JP2016522822A - Emulsifiable concentrate comprising pesticide, lactone and tri-C1-C6-alkyl phosphate - Google Patents

Abstract

The subject of the present invention relates to an emulsifiable concentrate comprising a water-insoluble pesticide as described herein, a) a lactone and b) a tri-C1-C6-alkyl phosphate. The invention further provides a process for producing said concentrate; an emulsion obtainable by mixing water, a water-insoluble pesticide, components a) and b); and phytopathogenic fungi and / or undesirable vegetation And / or a method for controlling undesired attacks by insects or ticks and / or for regulating plant growth, wherein the concentrate or emulsion is applied to the respective pests, their environment, Or on the crop plants to be protected from the respective pests, on the soil and / or on the undesired plants and / or on the crop plants and / or on their environment . [Selection figure] None

Description

The subject of the present invention relates to an emulsifiable concentrate comprising a water-insoluble pesticide as described herein, a) a lactone, and b) a tri-C ₁ -C ₆ -alkyl phosphate. The present invention further provides a process for producing said concentrate; an emulsion obtainable by mixing water, a water-insoluble pesticide, components a) and b); and phytopathogenic fungi and / or undesirable vegetation And / or a method for controlling undesired attacks by insects or ticks and / or for regulating plant growth, wherein the concentrate or emulsion is applied to the respective pests, their environment, Or on the crop plants to be protected from the respective pests, on the soil and / or on the undesired plants and / or on the crop plants and / or on their environment .

  Emulsifiable concentrates (also referred to as EC) are formulations that are widely used in crop protection. Disadvantages of known emulsion concentrates are inadequate low temperature stability, a significant tendency to crystallize and a low pesticide concentration.

  The object of the present invention is to provide an emulsifiable concentrate that overcomes these disadvantages.

Its purpose is water-insoluble pesticides,
a) a lactone, and
b) Achieved with an emulsifiable concentrate containing tri-C ₁ -C ₆ -alkyl phosphate.

  Generally, an emulsifiable concentrate is taken to mean a composition that mixes with water (eg, in a weight ratio of 1 part concentrate to 99 parts water) to form an oil-in-water emulsion. The emulsion usually occurs spontaneously. In various forms, the resulting emulsion can have an average droplet diameter of greater than 0.1 μm, greater than 0.5 μm, greater than 0.8 μm, or greater than 1.1 μm. This average droplet diameter can be measured by laser diffraction, for example with a Malvern Mastersizer 2000.

  This concentrate is preferably present as a homogeneous solution. It is usually substantially free of dispersed particles.

  Examples of the lactone include γ-butyrolactone (gamma-butyrolactone).

  In various embodiments, the concentrate can comprise at least 5 wt%, at least 20 wt%, at least 35 wt%, or at least 45 wt% lactone (such as γ-butyrolactone). In other embodiments, the concentrate can comprise 80 wt% or less, 70 wt% or less, or 60 wt% or less of a lactone.

An example of tri-C ₁ -C ₆ -alkyl phosphate is tributyl phosphate.

In various embodiments, the concentrate, 60 wt% or less, 45 wt% or less, or 30 wt% or less of phosphoric acid tri -C ₁ -C ₆ - can contain alkyl. In other embodiments, the concentrate can comprise at least 5%, at least 10%, or at least 15% by weight of tri-C ₁ -C ₆ -alkyl phosphate. The tri-C ₁ -C ₆ -alkyl phosphate may be tributyl phosphate.

The concentrate may further comprise a hydrocarbon in addition to the solvent a) lactone and b) tri-C ₁ -C ₆ -alkyl phosphate described above. In various embodiments, the concentrate can include up to 40 wt%, up to 20 wt%, or up to 10 wt% hydrocarbon. In other embodiments, the concentrate can comprise at least 1 wt%, at least 20 wt%, or at least 35 wt% hydrocarbon. Hydrocarbons include aromatic petroleum derivatives (aromatic hydrocarbons) that have a water solubility of less than 0.1% (w / w) and a distillation temperature range of 130 ° C to 300 ° C (under the brand names below) Available: Solvesso ™ 100, Solvesso ™ 150, Solvesso ™ 200, Solvesso ™ 150ND, Solvesso ™ 200ND, Aromatic 150, Aromatic 200, Hydrosol A 200, Hydrosol A 230/270, Caromax (Trade mark) 20, Caromax (trade mark) 28, Aromat K 150, Aromat K 200, Shellsol (trade mark) A 150, Shellsol (trade mark) A 100, Fin FAS-TX 150, Fin FAS-TX 200) . In one embodiment, the hydrocarbon is an aromatic hydrocarbon.

In one embodiment, the concentrate, 5 to 50 wt% lactone (for example, .gamma.-butyrolactone) 10 to 35 wt% of phosphoric acid tri -C ₁ -C ₆ - alkyl (e.g., tributyl phosphate), and Optionally, it can contain 1-40% by weight of hydrocarbons (eg aromatic hydrocarbons), where the amount of these components totals 40-90% by weight.

