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WO2025233453A1 - Nouvelles formulations agrochimiques - Google Patents

Nouvelles formulations agrochimiques

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Publication number
WO2025233453A1
WO2025233453A1 PCT/EP2025/062620 EP2025062620W WO2025233453A1 WO 2025233453 A1 WO2025233453 A1 WO 2025233453A1 EP 2025062620 W EP2025062620 W EP 2025062620W WO 2025233453 A1 WO2025233453 A1 WO 2025233453A1
Authority
WO
WIPO (PCT)
Prior art keywords
fatty acid
formulation
water
water immiscible
valerolactone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/062620
Other languages
English (en)
Inventor
Christian Sowa
Marcus Annawald
Indre THIEL
Adam BLANAZS
Calvin Michael SCHALOSKE
Ingo Fleute-Schlachter
Peter Hofer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025233453A1 publication Critical patent/WO2025233453A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention is directed to liquid formulations comprising: a. one or more pesticides P, b. gamma-valerolactone, c. optionally further water miscible solvents different from gamma-valerolactone, d. a water immiscible solvent, e. surfactants, comprising a mixture of anionic and nonionic surfactants.
  • pesticide P is complete dissolved at 20 °C and where the formulation contains 15 to 90 wt% of said water immiscible solvent, preferably 20 to 70 wt%, where the ratio of said water immiscible solvent to gamma-valerolactone is higher than 0.7, preferably higher than 1.0.
  • WO 2011/110292 discloses biocide compositions comprising valerolactone or its derivatives.
  • the objective of the present invention was therefore to provide formulations of pesticides with improved stability and biologically efficacy.
  • This objective has been achieved by liquid agrochemical formulations comprising: a. one or more pesticides P, b. gamma-valerolactone, c. optionally further water miscible solvents different from gamma-valerolactone, d. a water immiscible solvent, e. surfactants, comprising a mixture of anionic and nonionic surfactants.
  • pesticide P is complete dissolved at 20 °C and where the formulation contains 15 to 90 wt% of said water immiscible solvent, preferably 20 to 70 wt%, where the ratio of said water immiscible solvent to gamma-valerolactone is higher than 0.7, preferably higher than 1.0.
  • liquid agrochemical formulations comprising: a. one or more pesticides P, b. gamma-valerolactone, c. optionally further water miscible solvents different from gamma-valerolactone, d. a water immiscible solvent, e. surfactants, comprising a mixture of anionic and nonionic surfactants.
  • pesticide P is complete dissolved at 20 °C, where the formulation does not comprise pendimethalin and imazamox, and where the formulation contains 15 to 90 wt% of said water immiscible solvent, preferably 20 to 70 wt%, where the ratio of said water immiscible solvent to gamma-valerolactone is higher than 0.7, preferably higher than 1.0.
  • Formulations of the invention comprise at least one pesticide P.
  • composition and “formulation” are used synonymously.
  • pesticides refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators.
  • Pesticide P can in principle be any kind of pesticide that is soluble in solvent system S.
  • Preferred pesticides P are fungicides, insecticides, herbicides, and growth regulators. I n one embodiment, pesticides P are insecticides. In one embodiment, pesticides P are fungicides. In one embodiment, pesticides P are herbicides. Mixtures of pesticides from two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London.
  • formulations of the invention do not comprise imazamox. In one embodiment, formulations of the invention do not comprise pendimethalin. In one embodiment, formulations of the invention do not comprise pendimethalin and imazamox.
  • the composition may comprise one or more pesticides.
  • pesticide P is water insoluble.
  • water insoluble means that a component has a solubility in water at 20 °C and at neutral pH of 10 g/L or less, preferably 1 g/L or less or of 0.1 g/L or less or of 0.01 g/L or less.
  • Respiration inhibitors inhibitors of complex III at Qo site azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyribencarb, trie I opy rica r b/c h I o ro- id i n ca r b, famoxadone, fenamidone, pyriminostrobin, bifujunzhi, metyltetraprole; inhibitors of complex II I at Qi site: cyazofamid, amisulbrom, f
  • Sterol biosynthesis inhibitors SBI fungicides
  • C14 demethylase inhibitors triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluoride
  • Inhibitors of 3-keto reductase fenhexamid, fenpyrazamine; other Sterol biosynthesis inhibitors: chlorphenomizole;
  • RNA polymerase I inhibitors benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixyl; other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, ipflufenoquin, quinofumelin;
  • Inhibitors of cell division and cytoskeleton tubulin polymerization inhibitors benomyl, carbendazim, fuberidazole, thiabendazole, th io ph a nate- methyl, pyridachlometyl; other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, phenamacril, fluopimomide;
  • Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors cyprodinil, mepanipyrim, pyrimethanil; protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloridehydrate, mildiomycin, streptomycin, oxytetracyclin;
  • MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil; mechanism unknown: quinoxyfen, proquinazid;
  • Phospholipid biosynthesis inhibitors edifenphos, iprobenfos, pyrazophos, isoprothiolane; lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; compounds affecting cell membrane permeability and fatty acides: propamocarb; inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin;
  • inorganic active substances Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid; guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, i m i noctad i ne-tris (a I bes i I
  • Cell wall synthesis inhibitors inhibitors of glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb; cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate;
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampe/omyces quisquaiis, Aspergillus flavus, Aureobasidium memeiuians, Bacillus aititudinis, B. amy/o/iquefaciens, B. amyloliquefaciens ssp. p /anta rum (also referred to as B. ve/ezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumi-/us, B. simplex, B. soiisaisi, B. subtiiis, B. subtilis var.
  • amyloliquefaciens B. ve/ezensis, Candida oieophiia, C. saitoana, Ciavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus aibidus, Diiophosphora aiopecuri, Fusarium oxysporum, Cionostachys rosea f. catenulate (also named Giiociadium catenuiatum), Giiociadium roseum, Lysobacter antibioticus, L.
  • Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity harpin protein, Reynoutria sachaiinensis extract;
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israeiensis, B. t. ssp. gaiieriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B.
  • Agrobacterium radiobacter Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israeiensis, B. t. ssp. gaiieriae, B. t. ssp. kurstaki, B. t. s
  • brongniartii Burkho/deria spp., Chromobacterium subtsugae, Cydia pomoneiia granuiovirus, Cryptoph/ebia ieucotreta granuiovirus, Fiavobacterium spp., Heiicoverpa armigera nucleopolyhedrovirus, Heiicoverpa zea nucleopolyhedrovirus, He/icoverpa zea single capsid nucleopolyhedrovirus, Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L.
