (see sample data array). Instinctive behavior for termites will be to immediately start tunneling downward for shelter and termites will usually penetrate through an untreated soil column in 24 to 48 hrs. Failure to penetrate into the soil column could be the result of repellent treatment in the soil or rapid toxicity. 0
- Test Arenas Tests were conducted in 100 x 20 mm polystyrene Petri dish. The inner sides of the dishes were painted with Fluon (Northern Products, Woonsocket, Rl) to prevent ant escape. Test arenas were prepared by dispensing a thin layer of 1 % agar into the dishes and then spreading 10g of Princeton Sandy Loam soil over the agar.
- Test treatments were applied as solutions, obtained by diluting composition Vl .2 or VI.4 with water. The solutions were sprayed @ 1 gal/1000 ft 2 with a DeVilbiss atomizer. Dish covers were used to conserve moisture and additional water added as needed. A small cotton dental wick was placed in each arena soaked with 20 % sucrose solution for food and water source for the duration of test. 15 ants were placed in each dish, and each treatment was replicated three times. Test dishes were maintained in the laboratory (22 0 C) and observed for mortality daily for 5 to 10 days.
- Test Arenas Tests were conducted in 10O x 20 mm Petri dishes. The inner sides of the dishes were painted with Fluon (Northern Products, Woonsocket, Rl) to prevent ant escape. Baits were mixed with a 40% honey/water solution. For honey/water incorporation, a stock solution containing 40% by weight of honey in distilled water was prepare.
- compositions VI2. or Vl .4 were diluted with water and then add to the honey water solution to bring the final solution up to the desired concentration of active ingredient and 40% honey water.
- 0.2 ml of treated honey water solution was applied to a micro weigh dish to hold the bait material. 15 ants were introduced into each test arena dish, starved for 24 hours before the introduction of the bait material. A water soaked dental wick was provided during the starvation period. The water soaked dental wick was removed upon the introduction of the bait solution. Test dishes were covered with the dish cover to maintain humidity, and maintained in laboratory (22° C) and observed for mortality and intoxicating effects for 5 days.
- Formulation Vl.4 resulted in 100% mortality by 3 DAT.
- Formulation VI.2 resulted in 100% mortality by 5 DAT.
- Test Arenas Grease (3 parts petroleum jelly ⁇ Vaseline ⁇ , and 2 parts mineral oil) were placed on the top 3-4 cm of clear plastic Rubbermaid containers measuring 20L X 21 W X12 H cm to prevent the insects from escaping. Water was provided with a 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.
- Bait was prepared using ground cat chow and composition VI.2 or Vl .4 was incorporated on a weight-to-weight ratio of a.i. to chow. For each treatment, a total of 1 gram of treated chow was prepared using a total volume of 1 ml of diluted composition to completely wet the chow with each rate of compound. The roaches were placed in test arenas and starved for 24 hours prior to bait introduction, with a water source at all times. Treatments were replicated three times. The amount of treated chow for each arena was weighed out to approximately 0.03 grams, and placed in a plastic weigh boat (45 mm x 45 mm). Arenas were placed in the laboratory (22 ° C) and covered with blotter paper. Mortality was observed for 3 days.
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Catching Or Destruction (AREA)
Abstract
Description
Claims
Priority Applications (12)
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CA2570358A CA2570358C (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
DE602005026291T DE602005026291D1 (en) | 2004-07-06 | 2005-07-05 | LIQUID PESTICIDE COMPOSITIONS |
US11/631,462 US8741324B2 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
AT05772409T ATE497696T1 (en) | 2004-07-06 | 2005-07-05 | LIQUID PESTICIDE COMPOSITIONS |
MXPA06014862 MXPA06014862A (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
AP2007003879A AP2007003879A0 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
PL05772409T PL1773121T3 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
BRPI0513023-9A BRPI0513023A (en) | 2004-07-06 | 2005-07-05 | pesticide composition, use thereof, and methods for combating organisms that are harmful to plants, to protect crops from attack or infestation by harmful organisms, and to protect seeds from attack or infestation by harmful organisms |
EP05772409A EP1773121B1 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
AU2005259394A AU2005259394A1 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
JP2007519703A JP5179865B2 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide composition |
IL180009A IL180009A0 (en) | 2004-07-06 | 2006-12-12 | Liquid pesticide compositions |
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US58507304P | 2004-07-06 | 2004-07-06 | |
US60/585,073 | 2004-07-06 |
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PCT/EP2005/007256 WO2006002984A1 (en) | 2004-07-06 | 2005-07-05 | Liquid pesticide compositions |
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US (1) | US8741324B2 (en) |
EP (1) | EP1773121B1 (en) |
JP (1) | JP5179865B2 (en) |
KR (1) | KR20070029242A (en) |
CN (1) | CN1980572A (en) |
AP (1) | AP2007003879A0 (en) |
AR (1) | AR049665A1 (en) |
AT (1) | ATE497696T1 (en) |
AU (1) | AU2005259394A1 (en) |
BR (1) | BRPI0513023A (en) |
CA (1) | CA2570358C (en) |
CR (1) | CR8814A (en) |
DE (1) | DE602005026291D1 (en) |
EC (1) | ECSP077128A (en) |
ES (1) | ES2361030T3 (en) |
IL (1) | IL180009A0 (en) |
IN (1) | IN2006KO03744A (en) |
MA (1) | MA28735B1 (en) |
MX (1) | MXPA06014862A (en) |
NL (1) | NL1029431C2 (en) |
PA (1) | PA8638401A1 (en) |
PE (1) | PE20060110A1 (en) |
PL (1) | PL1773121T3 (en) |
RU (1) | RU2358427C2 (en) |
TW (1) | TW200605783A (en) |
UA (1) | UA85264C2 (en) |
UY (1) | UY29005A1 (en) |
WO (1) | WO2006002984A1 (en) |
ZA (1) | ZA200701037B (en) |
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