In another embodiment, a concentrate of 10 to 35 wt% lactone (for example, .gamma.-butyrolactone), 15-25% by weight of phosphoric acid tri -C ₁ -C ₆ - alkyl (e.g., tributyl phosphate), And optionally 2-30% by weight of hydrocarbons (eg aromatic hydrocarbons), where the amount of these components totals 45-80% by weight.

In yet another embodiment, the concentrate, 50-65 wt% of a lactone (e.g., .gamma.-butyrolactone) 20 to 45 wt% tri -C phosphate ₁ -C ₆ - alkyl (e.g., tributyl phosphate) And optionally from 5 to 50% by weight of hydrocarbons (eg, aromatic hydrocarbons), where the amount of these components totals 50 to 95% by weight.

  In most cases, the concentrate does not contain water. In another form, the concentrate is substantially free of water. In various embodiments, the concentrate can comprise 3 wt% or less, 1 wt% or less, or 0.5 wt% or less of water. In another embodiment, the concentrate may contain no more than 0.3 wt% water, and in different forms no more than 0.1 wt% water.

  The concentrate may contain additional solvents (eg, organic solvents listed below) in addition to components a), b), and hydrocarbons. In various embodiments, the concentrate can include up to 30 wt%, up to 10 wt%, or up to 1 wt% of additional solvent.

  The term pesticide refers to at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators. Pesticides include fungicides, insecticides, herbicides and growth regulators. In one embodiment, the pesticide is a fungicide. Mixtures of pesticides from two or more of the above types can also be used. Those skilled in the art are familiar with such pesticides, for example, “Pesticide Manual, 15th edition, (2009), The British Crop Protection Council, “London”, the entire contents of which are incorporated herein by reference. As an example, the following pesticides are suitable (pesticides A) to K) are fungicides):

A) Respiratory inhibitor
- Q _o inhibitor of Complex III at the site (e.g., strobilurin): azoxystrobin, click methoxy Azoxystrobin, spider azoxystrobin, dimoxystrobin, enestroburin, phenazine Minsuto Robin, phenoxy cysts Robin / Fluphenoxystrobin, Fluoxastrobin, Cresoxime-methyl, Metominostrobin, Orisastrobin, Picoxystrobin, Pyraclostrobin, Pyrametostrobin, Pyroxystrobin, Trifloxystrobin, 2- [2- (2 , 5-dimethylphenoxymethyl) phenyl] -3-methoxyacrylic acid methyl ester, and 2- (2- (3- (2,6-dichlorophenyl) -1-methyl-allylideneaminooxymethyl) phenyl) -2- Methoxyimino-N-methyl-acetamide, Pyribencarb, Triclopyricarb / Chlorozine carb, Famoki Don, fenamidone;
-Inhibitors of complex III at Q _i site: cyazofamid, amisulbrom, [(3S, 6S, 7R, 8R) -8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl) amino ] -6-Methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S, 6S, 7R, 8R) -8-benzyl-3-[[3- (Acetoxymethoxy) -4-methoxy-pyridin-2-carbonyl] amino] -6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S, 6S , 7R, 8R) -8-Benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl) amino] -6-methyl-4,9-dioxo-1,5-dioxonan- 7-yl] 2-methylpropanoate, [(3S, 6S, 7R, 8R) -8-benzyl-3-[[3- (1,3-benzodioxol-5-ylmethoxy) -4-methoxy -Pyridin-2-carbonyl] amino] -6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate; (3S, 6S, 7R, 8R) -3-[[(3-Hydroxy-4-methoxy-2-pyridinyl) carbonyl] amino] -6-methyl-4,9-dioxo-8- (phenylmethyl) -1,5- Dioxonan-7-yl 2-methylpropanoate
-Inhibitors of complex II (e.g. carboxamides): benodanyl, benzobindiflupyr, bixafen, boscalid, carboxin, fenfram, fluopyram, flutolanil, fluxapiloxad, flametopyr, isopyrazam, mepronil, oxycarboxyl, penflufen , Pentiopyrad, sedaxane, teclophthalam, tifluzamide, N- (4′-trifluoromethylthiobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N- (2- (1, 3,3-trimethyl-butyl) phenyl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- (1,1,3-trimethyl Indan-4-yl) pyrazole-4-carboxamide, 3- (trifluoromethyl) -1-methyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide, 3- (trifluoromethyl) -1,5-dimethyl-N- (1,1 , 3-Trimethylindan-4-yl) pyrazole-4-carboxamide, 3- (difluoromethyl) -1,5-dimethyl-N- (1,1,3-trimethylindan-4-yl) -pyrazol-4- Carboxamide, 1,3,5-trimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide;
-Other respiratory inhibitors (e.g. complex I, uncoupler): diflumetrim, (5,8-difluoroquinazolin-4-yl)-{2- [2-fluoro-4- (4-trifluoromethylpyridine) -2-yloxy) -phenyl] -ethyl} -amine; nitrophenyl derivatives; binapacryl, dinobutone, dinocup, fluazinam; ferrimzone; organometallic compounds: fentin salts such as fentin acetate, fentin chloride or hydroxylated fentin; amethocrazine; And silthiofam;

