WO2017220680A1 - Liquid sulfonylurea- and li-salt containing herbicidal compositions - Google Patents
Liquid sulfonylurea- and li-salt containing herbicidal compositions Download PDFInfo
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- WO2017220680A1 WO2017220680A1 PCT/EP2017/065289 EP2017065289W WO2017220680A1 WO 2017220680 A1 WO2017220680 A1 WO 2017220680A1 EP 2017065289 W EP2017065289 W EP 2017065289W WO 2017220680 A1 WO2017220680 A1 WO 2017220680A1
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- methyl
- lithium
- sulfonylurea
- salts
- iodosulfuron
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—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 ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
Definitions
- This invention relates to liquid herbicidal compositions comprising a non-aqueous solvent system, at least one sulfonylurea herbicide and at least one lithium salt as will be described herein.
- the invention also relates to the use of a lithium salt as will be described herein to improve chemical stabilisation of sulfonylurea herbicides in liquid compositions that comprise non-aqueous solvent systems.
- Typical liquid formulations include oil-based formulations such as oil dispersions (OD), emulsifiable concentrates (EC), and soluble concentrates (SL) where one or more active ingredients are dissolved in and/or suspended in the liquid media of the formulation.
- OD oil dispersions
- EC emulsifiable concentrates
- SL soluble concentrates
- Sulfonylureas are a well-known and important class of herbicides comprising more than 30 active-ingredients that are widely used for controlling a range of annual and perennial broad- leaved weeds and grasses in a wide variety of agricultural and horticultural crops, as well as in turf, pastures and non-crop situations.
- sulfonylureas are known to be unstable as they have a tendency to hydrolyse via cleavage at the sulfonylurea bridge. While this instability is sometimes considered favourable in terms of achieving low soil residues of these compounds, it poses serious problems commercially with respect to the storage stability of the formulated products.
- sulfonylurea herbicides are also prone to degradation due to chemical incompatibilities when other herbicidal ingredients are incorporated in the formulation.
- liquid herbicidal formulations such as oil dispersions have been commercially available for a long time (with early patents dating from the 1980's and 1990's such as GB 2,059,773 and US 5,707,928), the inherent chemical instability of sulfonylurea herbicides has limited their widespread use in liquid formulations.
- sulfonylurea compounds are normally formulated as powders, granules and tablets (e.g. see EP 0 764 404 Al, WO 98/34482 Al , WO 93/13658 Al , and WO 02/17718 Al).
- EP 0 764 404 Al, WO 98/34482 Al , WO 93/13658 Al , and WO 02/17718 Al are normally formulated as powders, granules and tablets.
- WO 2007/027863 A2 (E.I. du Pont de Nemours & Co.) is also concerned with providing stable sulfonylurea-containing liquid compositions and describes an oil suspension concentrate comprising one or more sulfonylurea herbicides, additionally one or more fatty acid esters of Cl- C4 alkanols, and a lignosulfonate.
- the stability of these compositions was found to vary dependent on the sulfonylurea that was used. Although the document is concerned with providing stable compositions, up to 66.5% of tribenuron-methyl was lost after only one week of storage at 40°C.
- US 5,731,264 (ISP Investments Inc.) describes a liquid emulsifiable concentrate comprising a sulfonylurea and a mixture of anionic and non-ionic surfactants dissolved in a solvent selected from gamma-butyrolactone, propylene glycol or propylene carbonate or mixtures thereof.
- a solvent selected from gamma-butyrolactone, propylene glycol or propylene carbonate or mixtures thereof.
- the obtained formulations comprising metsulfuron- methyl which is considered to be of average stability, are reported to have a half-life of 5.8 days at 52°C. After 5 days, between 25-30% of the metsulfuron methyl was lost depending on the selected solvent.
- WO 2008/155108 A2 (GAT Microencapsulation AG) describes oil suspensions of sulfonylureas and organomodified silane compounds that are reportedly stable when stored at comparatively gentle accelerated storage conditions of 35°C for 15 days.
- WO 2009/152827 A2 also GAT Microencapsulation AG
- the more usual accelerated storage conditions of 54°C for two weeks are used but in this document the chemical stability of the sulfonylurea in the suspension concentrates is not reported.