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity Azospirillum amazonense, A. brasi/ense, A. Hpoferum, A. irakense, A. ha/opraeferens, Bradyrhizobium spp., B. e/kanii, B. japonicum, B. Haoningense, B. lupini, De/ftia acidovorans, G torn us intraradices, Mesorhizobium spp., Rhizobium /eguminosarum bv. phaseoH, R. /. bv. trifoHi, R. /. bv. viciae, R. tropici, Sino-rhizobium melilotr,
  • Acetylcholine esterase (AChE) inhibitors aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos,
  • Sodium channel modulators acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin,
  • Nicotinic acetylcholine receptor (nAChR) agonists acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;
  • Nicotinic acetylcholine receptor allosteric activators spinosad, spinetoram;
  • Chloride channel activators abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
  • miscellaneous non-specific (multi-site) inhibitors methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
  • Mite growth inhibitors clofentezine, hexythiazox, diflovidazin; etoxazole;
  • 0.11 Microbial disruptors of insect midgut membranes Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl;
  • Inhibitors of mitochondrial ATP synthase diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers bensultap, cartap hydrochloride, thiocyclam, thio-sultap sodium;
  • Inhibitors of the chitin biosynthesis type 0 bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
  • Ecdyson receptor agonists methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;
  • Octopamin receptor agonists amitraz
  • Mitochondrial complex III electron transport inhibitors hydramethylnon, acequinocyl, fluacrypyrim, bifenazate
  • Mitochondrial complex I electron transport inhibitors fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;
  • Inhibitors of the of acetyl CoA carboxylase spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat;
  • Mitochondrial complex IV electron transport inhibitors aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;
  • Mitochondrial complex II electron transport inhibitors cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide;
  • GABA-gated chloride channel allosteric modulators broflanilide, fluxametamide, isocycloseram;
  • O.UN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropylate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindolizine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflan
  • ACC-herbicides alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cy-cloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop- methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop- P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-
  • ALS inhibitors sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosu Huron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl- sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl,
  • P3) photosynthesis inhibitors amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron,
  • protoporphyrinogen-IX oxidase inhibitors acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfen-trazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyrafluorf
  • PDS inhibitors beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;
  • HPPD inhibitors benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tol pyralate, toprame-zone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione; bleacher, unknown target: aclonifen, amitrole flumeturon, bixlozone;
  • EPSP synthase inhibitors glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate- trimesium (sulfosate);
  • glutamine synthase inhibitors bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;
  • mitosis inhibitors group KI: dinitroanilines: benf luralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, prodiamine and trifluralin; phosphoramidates: amiprophos, amiprophos- methyl, and butamiphos; benzoic acid herbicides: chlorthal, chlorthal-dimethyl; pyridines: dithiopyr and thiazopyr; benzamides: propyzamide and tebutam; group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham;
  • VLCFA inhibitors chloroacetamides: acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor, oxyacetanilides: flufenacet and mefenacet; acetanilides: diphenamid, naproanilide, napropamide and napropamide-M; tetrazolinones: fentrazamide; other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isoxazoline;
  • PH cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam;
  • P12) decoupler herbicides dinoseb, dinoterb and DNOC and its salts
  • 2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as a mi nopyralid -di methylammonium, a minopyral id -tris (2- hydroxy propyl) ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl, MC
  • auxin transport inhibitors diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium; P15) other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid,
  • pesticide P comprises metyltetraprole, mefentrifluconazole, fluxapyroxad, I npyrfluxam, Kresoxim methyl, Pyraclostrobin, Fluopyram, saflufenacil, broflanilide, dimpropyridaz, fenmezoditiaz, Cinnamaldehyde, Prothioconazole, Trifloxystrobin, Fluxapyroxad, Spiroxamine, afidopyropen, alpha-cypermethrin, fipronil, cyflumetofen, boscalid, epoxiconazole, metconazole, metrafenone, prothioconazole, bentazone, dimethenamide, tembotrione, trifludimoxazin, Mefenpyr-Diethyl, azoxystrobin, picoxystrobin, fluoxastrobin, oryzastrobin, dim
  • pesticide P comprises metyltetraprole, mefentrifluconazole, fluxapyroxad, Inpyrfluxam, Kresoxim methyl, Pyraclostrobin, Fluopyram, saflufenacil, broflanilide, dimpropyridaz, fenmezoditiaz, Cinnamaldehyde, Prothioconazole, Trifloxystrobin, Fluxapyroxad, Spiroxamine, afidopyropen, alpha-cypermethrin, fipronil, cyflumetofen, boscalid, epoxiconazole, metconazole, metrafenone, prothioconazole, bentazone, dimethenamide, tembotrione, trifludimoxazin, Mefenpyr-Diethyl or mixtures thereof.
  • pesticide P comprises metyltetraprole, mefentrifluconazol, fluxapyroxad, Inpyrfluxam, Kresoxim methyl, Pyraclostrobin, Fluopyram, Cinnamaldehyde, Prothioconazole, Trifloxystrobin, Fluxapyroxad, Spiroxamin, Mefenpyr-Diethyl, indiflin or mixtures thereof
  • pesticide P comprises a strobilurin pesticide.
  • strobilurin pesticides include azoxystrobin, kresoxim methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, trifloxystrobin and metyltetraprole.
  • pesticide P comprises Metyltetraprole or Prothioconazole or mixtures thereof. In one embodiment, pesticide P does not comprise imazamox. In one embodiment, pesticide P does not comprise pendimethalin. In one embodiment, pesticide P does not comprise pendimethalin and imazamox.
  • pesticide P is completely dissolved in the formulation at 20 °C.
  • At least one, more preferably all, of the one or more pesticides P has/have a water solubility of less than 2000 mg/L, more preferably of less than 1000 mg/L, most preferably of less than 500 mg/L.
  • formulations of the invention comprise gamma-Valerolactone, herein also referred to as “GVL”.
  • Gamma Valerolactone has the following structure:
  • gamma-valerolactone has a stereogenic center, meaning that it may exist in one of two enantiomeric forms (denoted L/D, R/S, +/- etc.).
  • the GVL may be either the L-form or the D- form or a mixture of the L- and D-forms. Mixtures can, for example, be in the ratio ranging from 99:1 to 1:99. Most preferably, the GVL is a 50:50 (i.e. racemic) mixture of the L- and D- forms.
  • GVL is miscible with water as well as with unpolar solvents.
  • GVL is comprised in formulations of the invention in an amount of 1 to 40 wt% or 1 to 35 wt%, preferably 2 to 35 wt% or 5 to 35 wt%, in each case based on the formulation.
  • Formulations of the inventions may comprise further water miscible solvents different from GVL.
  • water miscible in the context of solvents means that a solvent has a solubility in water at 20 °C at a pH of 7 of 10 g/L or more.
  • water immiscible in the context of solvents means that a solvent has a solubility in water at 20 °C at a pH of 7 of less than 10 g/L.
  • a water immiscible solvent may refer to one water immiscible solvent or it may refer to a mixture of water immiscible solvents.
  • water miscible solvents examples include N-alkyl pyrrolidone (especially N- methyl pyrrolidone, N-(n-butyl) pyrrolidone, N-(t-butyl) pyrrolidone or N-(sec-butyl) pyrrolidone), dimethylsulfoxide, N,N-dial kyl lactamide, especially N,N-dimethyl lactamide, propylene carbonate, gamma butyrolactone, hydroxyethyl pyrrolidone, methyl 5- (dimethylamino) 2-methyl-oxopentanoate, and 1,3 dimethyl-2-imidazolidinone.
  • water miscible solvents including GVL and further water miscible solvents are comprised in the formulation in an amount of 1 to 40 wt% or 1 to 35 wt%, preferably 2 to 35 wt%.
  • Formulations of the invention comprise one or more water immiscible solvents.
  • water immiscible solvents include mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • aromatic petroleum derivatives with a boiling point range from 130 °C to 300 °C
  • vegetable oils such as coco oil, palm kern oil, palm oil, soya oil, rapeseed oil, corn oil and the methyl or ethyl esters of the aforementioned oils, hydrocarbons such as aromatic depleted, linear paraffinic, isoparaffinic, cycloparaffinic having a flash point between 40 °C and 250 °C and a distillation range between 150 °C and 450 °C
  • ketones e.g.
  • acetophenone carbonates, e.g. dibutyl carbonate; esters, e.g. benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2-phenoxyethyl propionate; lactates, e.g.
  • 2-ethyl hexyl lactate dialkyl adipates, alkyl lactic esters, propylene glycol dibenzoate, dipropyleneglycol dibenzoate, fatty acid esters, fatty acids; phosphonates; fatty acid amines; pyrrolidones, such as N-butyl pyrrolidone, N-octylpyrrolidone, N-ethyl pyrrolidone, N-docedyl pyrrolidone, hydroxy ethyl pyrrolidone; fatty acid amides, e.g.