B) Sterol biosynthesis inhibitor (SBI fungicide)
-C14-demethylase inhibitor (DMI fungicide): Triazole: Azaconazole, Vitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Diniconazole-M, Epoxyconazole, Fenbuconazole, Fluquinconazole, Flucilazole, Flutria Hole, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, cimeconazole, tebuconazole, tetraconazole, triadimethone, triadimenol, Triticonazole, Uniconazole, 1- [rel- (2S; 3R) -3- (2-Chlorophenyl) -2- (2,4-difluorophenyl) -oxiranylmethyl] -5-thiocyanato-1H- [1 , 2,4] triazole, 2 -[rel- (2S; 3R) -3- (2-chlorophenyl) -2- (2,4-difluorophenyl) -oxiranylmethyl] -2H- [1,2,4] triazole-3-thiol; Imidazole: imazalyl, pefrazoate, prochloraz, triflumizole; pyrimidine, pyridine and piperazine: phenalimol, nuarimol, pyrifenox, triphorin;
-Delta 14 reductase inhibitors: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperaline, spiroxamine;
-3-keto reductase inhibitors: phenhexamide;

C) Nucleic acid synthesis inhibitor
-Phenylamide or acylamino acid fungicides: Benalaxyl, Benalaxyl-M, Kiraraxyl, Metalaxyl, Metalaxyl-M (Mefenoxam), Offrace, Oxadixyl;
-Others: Himexazole, Octynone, Oxophosphoric acid, Bupyrimate, 5-Fluorocytosine, 5-Fluoro-2- (p-tolylmethoxy) pyrimidin-4-amine, 5-Fluoro-2- (4-fluorophenylmethoxy) pyrimidine 4-amine;

D) Inhibitors of cell division and cytoskeleton
-Tubulin inhibitors (e.g. benzimidazoles, thiophanates): benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidine: 5-chloro-7- (4-methylpiperidin-1-yl) -6 -(2,4,6-Trifluorophenyl)-[1,2,4] triazolo [1,5-a] pyrimidine
-Other mitotic inhibitors: dietofencarb, ethaboxam, penccilone, fluopicolide, zoxamide, metolaphenone, pliophenone;

E) Inhibitors of amino acid and protein synthesis
-Methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil;
-Protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride hydrate, myrdiomycin, streptomycin, oxytetracycline, polyoxin, validamycin A;

F) Signal conversion inhibitor
-MAP / histidine kinase inhibitors: fluoroimide, iprodione, procymidone, vinclozolin, fenpiclonyl, fludioxonil;
-G-protein inhibitor: quinoxyphene;

G) Lipid and cell membrane synthesis inhibitors
-Phospholipid biosynthesis inhibitors: edifenphos, iprobenphos, pyrazophos, isoprothiolane;
-Lipid peroxidation: dichlorane, quintozen, technazen, tolcrophos-methyl, biphenyl, chloroneb, etridiazole;
-Phospholipid biosynthesis and cell wall deposition: Dimethomorph, Flumorph, Mandipropamide, Pyrimorph, Bench Avaricarb, Iprovaricarb, Variphenate and N- (1- (1- (4-Cyano-phenyl) ethanesulfonyl) but-2- Yl) carbamic acid- (4-fluorophenyl) ester;
-Compounds affecting cell membrane permeability and fatty acids: propamocarb, propamocarb-hydrochloride-fatty acid amide hydrolase inhibitor: oxathiapiproline;

H) Inhibitor with multi-site action
-Inorganic active substances: Bordeaux liquid, copper acetate, copper hydroxide, basic copper chloride, basic copper sulfate, sulfur;
-Thiocarbamate and dithiocarbamate: Felvam, Mancozeb, Maneb, Metam, Methylam, Propineb, Tiram, Zineb, Zillam;
-Organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafor, captan, phorpet, dichlorofluanide, dichlorophen, fursulfamide, hexachlorobenzene, pentachlorophenol and its salts, phthalide, Tolylfluoride, N- (4-chloro-2-nitro-phenyl) -N-ethyl-4-methylbenzenesulfonamide;
-Guanidine and others: guanidine, dodine, dodin free base, guazatine, guazatine acetate, iminoctadine, iminotazine triacetate, iminoctadine-tris (albesylate), dithianone, 2,6-dimethyl-1H, 5H- [1,4] Dithino [2,3-c: 5,6-c ′] dipyrrole-1,3,5,7 (2H, 6H) -tetraone;

I) Cell wall synthesis inhibitor
-Inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyrokilone, tricyclazole, carpropamide, dicyclomet, phenoxanyl;

J) Plant defense inducer
-Acibenzoral-S-methyl, probenazole, isothianyl, thiazinyl, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;