- EP 0554015 Al (Ishihara Sangyo Kaisha, Ltd.) describes a chemically stabilized herbicidal oil- based suspension, comprising N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl-3- dimethylaminocarbonyl-2-pyridinesulfonamide and/or its salt as an effective herbicidal component, urea, a vegetable oil and/or mineral oil, a surfactant and, optionally other ingredients such as an additional herbicidal component, a thickener, a solvent and other adjuvants.
- urea is added to suppress decomposition of the effective herbicidal component and to provide a chemically stabilized herbicidal oil-based suspension.
- GB 2496643 A (Rotam Agrochem International Company Ltd.) aims to improve the suspension concentrate described in EP 0554015 Al .
- This document is concerned with pyridine
- sulfonamides i.e. pyridylsulfonylureas
- sulfonamides i.e. pyridylsulfonylureas
- EP 0 124 295 A2 reports that aqueous suspensions of sulfonylureas can be stabilized by the presence of ammonium, substituted ammonium or alkali metal salts of carboxylic acid or inorganic acid provided that the salts exhibit specific solubility and pH properties.
- Exemplary salts are said to be diammonium hydrogen phosphate, ammonium acetate, lithium acetate, sodium acetate, potassium acetate, or sodium thiocyanate.
- WO 03/051 114 Al (ISP Investments Inc.) is concerned with increasing the shelf-life of an oil-in- water microemulsion containing a biologically active aza type compound.
- the oil-in-water microemulsion contains from 90 to 99.99 wt.% water. Shelf - life is said to be extended by the addition of a buffering agent to the emulsion.
- the buffering agent is an alkaline buffering agent such as an inorganic Na, K and or H 4 salt of a phenol, a polyphenol or a weak acid; an alkanol amine; a polyamine salt of a weak acid or a mixture of these buffering agents. No stability data is provided for any sulfonylurea-containing formulations.
- WO 2013/174833 Al (Bayer CropScience AG) describes an oil dispersion formulation of iodosulfuron-methyl sodium salt which comprise hydroxystearates, in particular lithium hydroxystearate as both a thickener and a stabilizer for the sulfonylurea.
- the present invention is based on the surprising finding that the chemical stability of many sulfonylureas in a liquid composition comprising a non-aqueous solvent system can be improved by incorporating into the composition at least one inorganic or organic lithium salt, wherein the organic lithium salt is selected from the C1-C12 carboxylic acid salts of lithium.
- the present invention relates to liquid herbicidal compositions comprising: a nonaqueous solvent system; at least one sulfonylurea herbicide; and at least one inorganic or organic lithium salt, wherein the at least one organic lithium salt is selected from the C1-C12 organic carboxylic acid salts of lithium.
- the inorganic and C1-C12 organic acid salt has a molecular weight of 250 or less.
- the C1-C12 organic carboxylic acids are mono or dicarboxylic acids.
- the C1-C12 organic carboxylic acid salt is selected from lithium acetate, lithium formate, lithium citrate, lithium succinate, lithium octanoate, and lithium benzoate.
- the inorganic acid salt of lithium is selected from lithium carbonate, lithium sulfate, lithium phosphate, lithium chloride, lithium iodide, lithium bromide, lithium nitrate, and lithium borate.
- the present invention is suitable for chemically stabilising liquid compositions comprising one, two, three, four or more different sulfonylurea compounds.
- the liquid herbicidal composition is preferably formulated as an oil dispersion (OD), a dispersible concentrate (DC), an emulsifiable concentrate (EC), or a soluble concentrate (SL).
- OD oil dispersion
- DC dispersible concentrate
- EC emulsifiable concentrate
- SL soluble concentrate
- At least one sulfonylurea is dissolved, suspended or otherwise contained in the non-aqueous solvent system.
- At least one inorganic or organic lithium salt as described herein is dissolved, suspended or otherwise contained in the non-aqueous solvent system.
- the liquid herbicidal composition of the invention may comprise one or more non-sulfonylurea herbicides that are suspended, dissolved or otherwise contained in the non-aqueous solvent system.