  • N,N- dimethyloctanamide N,N-dimethylnonaneamide, N,N-dimethyldecanamide, N,N-Dimethyl 9-decenamide, lauryl N,N-dimethylamide, lauryl N,N-dimethylamide, and mixtures thereof.
  • C 8 dimethylamide and “N,N-dimethyl octaneamide” shall be understood to mean ”C 8 fatty acid N,N-dimethylamide” (analogously for other chain lengths).
  • “Fatty acid” herein shall denote a linear or branched carboxylic acid with a saturated or unsaturated aliphatic chain.
  • said water immiscible solvent is selected from benzyl benzoate, benzyl acetate, benzyl alcohol, dipropyleneglycol dibenzoate, methyl oleate, fatty acid N,N- dimethylamides, fatty acid methyl esters, dialkyl adipates, alkyl lactic esters, propylene glycol dibenzoate, tris-alkyl phosphoric esters, aromatic hydrocarbons or mixtures thereof.
  • said water immiscible solvent is selected from benzyl benzoate, C 8 -fatty acid N,N-dimethylamide, C 10 fatty acid N,N-dimethylamide, C 12 fatty acid N,N- dimethylamide, C 6 fatty acid methyl ester, C 8 fatty acid methyl ester, C 10 fatty acid methyl ester, dibutyl adipate, ethyl hexyl lactic acid, propylene glycol dibenzoate, dipropyleneglycol dibenzoate, tris-ethyl hexyl phosphate, aromatic hydrocarbons, benzyl acetate, methyl oleate, or mixtures thereof.
  • said water immiscible solvent contains at least one heteroatom, i.e. does not contain only hydrogen and carbon atoms.
  • the water immiscible solvent may be selected from benzyl benzoate, benzyl acetate, benzyl alcohol, dipropyleneglycol dibenzoate, methyl oleate, fatty acid N,N-dimethylamides, fatty acid methyl esters, dialkyl adipates, alkyl lactic esters, propylene glycol dibenzoate, tris-alkyl phosphoric esters or mixtures thereof.
  • said water immiscible solvent is selected from benzyl benzoate, C 8 -fatty acid N,N-dimethylamide, C 10 fatty acid N,N- dimethylamide, C 12 fatty acid N,N-dimethylamide, C 6 fatty acid methyl ester, C 8 fatty acid methyl ester, C 10 fatty acid methyl ester, dibutyl adipate, ethyl hexyl lactic acid, propylene glycol dibenzoate, dipropyleneglycol dibenzoate, tris-ethyl hexyl phosphate, benzyl acetate, methyl oleate, or mixtures thereof.
  • water immiscible solvent is selected from the group consisting of dimethyl hexanamide, dimethyl heptanamide, dimethyl octanamide, dimethyl nonanamide, dimethyl decanamide, dimethyl undecanamide, dimethyl dodecanamide, dimethyl tridecanamide, dimethyl tetradecanamide, dimethyl pentadecanamide, dimethyl hexadecanamide, dimethyl heptadecanamide, dimethyl octadecanamide, dimethyl nonadecanamide, dimethyl icosanamide and unsaturated variants thereof, such as dimethyl soyate amide, dimethyl canolate amide and dimethyl oleanamide, as well as fatty acid dimethylamide mixtures, such as C 6 -C 10 fatty acid dimethylamide and C 12 -C 18 fatty acid dimethylamide, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate,
  • water immiscible solvent is selected from the group consisting of solvents comprising at least one ester moiety and/or at least on amide moiety.
  • the water immiscible solvent has a melting temperature in the range from -100 to 20 °C, more preferably in the range from -80 to 15 °C, most preferably in the range from -70 to 10 °C.
  • the water immiscible solvent has a water solubility of less than or equal to 4.00% w/w, more preferably of less than or equal to 2.00% w/w, most preferably of less than or equal to 1.00 % w/w.
  • the water immiscible solvent has a number of carbons in the range from 5 to 20, more preferably in the range from 6 to 17 most preferably in the range from 7 to 14.
  • the water immiscible solvent is a fatty acid amide solvent or a mixture of fatty acid amide solvents, i.e. one or more fatty acid amide solvents.
  • the water immiscible solvent is selected from the group consisting of dialkylamides of saturated or unsaturated fatty acids, more preferably dimethylamides of saturated or unsaturated fatty acids.
  • the saturated or unsaturated fatty acids preferably have from 5 to 20 carbon atoms, more preferably 7 to 17 carbon atoms, most preferably 9 to 14 carbon atoms.
  • At least one of, more preferably each of, the one or more fatty acid amide solvents are selected from the group consisting of dimethylamides of C 5 to C 20 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid amide solvents are selected from the group consisting of dialkylamides of C 7 to C 17 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid amide solvents are selected from the group consisting of dimethylamides of C 7 to C 17 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid amide solvents are selected from the group consisting of dialkylamides of C 9 to C 14 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid amide solvents are selected from the group consisting of dialkylamides of C 9 to C 14 saturated or unsaturated fatty acids.
  • the combined total of fatty acid amide solvents has a pour point, determined according to DIN ISO 3016, in the range from -100 to 20 °C, more preferably in the range from -60 to 15 °C, most preferably in the range from -40 to 10 °C.
  • At least one fatty acid amide solvent preferably each of the fatty acid amide solvents, has a pour point, determined according to DIN ISO 3016, in the range from -100 to 20 °C, more preferably in the range from -60 to 15 °C, most preferably in the range from -40 to 10 °C.
  • At least one fatty acid amide solvent preferably each of the fatty acid amide solvents has a flash point, determined according to ISO 2719, of at least 40 °C, more preferably at least 70 °C, more preferably of at least 100 °C, most preferably at least 130 °C.
  • At least one fatty acid amide solvent preferably each of the fatty acid amide solvents has a water solubility of less than or equal to 1.00% w/w, more preferably of less than or equal to 0.50% w/w, most preferably of less than or equal to 0.20 % w/w.
  • At least one fatty acid amide solvent is selected from the group consisting of dimethyl hexanamide, dimethyl heptanamide, dimethyl octanamide, dimethyl nonanamide, dimethyl decanamide, dimethyl undecanamide, dimethyl dodecanamide, dimethyl tridecanamide, dimethyl tetradecanamide, dimethyl pentadecanamide, dimethyl hexadecanamide, dimethyl heptadecanamide, dimethyl octadecanamide, dimethyl nonadecanamide, dimethyl icosanamide and unsaturated variants thereof, such as dimethyl soyate amide, dimethyl canolate amide and dimethyl oleanamide, as well as fatty acid dimethylamide mixtures, such as C 6 -C 10 fatty acid dimethylamide and C 12 -C 18 fatty acid dimethylamide, and combinations of any of the above.
  • the fatty acid moiety of at least one of the fatty acid amide solvents, preferably each of the fatty acid amide solvents, is a saturated fatty acid.
  • the water immiscible solvent is selected from the group consisting of alkyl esters of saturated or unsaturated fatty acids and mixtures thereof, more preferably methyl esters of saturated or unsaturated fatty acids and mixtures thereof.
  • the saturated or unsaturated fatty acids preferably have from 5 to 20 carbon atoms, more preferably 7 to 17 carbon atoms, most preferably 9 to 14 carbon atoms.
  • At least one of, more preferably each of, the one or more fatty acid ester solvents are selected from the group consisting of methyl esters of C 5 to C 20 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid ester solvents are selected from the group consisting of alkyl esters of C 7 to C 17 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid ester solvents are selected from the group consisting of methyl esters of C 7 to C 17 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid ester solvents are selected from the group consisting of alkyl esters of C 9 to C 14 saturated or unsaturated fatty acids.