K) Unknown mode of action
-Bronopol, Quinomethionate, Cyflufenamide, Simoxanyl, Dazomet, Debacarb, Diclomedin, Difenzo Coat, Difenzo Coat Methyl Sulfate, Diphenylamine, Fenpyrazamine, Flumetober, Fursulfamide, Fruthianyl, Metasulfocarb, Nitrapyrin, Nitrotal-isopropyl, Oxathiapiproline, 2- [3 , 5-Bis (difluoromethyl) -1H-pyrazol-1-yl] -1- [4- (4- {5- [2- (prop-2-yn-1-yloxy) phenyl] -4,5- Dihydro-1,2-oxazol-3-yl} -1,3-thiazol-2-yl) piperidin-1-yl] ethanone, 2- [3,5-bis (difluoromethyl) -1H-pyrazol-1- Yl] -1- [4- (4- {5- [2-fluoro-6- (prop-2-yn-1-yloxy) phenyl] -4,5-dihydro-1,2-oxazol-3-yl } -1,3-thiazol-2-yl) piperidin-1-yl] ethanone, 2- [3,5-bi (Difluoromethyl) -1H-pyrazol-1-yl] -1- [4- (4- {5- [2-chloro-6- (prop-2-yn-1-yloxy) phenyl] -4,5- Dihydro-1,2-oxazol-3-yl} -1,3-thiazol-2-yl) piperidin-1-yl] ethanone, oxine-copper, proquinazide, tebufloquine, teclophthalam, triazoxide, 2-butoxy-6-iodo -3-propylchromen-4-one, N- (cyclopropylmethoxyimino- (6-difluoro-methoxy-2,3-difluoro-phenyl) methyl) -2-phenyl-acetamide, N '-(4- (4 -Chloro-3-trifluoromethyl-phenoxy) -2,5-dimethyl-phenyl) -N-ethyl-N-methylformamidine, N '-(4- (4-fluoro-3-trifluoromethyl-phenoxy) -2,5-dimethyl-phenyl) -N-ethyl-N-methylformamidine, N '-(2-methyl-5-trifluoromethyl-4- (3-trimethylsilanyl-propoxy) phenyl) -N- Ethyl-N- Methylformamidine, N '-(5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy) -phenyl) -N-ethyl-N-methylformamidine, 2-methoxy-acetic acid 6-tert -Butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3- [5- (4-methylphenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine, 3- [5- (4-Chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine (pyridoxazole), N- (6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5 -Chloro-1- (4,6-dimethoxy-pyrimidin-2-yl) -2-methyl-1H-benzimidazole, 2- (4-chloro-phenyl) -N- [4- (3,4-dimethoxy- Phenyl) -isoxazol-5-yl] -2-prop-2-ynyloxy-acetamide;

M) Growth regulator
-Abscisic acid, amidochlor, ansimidol, 6-benzylaminopurine, brassinolide, butralin, chlormecote (chlormecote chloride), choline chloride, cyclanilide, daminozide, dikeglac, dimethipine, 2,6-dimethylprizine, ethephone, flumetraline, Flurprimidol, fluthiaset, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthalene acetic acid, N-6-benzyladenine, paclobutrazol, pro Hexadione (prohexadione-calcium), prohydrojasmon, thiazulone, tripentenol, tributyl phosphorotrithioate, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and sea urchin Nazoru;