- the present invention is particularly suitable for improving the chemical stability of a sulfonylurea in the presence of a non-sulfonylurea herbicide that would ordinarily impair its chemical stability.
- the liquid herbicidal composition may comprise one or more safeners.
- the liquid herbicidal composition may also comprise co-formulants such as surfactants, particularly non-ionic surfactants.
- the invention also relates to the use of a lithium salt to improve chemical stabilisation of a sulfonylurea herbicide in a liquid composition comprising a non-aqueous solvent system, wherein the lithium salt is an inorganic lithium salt or an organic lithium salt selected from the C 1 -C 12 organic carboxylic acid salts of lithium. 4. DETAILED DESCRIPTION OF THE INVENTION
- compositions that comprises a list of components is not necessarily limited to only those components but may include other components that are not expressly listed or inherent to such a composition. That said, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having” or any other variation thereof also cover the disclosed embodiment having no further additional components (i.e. consisting of those components).
- compositions comprising a sulfonylurea, a lithium salt, an organic solvent, and a surfactant discloses the composition with just these four components as well as compositions comprising these four components along with other unmentioned components.
- the herbicidal composition of the invention is a liquid.
- liquid is meant that the composition takes the form of a liquid at standard temperature and pressure.
- suitable liquid compositions that can be used in the present invention include the oil-based liquid formulations defined in the "Catalogue of pesticide formulation types and international coding system", Technical
- Exemplary liquid compositions for use in the present invention include a dispersible concentrate (DC), an emulsifiable concentrate (EC), the liquid part(s) of a solid/liquid (KK) or liquid/liquid (KL) combi-pack, an oil dispersion (OD), an oil miscible flowable concentrate (OF), an oil miscible liquid (OL), an oil-based soluble concentrate (SL), a spreading oil (SO), an oil-based ultra-low volume liquid (UL) or suspension (SU), or any other oil-based liquid not yet designated by a specific code in the CropLife monograph (AL).
- DC dispersible concentrate
- EC emulsifiable concentrate
- KK emulsifiable concentrate
- KL liquid/liquid
- OD oil dispersion
- OF oil miscible flowable concentrate
- OOL oil miscible liquid
- SL oil-based soluble concentrate
- SO spreading oil
- UL ultra-low volume liquid
- SU suspension
- oil dispersions OD
- DC dispersible concentrates
- EC emulsifiable concentrates
- SL oil-based soluble concentrates
- oil dispersions OD
- EC emulsifiable concentrates
- SL soluble concentrates
- oil dispersion is to be understood as meaning a dispersion concentrate based on a non-aqueous solvent in which one or more solid active compounds are suspended and wherein further active ingredients are optionally dissolved in the non-aqueous solvent.
- at least one sulfonylurea compound is suspended in the non-aqueous solvent system. Additional sulfonylurea compounds may be co-suspended and/or dissolved in the non-aqueous solvent system.
- one or more non- sulfonylurea herbicidal compounds may be suspended and/or dissolved in the non-aqueous solvent system.
- the inorganic or C1-C12 organic lithium salt is also suspended in the non-aqueous solvent system.
- the terms "suspended” and “dissolved” take their ordinary meaning in this technical field. Whether a compound is suspended or dissolved can be determined at standard temperature and pressure. For the avoidance of any doubt, the term “suspended” can be taken to mean that 80 wt.% or more, preferably 90 wt.% or more, even more preferably 95 wt.% or more of the compound in question is suspended within the liquid composition whereas the term “dissolved” can be taken to mean that 90 wt.% or more, preferably 95 wt.% or more, even more preferably 99 wt.% or more of the compound in question is dissolved in the liquid composition.
- the liquid composition of the present invention comprises a sulfonylurea.
- the sulfonylurea is not particularly limited and can be any herbicidal sulfonylurea known in the art or described in the patent literature.
- the sulfonylurea may be selected from the sulfonylureas listed in the 16 th Edition of "7%e Pesticide Manual" (ISBN- 10: 190139686X).