  • At least one of, more preferably each of, the one or more fatty acid ester solvents are selected from the group consisting of methyl esters of C 9 to C 14 saturated or unsaturated fatty acids.
  • at least one fatty acid ester solvent, preferably each of the fatty acid ester solvents has a flash point, determined according to ISO 2719, of at least 40 °C, more preferably of at least 50 °C, most preferably at least 60 °C.
  • At least one fatty acid ester solvent preferably each of the fatty acid ester solvents has a water solubility of less than or equal to 4.00% w/w, more preferably of less than or equal to 2.00% w/w, most preferably of less than or equal to 1.00 % w/w.
  • At least one fatty acid ester solvents preferably each of the fatty acid ester solvents has a melting temperature in the range from -100 to 40 °C, more preferably in the range from -80 to 20 °C, most preferably in the range from -70 to 10 °C.
  • the fatty acid moiety of at least one of the fatty acid ester solvents, preferably each of the ester solvents, is a saturated fatty acid.
  • water immiscible solvents are comprised in the formulation in an amount of 15 to 90 wt%, preferably 20 to 85, or 30 to 80 wt%, in each case based on the formulation.
  • the ratio of water immiscible solvents to gamma-valerolactone in the formulations is higher than 0.7, preferably higher than 1.0. In one embodiment the ratio of water immiscible solvents to gamma-valerolactone in formulations of the invention 0.7 to 5 or 0.7 to 3. In one embodiment the ratio of water immiscible solvents to gamma- valerolactone in formulations of the invention 1.0 to 5 or 1.0 to 3.
  • Formulations of the invention comprise surfactants.
  • Surfactants inter alia support the emulsification of the formulation upon its dilution with water. Some surfactants can also act as adjuvants.
  • formulations of the invention comprise one or more anionic and/or nonionic surfactant.
  • Formulations of the invention typically comprise nonionic surfactants.
  • formulations of the invention comprise a mixture of anionic and nonionic surfactants.
  • anionic and/or nonionic surfactant can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant.
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • formulations of the invention comprise anionic surfactants selected from alkylated aromatic sulfonates, sulfonates of dialkylsuccinic esters, tristyryl phenol ethoxylate sulfate or mixtures thereof.
  • formulations of the invention comprise anionic surfactants selected from salts of alkyl benzene sulfonate, especially dodecyl benzene sulfonate, especially calcium dodecyl benzene sulfonate, dioctyl sul-fosuccinates, especially sodium dioctyl sulfosuccinate, tristyryl phenol ethoxylate sulfate, especially tristyryl phenol ethoxylate sulfate comprising 10 to 20 ethyleneoxy units, or mixtures thereof.
  • anionic surfactants selected from salts of alkyl benzene sulfonate, especially dodecyl benzene sulfonate, especially calcium dodecyl benzene sulfonate, dioctyl sul-fosuccinates, especially sodium dioctyl sulfosuccinate, tristyryl phenol e
  • formulations of the invention comprise anionic surfactants selected from linear alkyl benzene sulfonate, e.g. calcium dodecyl benzene sulfonate.
  • Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vi nyla Icohols, or vinylacetate.
  • R 1 and R 2 are independently a C 6 -C 32 hydrocarbon group
  • AO 1 and AO 2 are independently a C 2 -C 6 alkyleneoxy group
  • n and m are independently a value from 2 to 100.
  • the surfactant is of the formula (I) where R 1 and R 2 are independently a linear or branched, saturated or unsaturated C 8 -C 20 alkyl, AO 1 and AO 2 are ethyleneoxy, and n and m are independently from 2.5 to 20.
  • the surfactant is of the formula (I) where R 1 and R 2 are 2-propyl heptyl, AO 1 and AO 2 are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently from 2 to 30. In one embodiment the surfactant is of the formula (I) where R 1 and R 2 are independently linear C 12 -C 18 alkyl, AO 1 and AO 2 are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently from 2 to 30.
  • the surfactant is of the formula (I) where R 1 and R 2 are independently branched C 13 alkyl, AO 1 and AO 2 are independently ethyleneoxy, or ethyleneoxy and propyleneoxy, and n and m are independently from 2 to 30.
  • the surfactant is of formula (I), AO 1 and AO 2 being ethyleneoxy, R 1 and R 2 being a linear or branched, saturated or unsaturated C 8 -C 20 alkyl, and n and m are independently from 2.5 to 20
  • the surfactant is of formula (I), AO 1 and AO 2 being ethyleneoxy, R 1 and R 2 being a linear or branched, saturated or unsaturated C 8 -C 20 alkyl, and n and m are independently from 3 to 10.
  • the surfactant is of formula (I), AO 1 and AO 2 being ethyleneoxy, R 1 and R 2 being a linear or branched, saturated or unsaturated C 8 -C 20 alkyl, and n and m are independently from 3 to 10.
  • the surfactant of formula (I), where AO 1 and AO 2 are ethyleneoxy This form corresponds to the alkoxylate of formula (II)
  • the surfactant is of formula (II), R 1 and R 2 being a linear or branched, saturated or unsaturated C 12 -C 18 alkyl, and n and m are independently from 4 to 9.
  • the surfactant are compounds according to formula (II) wherein R 1 and R 2 are C 12 -C 18 alkyl and n and m are 6 to 8.
  • the surfactant are compounds according to formula (II) wherein R 1 and R 2 are C 12 -C 18 alkyl and n and m are 6.5 to 7.5.
  • formulations of the invention comprise 2 to 15 wt% of at least one surfactant of formula (I) and 0 to 15 wt% of at least one anionic and/or nonionic surfactant different from surfactant C
  • formulations of the invention comprise 2 to 15 wt% of at least one surfactant of formula (I) and 2 to 15 wt% of at least one anionic and/or nonionic surfactant different from surfactant C
  • formulations of the invention comprise at least one surfactant of the general formula (the adju-vant is of the formula (III)
  • R 1 is a C 12-20 alkyl
  • EO is ethyleneoxy
  • PO is propyleneoxy
  • m has a value from 1 to 20
  • n has a value from 1 to 30
  • o has a value from 1 to 10.
  • R 1 in formula (III) is a linear or branched C 14-20 alkyl, the index m is from 2 to 15, the index n is from 5 to 30 and the index o is from 3 to 10.
  • R 1 formula (III) is a linear C 14-18 alkyl, the index m is from 3 to 15, the index n is from 9 to 25 and the index o is from 3 to 6.5.
  • R 1 formula (III) is a linear or branched C 16-18 alkyl, the index m is from 3 to 8, the index n is from 11 to 20 and the index o is from 3.5 to 5.5.
  • formulations of the invention comprise at least one surfactant of the general formula (IV)
  • R 2 is a C 6-n alkyl
  • EO is ethyleneoxy
  • PO is propyleneoxy
  • x has a value from 1 to 20
  • y has a value from 1 to 30
  • z has a value from 0 to 10.
  • R 2 in formula (IV) is usually a linear or branched (preferably branched) monovalent C 6-n aliphatic hydrocarbon group, or a mixture thereof, preferably a linear or branched C 8-10 aliphatic hydrocarbon group. More preferably, R 2 is a linear or branched, saturated or unsaturated C 8-10 aliphatic hydrocarbon group, especially preferred linear or branched C 10 alkyl, or a mixture thereof. Typical examples for R 2 are linear or branched (preferably branched) hexyl, heptyl, octyl, nonyl, decyl and undecyl, or a mixture of the aforementioned residues.
  • R 2 is linear or branched (preferably branched) octyl, nonyl and decyl, or a mixture of the aforementioned resi-dues.