N) Herbicide
-Acetamide series: acetochlor, alachlor, butachlor, dimethachlor, dimethenamide, flufenacet, mefenaset, metolachlor, metazachlor, napropamide, naproanilide, petoxamide, pretilachlor, propachlor, tenyl chlor;
-Amino acid derivative systems: vilanaphos, glyphosate, glufosinate, sulphosate;
-Aryloxyphenoxypropionate series: clodinahop, cyhalohop-butyl, phenoxaprop, fluazifop, haloxyhop, metamihop, propaxahop, quizalofop, xylohop-P-tefryl;
-Bipyridyl series: Diquat, paraquat;
-(Thio) carbamate series: aslam, butyrate, carbetamid, desmedifane, dimepiperate, eptam (EPTC), esprocarb, molinate, olvencarb, fenmedifam, prosulfocarb, pyributycarb, thiobencarb, trialate;
-Cyclohexanedione series: butroxidim, cretodim, cycloxydim, profoxydim, cetoxydim, teplaloxidim, tolalkoxydim;
-Dinitroaniline series: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
-Diphenyl ether series: acifluorfen, acronifene, bifenox, diclohop, ethoxyphen, fomesafen, lactofen, oxyfluorfen;
-Hydroxybenzonitriles: bromoxynyl, diclobenil, ioxynil;
-Imidazolinones: Imaza Metabenz, Imazamox, Imazapic, Imazapill, Imazaquin, Imazetapill;
-Phenoxyacetic acid system: Chlomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichloroprop, MCPA, MCPA thioethyl, MCPB, mecoprop;
-Pyrazines: chloridazone, flufenpyr-ethyl, fluthiaset, norflurazon, pyridate;
-Pyridine series: aminopyralide, clopyralide, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinaphene, thiazopyr;
-Sulfonylureas: amidosulfuron, azimusulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, synosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetsulfuron, flupirsulfuron, foramsulfuron, Halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primsulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfomethuron, sulfosulfuron, thifensulfuron, trisulfuron, tribenuron , Trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl-imidazo [1,2-b] pyridazin-3-yl) sulfonyl) -3- ( 4,6-dimethoxy-pyrimidin-2-yl) urea;
-Triazines: amethrin, atrazine, cyanazine, dimetamethrin, etiodin, hexazinone, metamitron, metribudine, promethrin, simazine, terbutyrazine, terbutrin, triadifram;
-Urea series: chlorotoluron, diemron, diuron, fluometuron, isoproturon, linuron, metabenzthiazurone, tebuthiuron;
-Other acetolactate synthase inhibitors: bispyribac-sodium, chloransram-methyl, diclosram, flurosum ram, flucarbazone, flumethram, methotram, ortho-sulfamlone, penoxthram, propoxycarbazone, pyrivambenz-propyl, pyribenzoxime, pyriftalide, pyriminobac-methyl, Pyrimisulphan, pyrithiobac, pyroxasulfone, piroxithram;
-Others: Amicarbazone, aminotriazole, anilophos, beflubutamide, benazoline, bencarbazone, benflurecetate, benzophenap, bentazone, benzobicyclone, bicyclopyrone, bromacil, bromobutide, butaphenacyl, butamifos, caventrolol, carfentrazone, sinidone-ethyl, Chlortal, symmetrine, clomazone, cumyluron, cyprosulfamide, dicamba, difenzocort, diflufenzopyr, Drechslera monoceras, endtal, etofumecetate, ettobenzanid, phenoxasulfone, fentrazamide, full microlac-pentyl , Flumioxazin, flupoxam, flurochloridone, flurtamone, indanophan, isoxaben, isoxaflu , Lenacyl, propanil, propizzamide, quinclolac, quinmerac, mesotrione, methylarsonic acid, naptalam, oxadiargyl, oxadiazone, oxadichromemephone, pentoxazone, pinoxaden, pyraclonyl, pyraflufen-ethyl, pyrasulfotol, pyrazoxifene, pyrazolinate, quinoclamine, saflufenacil , Sulcotrione, sulfentrazone, terbacil, tefryltrione, tembotrione, thiencarbazone, topramezone, (3- [2-chloro-4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoro Methyl-3,6-dihydro-2H-pyrimidin-1-yl) -phenoxy] -pyridin-2-yloxy) -acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid Methyl ester, 6-chloro-3- (2-cycline Ropropyl-6-methyl-phenoxy) -pyridazin-4-ol, 4-amino-3-chloro-6- (4-chloro-phenyl) -5-fluoro-pyridine-2-carboxylic acid, 4-amino-3- Chloro-6- (4-chloro-2-fluoro-3-methoxy-phenyl) -pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6- (4-chloro-3-dimethylamino- 2-Fluoro-phenyl) -pyridine-2-carboxylic acid methyl ester