- the sulfonylurea may be a compound according to Formula (I) as described in
- R is H or CH 3 ;
- R 1 is F, CI, Br, N0 2 , C C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 cycloalkyl, C 2 -C 4 haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C 2 -C 4 alkoxyalkoxy, C0 2 R 14 , C(0)NR 15 R 16 , S02NR 17 R 18 , S(0) n R 19 , C(0)R 20 , CH 2 CN or L;
- R 2 is H, F, CI, Br, I, CN, CH 3 , OCH 3 , SCH 3 , CF 3 or OCF 2 H;
- R 3 is CI, N0 2 , C0 2 CH 3 , C0 2 CH 2 CH 3 , C(0)CH 3 , C(0)CH 2 CH 3 , C(0)-cyclopropyl, S0 2 N(CH 3 ) 2 , S0 2 CH 3 , S0 2 CH 2 CH 3 , OCH 3 or OCH 2 CH 3 ;
- R 4 is Ci-C 3 alkyl, C C 2 haloalkyl, C C 2 alkoxy, C 2 -C 4 haloalkenyl; F, CI, Br, N0 2 , C0 2 R 14 , C(0)NR 15 R 16 , S0 2 NR 17 R 18 , S(0)nR 19 , C(O)R 20 or L;
- R 5 is H, F, CI, Br or CH 3 ;
- R 6 is Ci-C 3 alkyl optionally substituted with 0-3 F, 0-1 CI and 0-1 C 3 -C 4 alkoxyacetyloxy, or R 6 is C1-C2 alkoxy, C 2 -C 4 haloalkenyl, F, CI, Br, C0 2 R 14 , C(0)NR 15 R 16 , S0 2 NR 17 R 18 , S(0) n R 19 , C(0)R 20 or L;
- R 7 is H, F, CI, CH 3 or CF 3 ;
- R is H, Ci-C 3 alkyl or pyridyl
- R 9 is Ci-C 3 alkyl, C1-C2 alkoxy, F, CI, Br, N0 2 , C0 2 R 14 , S0 2 NR 17 R 18 , S(0) n R 19 , OCF 2 H, C(0)R 20 , C 2 -C 4 haloalkenyl or L;
- R 10 is H, CI, F, Br, d-C 3 alkyl or d-C 2 alkoxy;
- R 11 is H, Ci-C 3 alkyl, C C 2 alkoxy, C 2 -C 4 haloalkenyl, F, CI, Br, C0 2 R 14 , C(0)NR 15 R 16 ,
- R 12 is halogen, Ci-C 4 alkyl or Ci-C 3 alkylsulfonyl
- R 13 is C1-C4 alkyl
- R 14 is selected from the group consisting of allyl, propargyl, oxetan-3-yl and Ci-C 3 alkyl optionally substituted by at least one member independently selected from halogen, Ci-C 2 alkoxy and CN;
- R 15 is H, Ci-C 3 alkyl or C C 2 alkoxy
- R 16 is C1-C2 alkyl
- R 17 is H, Ci-C 3 alkyl, Ci-C 2 alkoxy, allyl or cyclopropyl;
- R 18 is H or C C 3 alkyl
- R 19 is Ci-C 3 alkyl, Ci-C 3 haloalkyl, allyl or propargyl;
- R 20 is Ci-C 4 alkyl, Ci-C 4 haloalkyl or C 3 -C 5 cycloalkyl optionally substituted by halogen; n is 0, 1 or 2;
- L 1 is CH 2 , NH or O
- R 21 is selected from the group H and C1-C3 alkyl
- X is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 haloalkyl, C1-C4 haloalkylthio, C1-C4 alkylthio, halogen, C2-C5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino and di(Ci-C3 alkyl)amino;
- Y is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino, di(Ci-C3 alkyl)amino, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C2-C5 alkylthioalkyl, C2-C5 alkylsulfinylalkyl, C2-C5 alkylsulfonylalkyl, C1-C4 haloalkyl, C2-C4 alkynyl, C3-C5 cycloalkyl, azido and cyano; and
- Z is selected from the group CH and N;
- alkylthio or “haloalkyl” includes a straight-chain or branched alkyl, such as, methyl, ethyl, n- propyl, /-propyl, or the different butyl isomers;
- cycloalkyl includes, for example, cyclopropyl, cyclobutyl and cyclopentyl;
- alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl isomers;
- alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-butadienyl;
- alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl isomers;
- alkynyl can also include moieties comprised of multiple triple bonds
- alkylsulfinylalkyl and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively; other substituents such as “alkylamino”, “dialkylamino” are defined analogously.