  • R 2 is linear or branched decyl, or a mixture of the aforementioned residues.
  • R 2 is 2-propylheptyL
  • R 2 is a linear or branched (preferably branched) hexyl, heptyl, octyl, nonyl, decyl and undecyl, or a mixture of the aforementioned residues; x has a value from 1 to 20; y has a value from 1 to 30; and z has a value from 1 to 10.
  • R 2 is a linear or branched (preferably branched) hexyl, heptyl, octyl, nonyl, decyl and undecyl, or a mixture of the aforementioned residues; x has a value from 3 to 15; y has a value from 2 to 10; and z has a value from 1.5 to 8.
  • R 2 is a linear or branched (preferably branched) hexyl, heptyl, octyl, nonyl, decyl and undecyl, or a mixture of the aforementioned residues; x has a value from 4 to 8; y has a value from 3 to 6; and z has a value from 2 to 4.
  • R 2 is a branched hexyl, heptyl, octyl, nonyl, decyl and undecyl, or a mixture of the aforementioned residues; x has a value from 5 to 6; y has a value from 4 to 5; and z has a value from 2 to 3.
  • R 2 is a C 8 -n alkyl; x has a value from 2 to 15; y has a value from 2 to 15; and z has a value of 0.
  • R 2 is a C 9-n alkyl; x has a value from 3 to 10; y has a value from 3 to 10; and z has a value of 0.
  • formulations of the invention comprise at least one surfactant that is a polyalkylene oxide block copolymer.
  • formulations of the invention comprise at least one surfactant that is a block polymer surfactant.
  • the block polymer surfactant may be a diblock polymer or a triblock polymer, wherein the triblock polymer is preferred.
  • the blocks of the block polymer surfactant may be of the A-B or A-B-A type, where the A-B-A type is preferred.
  • the block polymers surfactant is a nonionic surfactant.
  • formulations of the invention comprise at least one surfactant that is an alkoxylate block polymer, which may comprise blocks of polyethylene oxide and polypropylene oxide.
  • the alkoxylate block polymers comprise usually at least 20 wt%, preferably at least 30 wt% of polymerized ethylene oxide. In a preferred form the alkoxylate block polymers comprise at least 10 wt%, preferably at least 15 wt% of polymerized ethylene oxide.
  • the alkoxylate block polymers is preferably a block polymers A-B-A type comprising blocks of polyethylene oxide (block “A”) and polypropylene oxide (block “B”).
  • the alkoxylate block polymers are in one embodiment terminated on both ends by hydroxyl groups.
  • the alkoxylate block polymers terminated on both ends by alkyl groups like methyl, ethyl or butyl. In one embodiment, the alkoxylate block polymers terminated on both ends by n-butyl groups. In one embodiment, the alkoxylate block polymers terminated on one end a hydroxy group and on one end by alkyl groups like methyl, ethyl or butyl.
  • the molecular weight of the block polymer surfactant (e.g. the alkoxylate block polymer) may be from 1000 to 30000 Da, preferably from 2000 to 15000 Da.
  • the block polymer surfactant e.g. the alkoxylate block polymer
  • the block polymer surfactant may have a solubility in water at 20 °C of at least 3 wt%, preferably at least 5 wt%, and in particular at least 8 wt%.
  • the block polymer surfactant (e.g. the alkoxylate block polymer) may have a HLB value in the range from 8 to 22, preferably from 10 to 20.
  • the block polymer surfactant (e.g. the alkoxylate block polymer) may have a HLB value in the range from 1 to 10, preferably from 1 to 8.
  • the HLB may be calculated by known methods.
  • the block polymer surfactant is an alkoxylate block polymer of the A-B- A type comprising blocks of polyethylene oxide (block “A”) and polypropylene oxide (block “B”), and wherein the alkoxylate block polymer is terminated on both ends by hydroxyl groups.
  • the surfactant is an alkoxylated alcohol.
  • the alkoxylate is a short chain alkoxylated alkanol, which is an alkoxylated alkanol of the formula I, in which R a is straight-chain or branched alkyl with from 1 to 8, preferably from 2 to 6, and in particular 3 to 5 carbon atoms.
  • the alkoxylate is a short chain alkoxylated alkanol, which is an alkoxylated alkanol of the for-mula II, in which R b is straight-chain or branched alkyl with from 1 to 8, preferably from 2 to 6, and in particular 3 to 5 carbon atoms.
  • the composition may comprise at least 0.1 wt%, at least 0.5 wt%, preferably at least 1 wt%, and in particular at least 1.5 wt% of the short chain alkoxylated alkanol.
  • the composition may comprise from 0.1 to 20 wt%, preferably from 0.5 to 15 wt%, and in particular from 1 to 8 wt% of the short chain alkoxylated alkanol.
  • formulations of the invention comprise non-ionic surfactants selected from alkoxylates, preferably selected from block copolymers of ethylene oxide and propylene oxide, alkoxylates of mono or disaccharides, alkoxylates of fatty alcohols, alkoxylates of vegetable oils, alkoxylates of fatty acids or mixtures thereof.
  • non-ionic surfactants selected from alkoxylates, preferably selected from block copolymers of ethylene oxide and propylene oxide, alkoxylates of mono or disaccharides, alkoxylates of fatty alcohols, alkoxylates of vegetable oils, alkoxylates of fatty acids or mixtures thereof.
  • formulations of the invention comprise non-ionic surfactants selected from alkoxylates, preferably selected from block copolymers of ethylene oxide and propylene oxide, alkoxylates of mono or disaccharides, alkoxylates of fatty alcohols, a I koxy lates of vegetable oils, alkoxylates of fatty acids or mixtures thereof and anionic surfactants selected from alkylated aromatic sulfonates, sulfonates of dialkyl succinic esters, tristyryl phenol ethoxylate sulfate or mixtures thereof.
  • non-ionic surfactants selected from alkoxylates, preferably selected from block copolymers of ethylene oxide and propylene oxide, alkoxylates of mono or disaccharides, alkoxylates of fatty alcohols, a I koxy lates of vegetable oils, alkoxylates of fatty acids or mixtures thereof and anionic surfactants selected from alkylated aromatic sulfonates, s
  • formulations of the invention comprise non-ionic surfactants selected from alkoxylates, preferably selected from block copolymers of ethylene oxide and propylene oxide, alkoxylates of mono or disaccharides, alkoxylates of fatty alcohols, alkoxylates of vegetable oils, alkoxylates of fatty acids or mixtures thereof and anionic surfactants selected from salts of alkyl benzene sulfonate, especially dodecyl benzene sulfonate, especially calcium do-decyl benzene sulfonate, dioctyl sulfosuccinates, especially sodium dioctyl sulfosuccinate, tristyryl phenol ethoxylate sulfate, especially tristyryl phenol ethoxylate sulfate comprising 10 to 20 ethyleneoxy units, or mixtures thereof.
  • anionic surfactants selected from alkyl benzene sulfonate,
  • formulations of the invention comprise 1 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt% and even more preferably 3 to 18 wt% of surfactants, in each case based on the formulation.
  • formulations of the invention comprise 1 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt% and even more preferably 3 to 18 wt% of anionic and/or nonionic surfactants, in each case based on the formulation.
  • formulations of the invention comprise: a. 0.1 to 70 wt% of one or more pesticides P, b. 1 to 40 wt% of gamma-valerolactone, c. 0 to 30 wt% of further water miscible solvents different from gamma-valerolactone, d. 15 to 90 wt% of water immiscible solvents, e. 1 to 40 wt% of surfactants.