O) Insecticide
-Organic (thio) phosphates: acephate, azamethiphos, azinephos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfotone, ethion, fenitrothion, fenthion, isoxathione, malathion, methamion thioth , Methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentoate, hosalon, phosmet, phosphamidone, folate, oxime, pyrimiphos-methyl, propenophos, prothiophos, sulfophos, tetrachlorvinphos, terbufos, triazophos, trichlorphone;
-Carbamate series: Alanicarb, Aldicarb, Bengiocarb, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Phenoxycarb, Frathiocarb, Methiocarb, Mesomil, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate;
-Pyrethroids: alletrin, bifenthrin, cyfluthrin, cyhalothrin, ciphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropatoline, fenvalerate, Imiprothrin, lambda-cyhalothrin, permethrin, praretrin, pyrethrins I and II, resmethrin, silafluophene, taufluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
-Insect growth regulator: a) Chitin synthesis inhibitor: Benzoylurea series: Chlorfluazuron, cilamazine, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novallon, teflubenzuron, triflumuron; buprofezin, geophenolan B) ecdysone antagonist system: halofenozide, methoxyphenozide, tebufenozide, azadirachtin; c) juvenile hormone-like substance: pyriproxyfen, methoprene, phenoxycarb; d) lipid biosynthesis inhibitor: spirodiclo Phen, spiromesifen, spirotetramat;
-Nicotine receptor agonist / antagonist compounds: clothianidin, dinotefuran, flupiradifuron, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1- (2-chloro-thiazol-5-ylmethyl) -2-nitrimino-3,5-dimethyl- [ 1,3,5] triazinan;
-GABA antagonist compounds: endosulfan, etiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1- (2,6-dichloro-4-methyl-phenyl) -4-sulfinamoyl-1H-pyrazole-3-carbothio Acid amides;
-Macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
-Mitochondrial electron transport inhibitor (METI) I acaricide: phenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
-METI II and III compounds: acequinosyl, fluacyprim, hydramethylnon;
-Uncoupler: chlorfenapyr;
-Oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutasine oxide, propargite;
-Molting disruptor compound: cryomazine;
-Mixed function oxidase inhibitor: piperonyl butoxide;
-Sodium channel blockers: indoxacarb, metaflumizone;
-Ryanodine receptor inhibitors: chlorantraniliprole, cyantraniliprole, fulvendiamide, N- [4,6-dichloro-2-[(diethyl-lambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-Chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide; N- [4-Chloro-2-[(diethyl-lambda-4-sulfanilidene) carbamoyl] -6-methyl-phenyl ] -2- (3-Chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide; N- [4-Chloro-2-[(di-2-propyl-lambda-4-sulfanilidene) Carbamoyl] -6-methyl-phenyl] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide; N- [4,6-dichloro-2-[(di- 2-propyl-lambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carbo N- [4,6-dichloro-2-[(diethyl-lambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (difluoromethyl) pyrazole-3 N- [4,6-Dibromo-2-[(di-2-propyl-lambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro-2-pyridyl) -5- (tri Fluoromethyl) pyrazole-3-carboxamide; N- [4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene) carbamoyl] -6-cyano-phenyl] -2- (3-chloro-2 -Pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide; N- [4,6-dibromo-2-[(diethyl-lambda-4-sulfanilidene) carbamoyl] -phenyl] -2- (3-chloro -2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide;
-Other insecticides: Benclothiaz, Bifenazate, Cartap, Flonicamid, Pyridalyl, Pymetrozine, Sulfur, Thiocyclam, Sienopyrafen, Flupirazophos, Cyflumethofen, Amidoflumet, Imiciaphos, Bistrifluron, Pyrifluquinazone and 1,1 '-[(3S, 4R, 4aR, 6S, 6aS, 12R, 12aS, 12bS) -4-[[(2-Cyclopropylacetyl) oxy] methyl] -1,3,4,4a, 5,6,6a, 12,12a, 12b-decahydro -12-hydroxy-4,6a, 12b-trimethyl-11-oxo-9- (3-pyridinyl) -2H, 11H-naphtho [2,1-b] pyrano [3,4-e] pyran-3,6 -Diyl] cyclopropaneacetic acid ester.

  Pesticides are water insoluble. Usually, it can be dissolved in water at 25 ° C. of 1 g / l or less, preferably 200 mg / l or less, in particular 50 mg / l or less. An example of a water-insoluble pesticide is linuron. Using simple preliminary tests, one skilled in the art can select a pesticide with the appropriate water-solubility from the above list of pesticides.

  In various embodiments, the pesticide can have a melting point greater than 50 ° C, greater than 70 ° C, or greater than 90 ° C.

  The pesticide can be present in the concentrate in dissolved form. Using simple preliminary tests, one skilled in the art can select a pesticide with the appropriate solubility from the above list of pesticides.

  In addition to the water-insoluble pesticide, the concentrate can contain one or more additional pesticides. The additional pesticide may be water insoluble. Usually it can be dissolved in water at 25 ° C. below 1 g / l, below 200 mg / l or below 50 mg / l. Using simple preliminary tests, one skilled in the art can select a pesticide with the appropriate water-solubility from the above list of pesticides. In one embodiment, the pesticide is dimethenamide-p.

  In one embodiment, the concentrate comprises a water-insoluble pesticide linuron and optionally an additional pesticide (eg, dimethenamide-p). In another embodiment, the concentrate can include a third pesticide.

  In various embodiments, the concentrate is 0.1 to 60 wt%, 1 to 25 wt%, or 5 to 15 wt% pesticide, based on the sum of all pesticides present in the concentrate An agent may be included.

  The emulsifiable concentrate can further comprise auxiliary agents commonly used in crop protection products. Suitable auxiliaries are solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetrants, protective colloids, adhesives, thickeners, bactericides, antifreeze agents Antifoaming agents, colorants, adhesives and binders.

  Suitable solvents and liquid carriers are organic solvents such as mineral oil fractions having medium to high boiling points, such as kerosene, diesel oil, etc .; oils of vegetable or animal origin; aliphatic and cyclic hydrocarbons such as toluene, Paraffin, tetrahydronaphthalene, alkylated naphthalene; alcohol, such as ethanol, propanol, butanol, cyclohexanol; glycol; ketone, such as cyclohexanone; ester, such as carbonate, fatty acid ester; fatty acid; phosphonate; amine; amide, such as N-methylpyrrolidone; as well as mixtures thereof.

  Suitable surfactants are surface active compounds such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetrants, protective colloids, or auxiliaries. Examples of surfactants are described in McCutcheon Volume 1: Emulsifiers and Detergents, McCutcheon's Directories, Glenlock, USA, 2008 (international or North American version), in its entirety. The contents of are incorporated into the reference.

  Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkyl aryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkyl phenol sulfonates, alkoxylated aryl phenol sulfonates, fused naphthalene sulfonates, dodecyl and tridecyl benzenes. Sulfonates, naphthalene and alkylnaphthalene sulfonates, sulfosuccinates or sulfosuccinates. Examples of sulfates are fatty acid and oil sulfates, ethoxylated alkylphenol sulfates, alcohol sulfates, ethoxylated alcohol sulfates, or fatty acid ester sulfates. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates. In one embodiment, anionic surfactants include sulfates and sulfonates.

  Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that are alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide can be used for its alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamide or fatty acid alkanolamide. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol, or vinyl acetate. Examples of nonionic surfactants include alkoxylates. Nonionic surfactants such as alkoxylates may also be used as adjuvants.

  Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are A-B or A-B-A type block polymers containing polyethylene oxide and polypropylene oxide blocks, or AB-C type block polymers containing alkanols, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids and polybases. Examples of polyacids are alkali salts of polyacrylic acid or comb polymers of polyacids. Examples of polybases are polyvinylamine or polyethyleneamine.

  Suitable adjuvants are compounds that themselves can be ignored or, moreover, have zero pesticidal activity and improve the biological performance of the compound against the target. Examples of surfactants are mineral or vegetable oils and other auxiliaries. Further examples are described by Knowles in Adjuvants and Additives, Agrow Reports DS256, T & F Informa UK, 2006, Chapter 5.

  Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyl isothiazolinone and benzisothiazolinone. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol. Suitable antifoaming agents are silicones, long chain alcohols, and fatty acid salts. Suitable colorants (eg, red, blue, or green) are pigments that are slightly insoluble in water, and water-soluble dyes. Examples are inorganic colorants (eg iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (alizarin, azo and phthalocyanine colorants).

  The concentrate may comprise at least one anionic surfactant. In various embodiments, the concentrate comprises 0.5% or more, 2% or more, or 3% or more by weight of an anionic surfactant. In other embodiments, the composition can comprise 30 wt% or less, 15 wt% or less, or 10 wt% or less of an anionic surfactant.

  The concentrate preferably includes at least one nonionic surfactant (eg, alkoxylate). In various embodiments, the concentrate can comprise 1 wt% or more, 5 wt% or more, or 10 wt% or more of a nonionic surfactant. In other embodiments, the composition can comprise 65 wt% or less, 45 wt% or less, or 35 wt% or less of a nonionic surfactant.

  In one embodiment, the concentrate includes a nonionic surfactant and an anionic surfactant.

The invention further relates to a process for producing an emulsifiable concentrate according to the invention by mixing a water-insoluble pesticide, a lactone and a tri-C ₁ -C ₆ -alkyl phosphate.

  The invention further relates to an emulsion obtainable (preferably obtained) by mixing water, a water-insoluble pesticide, components a) and b) according to the invention and optionally hydrocarbons. Emulsions usually occur spontaneously upon mixing. In most cases, the emulsion is an oil-in-water emulsion. The mixing ratio of water to concentrate can range from 1000 to 1 up to 1 to 1, preferably from 200 to 1 up to 3 to 1.

  The invention further provides a method for controlling phytopathogenic fungi and / or unwanted vegetation and / or unwanted attack by insects or ticks and / or for regulating plant growth, comprising The concentrate according to the invention or the emulsion according to the invention is applied to the respective pests, their environment or to the crop plants to be protected from each pest, to the soil and / or to the undesired plants. And / or a method of acting on crop plants and / or their environment. In general, therapeutic treatment of humans and animals is from methods for controlling phytopathogenic fungi and / or undesirable vegetation and / or undesirable attack by insects or ticks and / or regulating plant growth. Excluded.

  When used in crop protection, in certain embodiments, the rate of pesticide application is 0.001 to 2 kg per ha, 0.005 to 2 kg per ha, 0.05 to 0.9 kg per ha, depending on the nature of the desired effect, or 0.1 to 0.75kg per hectare. In the treatment of plant propagation material, e.g. seeds, for example by dusting, coating or irrigating the seeds, 0.1-1000 g, 1-1000 g, 1-100 g, or 5-100 kg per 100 kg of plant propagation material (preferably seeds) An amount of 100 g of active substance is generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the type of application area and the desired effect. The amount of active substance normally applied in the protection of the material is 0.001 g to 2 kg, or 0.005 g to 1 kg per cubic meter of material to be treated.

  Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) in premix form Or in some cases it can be added to the emulsion just before use (tank mixing). These agents can be admixed with the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, or 1:10 to 10: 1.

  The user usually applies the composition according to the invention from a pre-dosing device, a shoulder sprayer, a spray tank, a spray plane or an irrigation system. Usually, the pesticidal composition is formulated into the desired application concentration and ready-to-use spray liquid with water, buffer and / or further auxiliaries, or the pesticidal composition according to the invention is thus obtained. Usually, 20-2000 liters or 50-400 liters of ready-to-use spray solution is applied per hectare of agricultural effective area.