- C 1 -C 4 alkyl designates methyl through butyl, including the various isomers.
- C 2 alkoxyalkyl designates CH 3 OCH 2 ;
- C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or
- C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including
- halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, CICH 2 , CF 3 CH 2 and CF 3 CCI 2 .
- haloalkoxy "haloalkylthio" and the like, are defined analogously to the term “haloalkyl”.
- haloalkoxy examples include CF 3 0, CC1 3 CH 2 0, HCF 2 CH 2 CH 2 0 and CF 3 CH 2 0.
- haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
- preferable sulfonylureas according to Formula (I) include those where X is selected from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, halogen, di(Ci-C 3 alkyl)amino and Y is selected from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 haloalkoxy. More preferably, X is selected from CH 3 , OCH 3 , CI, OCHF 2 , and (CH 3 ) 2 and Y is selected from CH3, OCH3, OCHF2 and OCH2CF3.
- Preferable sulfonylureas according to Formula (I) also include those where J is J- l , R 1 is CI, CO 2 CH 3 , C0 2 C 2 H 5 , CH 2 CH 2 CF 3 , or 0CH 2 CH 2 C1, and R 2 is H; J is J-l , R 1 is C0 2 CH 3 , and R 2 is CH 3 ; J is J-2, R 3 is C0 2 C 2 H 5 , OCH 2 CH 3 , or COC 3 -cycloalkyl, L 1 is CH 2 , O, or NH, and R 2 is H; J is J-5, R 4 is C0 2 CH 3 , and R 5 is H; J is J-6, R 6 is CON(CH 3 ) 2 , S0 2 CH 2 CH 3 , or CF 3 , and R 7 is H; J is J- 10, R 8 is CH 3 , R 9 is C0 2 CH 3 and R 10 is CI.
- the sulfonylurea according to Formula (I), or any of the exemplary sulfonylureas mentioned herein, is to be understood as meaning all of the usual use forms in this technical field, such as acids, esters, salts and isomers.
- the salt includes acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
- salts formed with organic bases e.g., pyridine, ammonia, or triethylamine
- inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium.
- Preferred salts of the sulfonylureas according to Formula (I), or the exemplary sulfonylureas mentioned herein, include lithium, sodium, potassium, triethylammonium, and quaternary ammonium salts.
- esters for the purpose of this invention are the alkyl esters, in particular the Ci-Cio-alkyl esters, such as methyl and ethyl esters.
- Exemplary sulfonylureas according to Formula (I) that can be used for this invention include: amidosulfuron (N-[[[[[(4,6-dimethoxy-2-pyrimdinyl)amino]carbonyl]amino]sulfonyl]-N- methylmethanesulfonamide),
- chlorsulfuron (2-chloro-N-[[(4-methoxy-6-methyl-l ,3,5-triazin-2- yl)amino]carbonyl]benzenesulfonamide), cinosulfuron (N-[[(4,6-dimethoxy- 1 ,3,5-triazin-2-yl)amino]carbonyl]-2-(2- methoxyethoxy)- benzenesulfonamide),
- halosulfuron-methyl (methyl 3-chloro-5-[[[[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-l-methyl-lH-pyrazole- 4-carboxylate),
- mesosulfuron-methyl (methyl 2-[[[[[(4,6-dimethoxy-2- pyrimidinyl)amino] carbonyl] amino] - sulfonyl] -4- [ [(methylsulfonyl)amino] methyl]benzoate), metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl- 1 ,4,2- dioxazin-3-yl)-N-[[(4,6- dimethoxy-2-pyrimidinyl)amino]carbonyl]-l -methyl- lH-pyrazole-5- sulfonamide),
- metsulfuron-methyl methyl 2-[[[[[[(4-methoxy-6-methyl-l ,3,5-triazin-2- yl)amino]carbonyl]amino]sulfonyl]benzoate),
- nicosulfuron (2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N,N- dimethyl-3-pyridinecarboxamide), orthosulfamuron (2-[[[[[[(4,6-dimethoxy-2- pyrimidinyl)amino] carbonyl] amino] sulfonyl] amino] -N,N-dimethylbenzamide),
- oxasulfuron (3-oxetanyl 2-[[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate),
- sulfonylureas e.g. propyrisulfuron: 2-chloro-N-[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]-6-propylimidazo[ 1 ,2-3 ⁇ 4]pyridazine-3-sulfonamide
- propyrisulfuron 2-chloro-N-[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]-6-propylimidazo[ 1 ,2-3 ⁇ 4]pyridazine-3-sulfonamide
- Preferred salts of the sulfonylureas mentioned above include the sodium salt thereof and the potassium salt thereof.