  • formulations of the invention comprise: a. 0.1 to 70 wt% of one or more pesticides P, b. 1 to 40 wt% of gamma-valerolactone, c. 0 to 30 wt% of further water miscible solvents different from gamma-valerolactone, d. 15 to 90 wt% of water immiscible solvents, e. 1 to 40 wt% of surfactants, where the ratio of said water immiscible solvent to gamma-valerolactone is higher than 0.7, preferably higher than 1.0.
  • formulations of the invention comprise: a. 0.1 to 70 wt% of one or more pesticides P, b. 1 to 35 wt% of gamma-valerolactone, c. 0 to 20 wt% of further water miscible solvents different from gamma-valerolactone, d. 15 to 90 wt% of water immiscible solvents, e. 1 to 40 wt% of surfactants, comprising a mixture of anionic and nonionic surfactants.
  • formulations of the invention comprise: a. 0.1 to 70 wt% of one or more pesticides P, b. 1 to 35 wt% of gamma-valerolactone, c. 0 to 20 wt% of further water miscible solvents different from gamma-valerolactone, d. 15 to 90 wt% of water immiscible solvents, e. 1 to 40 wt% of surfactants, comprising a mixture of anionic and nonionic surfactants, where the ratio of said water immiscible solvent to gamma-valerolactone is higher than 0.7, preferably higher than 1.0.
  • formulations of the invention comprise: a. 0.1 to 70 wt% of one or more pesticides P, b. 1 to 40 wt% of gamma-valerolactone, c. 0 to 10 wt% of further water miscible solvents different from gamma-valerolactone, d.
  • water immiscible solvents selected from benzyl benzoate, benzyl acetate, benzyl alcohol, dipropylenegly-col dibenzoate, methyl oleate, fatty acid N,N- dimethylamides, fatty acid methyl esters, dialkyl adipates, alkyl lactic esters, propylene glycol dibenzoate, dipropylene glycol dibenzoate, tris-alkyl phosphoric esters, aromatic hydrocarbons, Benzylacetate, methyl oleate or mixtures thereof, e. 1 to 40 wt% of surfactants, comprising a mixture of anionic and nonionic surfactants.
  • surfactants comprising a mixture of anionic and nonionic surfactants.
  • formulations of the invention comprise: a. 0.1 to 70 wt% of one or more pesticides P, b. 1 to 40 wt% of gamma-valerolactone, c. 0 to 10 wt% of further water miscible solvents different from gamma-valerolactone, d.
  • water immiscible solvents selected from benzyl benzoate, benzyl acetate, benzyl alcohol, dipropylenegly-col dibenzoate, methyl oleate, fatty acid N,N- dimethylamides, fatty acid methyl esters, dialkyl adipates, alkyl lactic esters, propylene glycol dibenzoate, dipropylene glycol dibenzoate, tris-alkyl phosphoric esters, aromatic hydrocarbons, Benzylacetate, methyl oleate or mixtures thereof, e.
  • water immiscible solvents selected from benzyl benzoate, benzyl acetate, benzyl alcohol, dipropylenegly-col dibenzoate, methyl oleate, fatty acid N,N- dimethylamides, fatty acid methyl esters, dialkyl adipates, alkyl lactic esters, propylene glycol dibenzoate, dipropylene glycol dibenz
  • surfactants comprising a mixture of anionic and nonionic surfactants, where the ratio of said water immiscible solvent to gamma-valerolactone is higher than 0.7, preferably higher than 1.0.
  • the aqueous compositions according to the invention may also comprise further customary formulation auxiliaries different from anionic or non-ionic surfactants.
  • further auxiliaries include such as viscosity-modifying additives (thickeners), antifoam agents, preservatives, buffers, inorganic dispersants, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders etc., which are usually employed in aqueous formulations active ingredients.
  • the amount of auxiliaries will typically not exceed 25 wt% or 10% by weight, in particular 5% by weight of the total weight of the formulation.
  • Antifoam agents suitable for the compositions according to the invention are, for example, silicone emulsions (such as, for example, Silicone SRE-PFL from Wacker or Rhodorsil® from Bluestar Silicones), polysiloxanes and modified polysiloxanes including polysiloxane blockpolymers such as FoamStar® SI and FoamStar® ST products of BASF SE, long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • silicone emulsions such as, for example, Silicone SRE-PFL from Wacker or Rhodorsil® from Bluestar Silicones
  • polysiloxanes and modified polysiloxanes including polysiloxane blockpolymers such as FoamStar® SI and FoamStar® ST products of BASF SE, long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • compositions of the invention may also contain one or more adjuvants different from anionic or nonionic surfactants.
  • Suitable adjuvants are known to skilled persons and include surfactants, crop oil concentrates, spreader-stickers, wetting agents, and penetrants.
  • Suitable further surfactants are surface-active compounds, such as cationic, amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof.
  • Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.l: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North Ameri-can Ed.).
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of poly-ethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water-soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, bio-logical or synthetic waxes, and cellulose ethers.
  • Formulations of the invention are normally clear solutions at 20 °C. Upon dilution with water, for example in a ratio of 1 to 400 or more, they form an emulsion of droplets of said water immiscible solvent that are emulsified in the aqueous phase and where pesticide P is at least partially dissolved in said emulsified droplets of said water immiscible solvent.
  • Formulations of the invention are preferably stable in liquid form at 21 °C for at least 2 weeks.
  • Formulations of the invention are preferably stable in liquid form at -5 °C for at least 24 hours.
  • the formulations of the invention have a flash point, determined according to ISO 2719, of at least 40 °C, more preferably of at least 50 °C, most preferably at least 60 °C.
  • EW emulsion- in-water
  • the stability of an emulsion-in-water formulation may be evaluated by determining how much sedimentation or cream is formed following homogenization (i.e. following emulsification). Both cream and sedimentation represent a departure from idealized emulsion behavior, where the disperse particles either rise to the surface (creaming) or sink to the bottom (sedimentation) depending on their density. When determining the extent of creaming or sedimentation, it is not critical whether the emulsified droplets remain as such or aggregate to form a new continuous phase - both are sufficient to determine that the emulsion has broken down.
  • a stable emulsion is viewed as an emulsion that forms less than or equal to a given amount of cream and/or sedimentation 24 hours after homogenization.
  • the formulations of the invention are suitable for forming a wide range of emulsion-in-water (EW) formulations, when mixed with water and homogenized, which demonstrate unexpectedly beneficial emulsion stability.
  • EW emulsion-in-water
  • a model emulsion system comprising 5.0 mL of the formulation of the invention and 95.0 mL of water
  • a stable emulsion is defined as an emulsion that produces less than or equal to 1.5 mL of cream or sediment, 24 hours after formation of said emulsion.
  • the formulations of the invention form a stable emulsion when 5.0 mL of said formulation of the invention is combined with 95.0 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 1.5 mL of cream or sediment, 24 hours after formation of said emulsion.
  • the emulsion forms less than or equal to 1.0 mL of cream or sediment, 24 hours after formation of said emulsion. Most preferably the emulsion forms less than or equal to 0.5 mL of cream or sediment, 24 hours after formation of said emulsion.
  • the emulsion may be re-homogenized, i.e. re-emulsified, to reform a stable emulsion, wherein a stable emulsion is as defined as above, wherein less than or equal to 1.5 mL of cream or sediment is formed 30 minutes after re-homogenization, more preferably wherein less than or equal to 1.0 mL of cream or sediment is formed 30 minutes after rehomogenization, most preferably wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after re-homogenization.
  • the homogenization is carried out by gentle inversion of the emulsion 10 times and that the re-homogenization is likewise carried out by gentle inversion of the emulsion 10 times.
  • formulations of the invention comprise 0 to 10 wt%. preferably 0.1 to 10, more preferably 1 to 10 wt% of further formulation auxiliaries different from anionic and/or nonionic surfactants, in each case based on the formulation.