  The advantage of the present invention is that, inter alia, the concentrate is highly stable to low temperatures (eg even below 0 ° C.); the pesticide is at low temperatures (eg even below 0 ° C.). ) Not precipitate in the concentrate, do not cream or crystallize; the pesticide does not precipitate in the emulsion obtained from the concentrate, for example at low temperatures (eg even below 0 ° C.), It does not cream or crystallize; a high pesticide concentration in the concentrate can be used; the emulsion spontaneously occurs upon dilution of the concentrate with water; Can be stored over the course of 3 to 3 years; the concentrate does not require the presence of water (eg because water may freeze below 0 ° C. or may aid bacterial growth during storage) Concentrate Forming stable emulsions upon dilution with water; adjuvants can be included in the concentrate formulation; pesticides in emulsions obtained from the concentrate are water having a hardness of 34-342 ppm Is to maintain stability.

  The examples that follow illustrate the invention without any limitation.

(Example)
Surfactant A: Solid alkyl-terminated ethylene oxide / propylene oxide block copolymer, HLB about 17, cloud point 70-80 ° C.
Hydrocarbon A: Liquid aromatic hydrocarbon solvent, initial boiling point of about 225 to 240 ° C.

Example 1: Preparation of Emulsion Concentrate (EC) An emulsifiable concentrate of linuron, pendimethalin and dimethenamide-p (DMTA-p), the components of which are tributyl phosphate, γ-butyrolactone, hydrocarbon A, and the listed interfaces Prepared by mixing with the activators Agnique® MBL 510 H (hydrophilic emulsifier blend; commercially available from BASF SE) and Agnique® MBL 520 L (lipophilic emulsifier blend; commercially available from BASF SE). The concentrate mixtures are listed in Table 1 as Formulation A.

  As shown in Table 2, Formulation A exhibited safe solubility values at storage temperatures of -7 ° C.

  Formulation A provides excellent control of annual and broadleaf weeds with 4-6L per hectare product as pre-emergence application in soybean. No phytotoxicity was observed in soybean.

Example 2: Preparation of Emulsifiable Concentrate (EC) An emulsifiable concentrate of linuron, pendimethalin and dimethenamide-p (DMTA-p), the ingredients of which are tributyl phosphate, γ-butyrolactone, hydrocarbon A, and Prepared by mixing with surfactant Agnique® MBL 510 H, Agnique® MBL 520 L, and surfactant A. The concentrate mixtures are listed in Table 3 as Formulation B. Formulation B showed improved stability in the emulsion in soft water.

  As shown in Table 4, the active ingredient in Formulation B showed good chemical stability over a range of 25 ° C. to 40 ° C. for 3 months. Expected shelf life of 3 years of chemical stability.

  As shown in Table 5, the emulsions showed good physical stability over a range of 25 ° C. to 40 ° C. for various water hardness conditions and through freeze-thaw at −10 to −20 ° C. Crystals were not observed using a 200 mesh sieve.

  As shown in Table 6, Formulation B showed no evidence of crystal growth when examined on a 325 mesh screen (44 microns) or under a microscope.

Claims (13)

Water-insoluble pesticides,
a) a lactone, and
b) Emulsifiable concentrate containing tri-C ₁ -C ₆ -alkyl phosphate. At least 5 wt% of phosphoric acid tri -C ₁ -C ₆ - containing alkyl, concentrate of claim 1.   3. The concentrate according to claim 1 or 2, comprising at least 5% by weight of lactone.   The concentrate according to claim 1, comprising a hydrocarbon.   The concentrate according to claims 1 to 4, comprising up to 40% by weight of hydrocarbons. Containing 5 to 50% by weight of lactone, 10 to 35% by weight of tri-C ₁ -C ₆ -alkyl phosphate, and optionally 1 to 40% by weight of hydrocarbons, the amount of these components totaling 40 to 90 6. A concentrate according to claim 1 to 5% by weight.   The concentrate according to claims 1 to 6, wherein the lactone is γ-butyrolactone. Phosphoric acid tri -C ₁ -C ₆ - alkyl, phosphoric acid tributyl concentrate according to claims 1-7.   The concentrate according to claims 1 to 8, wherein the concentrate is present as a homogeneous solution.   The concentrate according to claims 1 to 9, wherein the concentrate contains little water. Water-insoluble pesticides, lactone, phosphoric acid tri -C ₁ -C ₆ - alkyl, toluenesulfonate, and hydrocarbons optionally a method of producing a concentrate according to claim 1-10. Water, a water-insoluble pesticide, a lactone according to any of claims 1 to 10, a tri-C ₁ -C ₆ -alkyl phosphate according to any of claims 1 to 10, and optionally a hydrocarbon An emulsion that can be obtained by mixing. A method for controlling phytopathogenic fungi and / or undesirable vegetation and / or unwanted attack by insects or ticks and / or for regulating plant growth, comprising: Or the emulsion according to claim 12 to the respective pests, their environment or to the crop plants to be protected from each pest, to the soil and / or Or act on undesired plants and / or crop plants and / or their environment.