- the sulfonylurea is preferably comprised in the liquid compositions of the invention in an amount of at least 0.1 wt.% based on the total weight of the liquid composition. More preferably, the sulfonylurea is comprised in an amount of at least 0.2 wt.%, at least 0.5 wt.%, at least 0.7 wt.%, at least 1 wt.%, at least 2 wt.%, at least 5 wt.% or at least 7 wt.%. Increasing the amount of sulfonylurea can improve its chemical stability.
- the sulfonylurea is preferably comprised in the composition in an amount of 60 wt.% or less.
- the sulfonylurea is comprised in an amount of 50 wt.% or less, 40 wt.% or less, 30 wt.% or less, 25 wt.% or less, 20 wt.% or less, 10 wt.% or less, 5 wt.% or less, 2 wt.% or less, or 1 wt.% or less. Any of the preferred lower wt.% limits for the amount of sulfonylurea can be combined with any of the preferred upper wt.% limits to define further suitable wt.% ranges for the present invention.
- further exemplary ranges for the amount of sulfonylurea in the liquid composition include 0.1 to 60 wt.%, 1 to 50wt.%, 2 to 40 wt.%, 5 to 30 wt.%, 0.5 to 20 wt.%, 7 to 30 wt.%, 5 to 10 wt.%, 0.2 to 5 wt.%, 0.5 to 2 wt.% and 0.5 to 1 wt.%.
- the wt.% amounts that are described herein refer to the weight amount of the modified sulfonylurea.
- the amounts described herein refer to the sum amount of all the sulfonylureas present in the composition.
- the liquid composition is an oil dispersion of a sulfonylurea
- the sulfonylurea has a particle size (D50) of at least 100 nm or more, at least 200 nm or more, at least
- the sulfonylurea has a particle size (D50) of 30 ⁇ or less, 15 ⁇ or less, 10 ⁇ or less, 7 ⁇ or less, 5 ⁇ or less, 3 ⁇ or less, 1 ⁇ or less, 500 nm or less.
- D50 particle size
- Any of the preferred lower limits for the sulfonylurea particle size can be combined with any of the preferred upper limits to define further suitable particle size ranges for the present invention.
- further exemplary ranges for the particle size (D50) of the sulfonylurea include 0.1- 30 ⁇ , 0.2-15 ⁇ , 0.5-10 ⁇ , 0.1-0.5 ⁇ , 0.2-1 ⁇ , 0.5-3 ⁇ , 1-15 ⁇ , 1-10 ⁇ , 1-7 ⁇ , 2-15 ⁇ , 2-10 ⁇ , 2-7 ⁇ , 3-15 ⁇ , 3-10 ⁇ , and 3-7 ⁇ .
- D50 refers to the volume median particle size and can be determined by laser light scattering using the method described in CIPAC MT187.
- the liquid composition of the invention may comprise more than one sulfonylurea herbicide compound.
- the liquid composition may comprise any combination of sulfonylureas as disclosed herein.
- the liquid composition may comprise tribenuron-methyl and any other sulfonylurea described herein; the liquid composition may comprise metsulfuron-methyl and any other sulfonylurea described herein; the liquid composition may comprise nicosulfuron and any other sulfonylurea described herein; the liquid composition may comprise iodosulfuron and any other sulfonylurea described herein; or the liquid composition may comprise halosulfuron-methyl and any other sulfonylurea described herein.