  • Another aspect of the present invention are processes for making formulations of the invention.
  • Formulations of the invention are typically prepared by contacting components a. to e. as well as optionally any further formulation auxiliaries.
  • Another aspect of the present invention are non-therapeutic methods of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the liquid formulations of the invention are allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
  • Another aspect of the present invention are seeds containing the formulations of the invention.
  • compositions of the invention are suitable for the purposes of treatment of plant propagation materials, particularly seeds.
  • the formulations in question give, after two-to- tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating the pesticide and formulations thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the pesticide or the formulations thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most prefer-ably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the formulations comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the formulations according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • the concentration of the alkoxylate of the formula (I) in the ready-to-use preparation is in most cases in the range of from 0.01 to 50 g/L, preferably 0.08 to 10 g/L and in particular 0.5 to 8 g/L.
  • the concentration of water in the ready-to-use preparation is in most cases at least 60 wt%, preferably at least 75 wt%, and in particular at least 90 wt%.
  • the tank mix is usually an aqueous liquid, which is ready to be applied (e.g. by spraying) in the method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants.
  • the user applies the formulation according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, a drone, an unmanned aerial vehicle or an irrigation system.
  • the agrochemical formulation is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical formulation according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • individual components of the formulation according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the formulation according to the invention or partially pre-mixed components e. g. components comprising the pesticide and the adjuvant
  • either individual components of the formulation according to the invention or partially premixed components, e. g. components comprising the pesticide and/or the adjuvant can be applied jointly (e.g. after tank mix) or consecutively.
  • the present invention furthermore relates to a method of preparing the formulation according to the invention by bringing the adjuvant of the formula (I) and the pesticide into contact, e.g. by mixing.
  • the contacting may be done between 5 to 95 °C.
  • a tank mix or an agrochemical formulation may be prepared.
  • the present invention furthermore relates to a non-therapeutic method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the liquid formulations of the invention are allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
  • suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and
  • crop plants also includes those plants which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed.
  • Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material).
  • one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant’s properties.
  • Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of glycosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.
  • the present invention also relates to seed (such as seeds or other plant propagation materials) comprising the formulation according to the invention or that have been treated with formulations of the invention.
  • Plant propagation materials can be treated preventively with the formulation according to the invention at the point of or even before sowing or at the point of or even before transplanting.
  • the formulations of the invention can be applied to the propagation materials, in particular seed, in undiluted form or, preferably, in diluted form.
  • the formulation in question can be diluted 2- to 10 fold, so that from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, of active substance is present in the formulations used for the seed dressing.
  • the application may be effected before or during sowing.
  • the treatment of plant propagation material in particular the treatment of seed, is known to the skilled worker and carried out by dusting, coating, pelleting, dipping or soaking the plant propagation material, the treatment preferably being carried out by pelleting, coating and dusting or by in-furrow treatment so that, for example, untimely early germination of the seed is prevented.
  • suspensions for the treatment of seed.
  • formulations comprise from 1 to 800 g/L of active substance, from 1 to 200 g/L of surfactants, from 0 to 200 g/L of antifreeze agents, from 0 to 400 g/L of binders, from 0 to 200 g/L of colorants and solvent, preferably water.
  • the advantages of the invention include high stability of the formulation and of the spray mixture, little formation of precipitate and/ or crystalline pesticide, easy applicability, little clogging of spraying equipment, good emulsifiability of the formulation in water, high biological activity, increased solubility of the pesticides in the formulation, increased uptake of the pesticides into the plant.
  • Other advantages are the low toxicity of the components, the low harmful effect against crop plants, i.e. low phytotoxic effects.
  • the formulations of the invention are particularly suitable for forming highly stable emulsion-in-water (EW) formulations.
  • the present invention is directed to an emulsion-in-water (EW) formulation, comprising an aqueous phase and a non-aqueous phase, wherein the nonaqueous phase is a formulation as described above.
  • EW emulsion-in-water
  • the precise amounts of the formulation of the invention and water present in the emulsion- in-water (EW) formulation are not critical; however, it is preferred that the emulsion-in- water (EW) formulation comprises, more preferably consists of, an amount in the range from 0.01 to 80.0% w/w of the formulation of the invention and an amount in the range of from 20.0 to 99.99% w/w of water, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.
  • the emulsion-in-water (EW) formulation comprises, more preferably consists of, an amount in the range from 0.1 to 50.0% w/w of the formulation of the invention and an amount in the range of from 50.0 to 99.9% w/w of water, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.
  • the emulsion-in-water (EW) formulation comprises, more preferably consists of, an amount in the range from 0.5 to 5.0% w/w of the formulation of the invention and an amount in the range of from 95.0 to 99.5% w/w of water, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.
  • the emulsion-in-water (EW) formulation may further contain adjuvants conventionally used for agrochemical formulations (co-called tank adjuvants), the choice of the adjuvants depending on the specific use form, the type of formulation or the active substance.
  • adjuvants conventionally used for agrochemical formulations (co-called tank adjuvants), the choice of the adjuvants depending on the specific use form, the type of formulation or the active substance.
  • Suitable adjuvants are surface-active substances (such as solubilisers, protective colloids, wetters and tackifiers), retention agents, wetting agents, spreaders, uptake enhancers, penetration agents, spray drift controllers, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, optionally colorants and adhesives (for example for the treatment of seed) or conventional adjuvants for bait formulations (for example attractants, feedants, bittering substances).
  • surface-active substances such as solubilisers, protective colloids, wetters and tackifiers
  • retention agents such as solubilisers, protective colloids, wetters and tackifiers
  • wetting agents such as solubilisers, protective colloids, wetters and tackifiers
  • retention agents such as solubilisers, protective colloids, wetters and tackifiers
  • wetting agents such as solubilisers, protective colloids, wetters and t
  • the present invention is directed to a use of the emulsion-in-water (EW) formulation as described above for treating crop plants, thereby maintaining plant health.
  • EW emulsion-in-water
  • the present invention is directed to a use of gammavalerolactone (GVL) for improving the emulsion stability of an emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the nonaqueous phase comprises one or more water immiscible solvents.
  • VTL gammavalerolactone
  • the present invention is directed to a use of gamma-valerolactone (GVL) for improving the -5 °C stability of a crop protection composition (CPC) comprising one or more pesticides, one or more water immiscible solvents, and one or more surfactants.
  • VTL gamma-valerolactone
  • CPC crop protection composition
  • the melting temperature of the individual solvents is determined by differential scanning calorimetry (DSC) analysis.
  • pour point The pour point of individual solvents or mixtures of solvents was determined according to DIN ISO 3016. For individual solvents, the pour point is typically 0 to 5 °C higher than the melting point.
  • Flash point The flash point of individual solvents or mixtures of solvents was determined according to ISO 2719 (i.e. Pensky-Martens closed cup method). Values marked with two asterisks (i.e. 130**) were measured using DIN ISO 2592 (i.e. Cleveland open cup method), which typically gives values that are approximately 5-10 °C higher than when ISO 2719 is used.
  • Water solubility The water solubility of a solvent was determined according to a method based on CIPAC MT157.1 and OECD 105 via the assessment of undissolved solvent in water after vigorous mixing and standing. Herein, various amounts of solvent and water were mixed with vigorous shaking in a glass-stoppered graduated cylinder or separating funnel, followed by standing for at least 30 min to enable separation. For example, if undissolved solvent was observed after thorough mixing of 0.1 g solvent in 100 mL of water, the solvent had a water-solubility equal to or below 0.1% ( ⁇ 1 g/L). This method can be repeated with various amounts of solvent and water to enable the determination of the water-solubility of the solvent.
  • Solvesso 200 ND naphthalene depleted blend of C n aromatic hydrocarbons Surfactant SI Calcium dodecyl benzene sulfonate, 60 wt% in ethyl hexanol
  • C 6 fatty acid methyl ester has a Tm of -71 °C and C 10 fatty acid methyl ester has a Tm of -18 °C.
  • CIPAC D water Made in the lab using a standard recipe published by CIPAC “MT 18.1.4”: Standard Waters. The water has a hardness of 342 ppm, with a 4:1 mixture of Ca:Mg ions at pH 6-7.
  • the pesticides The pesticides were purchased from various commercial sources and have the following water solubilities:
  • the formulations obtained in examples 1 to 24 were diluted with CIPAC D standard water to obtain emulsions containing 0.5 wt% of the formulation in water having a temperature of 10 °C.
  • Two liters of the diluted emulsion so obtained were continuously pumped through a cascade of one 300 pm sieve and one 150 pm sieve at an initial flow rate that was set at 100 liters per hour.
  • the circulated spray liquid was in total 5 times replaced with fresh formulation after 1, 2, 2.5 and 4 hours on the first day and upon start of the second day and after 1 hour on the second day. Overall duration of the test was 12 hours over two days (six hours per day).
  • the application properties of the formulations were rated from “++“ to based on the flow of the diluted emulsion through the sieves in the final filtration cycle and visual evaluation of the residue in the sieves.
  • a rating of means that the sieves contained a high amount of residue and a slow flow of the diluted emulsion through the sieve
  • a rating of “++” means essentially unchanged flow of the diluted emulsion through the sieve and that almost no residue was collected in the sieves.
  • the flow at the end of the test had to be 90% or more of the initial flow rate (i.e. at least 90 l/h).
  • Table 1 Composition of examples 1 to 18 [contents in g/L] , density of the formulations was 1.06 g/cm 3
  • Examples CE9 and CE13 are not according to the invention. They did not yield a clear solution, the pesticides were partly insoluble in the solvent mixture at room temperature. All other examples yielded clear solutions.
  • Table 2 Composition of examples 20 to 21 [contents in g/L] , density of the formulations was 1.08 g/cm 3
  • the application test showed in loss of the flow of 13.4 %. In example 21, the application test showed a loss of the flow of 3.6 %.
  • CPC free-flowing crop protection composition
  • CPC free-flowing crop protection composition
  • the emulsion was tested for its dispersibility by the effect known as blooming.
  • the emulsions were assessed according to their spontaneous emulsification when the crop protection composition is added to water (known in the art as "blooming") with a visual assessment given on a scale of 1 to 5, whereby 1). Excellent, “cloud of emulsion”, does not sink to bottom of cylinder. 2). Good, “cloud of emulsion”, but sinks to bottom of cylinder 3). Okay, “poor emulsion cloud”, larger droplets 4). Poor, “no emulsion cloud”, small “particles” observed 5). Very poor, no emulsion, oil and water phases immediately separate.
  • Crop protection compositions were prepared in the following examples and the resulting 5% w/w emulsions in various water hardness at 21 °C after 24 hours were assessed. Emulsion stability was determined as a function of time, with the amount of either cream or sediment measured.
  • emulsion stability To measure emulsion stability, 5.0 mL of the crop protection composition was diluted in 95.0 mL CIPAC D water in a 100 mL measuring cylinder. The resulting oil-in-water emulsion stability was assessed after 1, 2, 4 and 24 hours. A highly stable emulsion does not form cream or sediment or has less than 1.5 mL cream or sediment after 24 hours, and can be readily re-emulsified after 24 h of standing without the formation of cream or sediment, with such re-emulsified emulsions assessed 30 minutes after re-emulsification. Both the initial emulsification and the re-emulsification were achieved by gently inverting the emulsion 10 times. In the following tables Y (i.e. yes) indicates that at most 1.5 mL cream or sediment is observed after 24 hours, whilst N (i.e. no) indicates that more than 1.5 mL cream or sediment is observed after 24 hours.
  • gammavalerolactone as a co-solvent with water immiscible solvents allows for higher pesticide concentrations than when the fatty acid amide is used as a solvent alone.
  • gamma-valerolactone is also beneficial for improving the stability of the crop protection composition at low temperatures.
  • RE7 and RE9 demonstrate the importance of including at least one heteroatom in the water immiscible solvent, since pure hydrocarbon water immiscible solvents have inferior EC stability/homogeneity.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne une formulation liquide contenant : a. un ou plusieurs pesticides P, b. de la gamma-valérolactone, c. éventuellement d'autres solvants miscibles à l'eau différents de la gamma-valérolactone, d. un solvant non miscible à l'eau, e. des tensioactifs, notamment un mélange de tensioactifs anioniques et non ioniques. Le pesticide P est complètement dissous à 20°C et la formulation contient 15 à 90 % en poids dudit solvant non miscible à l'eau, de préférence 20 à 70 % en poids, le rapport dudit solvant non miscible à l'eau à la gamma-valérolactone étant supérieur à 0,7, de préférence supérieur à 1,0.
PCT/EP2025/062620 2024-05-08 2025-05-08 Nouvelles formulations agrochimiques Pending WO2025233453A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110292A2 (fr) 2010-03-09 2011-09-15 Cognis Ip Management Gmbh Compositions biocides comprenant de la valérolactone ou ses dérivés
JP5300114B2 (ja) * 2001-09-26 2013-09-25 クミアイ化学工業株式会社 育苗箱
WO2019052898A1 (fr) * 2017-09-13 2019-03-21 Basf Se Nouvelles formulations agrochimiques
WO2022028944A1 (fr) * 2020-08-07 2022-02-10 Basf Se Formulations agrochimiques
WO2023272790A1 (fr) * 2021-06-28 2023-01-05 迈克斯(如东)化工有限公司 Composition herbicide, son procédé de préparation et son procédé d'application
WO2023111297A1 (fr) * 2021-12-17 2023-06-22 Basf Se Lactones pour améliorer l'activité d'agents antimicrobiens

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Publication number Priority date Publication date Assignee Title
JP5300114B2 (ja) * 2001-09-26 2013-09-25 クミアイ化学工業株式会社 育苗箱
WO2011110292A2 (fr) 2010-03-09 2011-09-15 Cognis Ip Management Gmbh Compositions biocides comprenant de la valérolactone ou ses dérivés
WO2019052898A1 (fr) * 2017-09-13 2019-03-21 Basf Se Nouvelles formulations agrochimiques
WO2022028944A1 (fr) * 2020-08-07 2022-02-10 Basf Se Formulations agrochimiques
WO2023272790A1 (fr) * 2021-06-28 2023-01-05 迈克斯(如东)化工有限公司 Composition herbicide, son procédé de préparation et son procédé d'application
WO2023111297A1 (fr) * 2021-12-17 2023-06-22 Basf Se Lactones pour améliorer l'activité d'agents antimicrobiens

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"Pesticide Manual", 2009, THE BRITISH CROP PROTECTION COUNCIL
GLEN ROCK: "Emulsifiers & Detergents, McCutcheon's Directories", vol. 1, 2008, INTERNATIONAL ED. OR NORTH AMERI-CAN ED
KERKEL FLORIAN ET AL: "The green platform molecule gamma-valerolactone - ecotoxicity, biodegradability, solvent properties, and potential applications", GREEN CHEMISTRY, vol. 23, no. 8, 17 March 2021 (2021-03-17), GB, pages 2962 - 2976, XP093071055, ISSN: 1463-9262, DOI: 10.1039/D0GC04353B *
KNOWLES: "Adjuvants and additives", 2006, T&F INFORMA UK

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