- the liquid herbicidal composition comprises at least one sulfonylurea that is not a pyridylsulfonylurea. In another aspect of the invention the herbicidal composition does not comprise a pyridylsulfonylurea. In one further aspect of the invention the herbicidal composition does not comprise nicosulfuron.
- composition of the present invention comprises an inorganic or organic lithium salt.
- the lithium salt has a molecular weight of 250 or less.
- a molecular weight of 250 or less is preferred because it allows more lithium to be introduced to the formulation per unit weight of lithium-containing compound. This can improve sulfonylurea stability with reduced thickening of the sulfonylurea-containing composition itself.
- the molecular weight of the lithium salt is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less. The fact that such lithium salts can stabilise a sulfonylurea in a non-aqueous system is surprising, more so when the lithium salt is not even dissolved in the composition but suspended therein.
- the inorganic lithium salt or the organic lithium salt can have more than one lithium cation (e.g. two, three or four lithium cations).
- the salt need not be one that is prepared by reacting lithium or a lithium-containing compound with the inorganic or organic acid. It suffices for the purpose of this invention that the salt is one containing one or more lithium cation components and one or more carboxylic acid anion components.
- the organic lithium salt is a salt of lithium and a C1-C12 organic acid.
- the organic lithium salt is a salt of lithium and a C1-C10 organic acid, more preferably a Ci-Cs organic acid, and even more preferably a Ci-C 6 organic acid. Salts of lithium and a C 2 -Cio organic acid, C 2 -Cs organic acid, C4-C10 organic acid, and C4-C8 organic acid are also contemplated and preferred.
- the organic acid may be saturated or unsaturated; it may be aliphatic, aromatic, or heterocyclic; and/or it may be straight-chained, branched or cyclic.
- C 1 -C 12 organic acid should be taken as a disclosure of an organic acid having each of the possible number of carbon atoms in the stated range: in this case, one, two, three, four, five, six, seven, eight, nine, ten, eleven or twelve carbon atoms.
- carboxylic acid groups in the organic acid, as well as the carbon atoms in any substituent on the organic acid are also counted when assessing the total number of carbon atoms in the organic acid.
- Lithium salts of small-chain fatty acids (C 1 -C5) or medium-chain fatty acids (C 6 -C 12 ) are particularly preferred for the stability that they provide to the sulfonylurea but with reduced thickening effect on the liquid formulation.
- small-chain fatty acids are most preferred.
- the small chain fatty acid is a C 1 -C4 organic acid, more preferably a C 1 -C3 organic acid, and most preferably a Ci- or C 2 -organic acid.
- the organic acid may have one, two, three or more carboxyl groups. Derivatives of the organic acid are acids which are mono-, di-, trior polysubstituted along the carbon chain or the cyclic structure.
- substituents of the organic acids of the invention include Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 6 -hydroxyalkyl, C 2 -C 6 -hydroxyalkenyl, aminomethyl, C 2 -C 6 -aminoalkyl, cyano, formyl, oxo, thioxo, hydroxyl, mercapto, amino, carboxyl or imino groups.
- Preferred substituents are Ci-C 6 -alkyl (e.g. methyl, ethyl, propyl), hydroxymethyl, hydroxyl, amino and carboxyl groups.
- organic acids that can be used for the lithium organic acid salt include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, citric acid, isobutyric acid, valeric acid, isovaleric acid, lauric acid, capric acid, caprylic acid, caproic acid, pivalic acid, oxalic acid, malonic acid, salicylic acid, tartaric acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, phthalic acid (0-, m-, or p-), naphthoic acid, benzoic acid, toluic acid, camphor
- the inorganic lithium salt is a salt of lithium and an inorganic acid.
- Exemplary inorganic acids include, but are not limited to, HA10 2 , HAl(OH) 4 , H 3 As0 4 , HAs0 2 , H 3 As0 3 , H 3 B0 3 , (HB0 2 ) n , H 2 B 4 O 7 , HB0 3 , HBr0 3 , HBr0 2 , HBrO, HBr0 4 , H 2 C0 3 , H 4 CO 4 , H 2 C 2 0 6 , H 2 C0 4 (or
- H 2 C0 3 H 2 0 2 ), HC10 3 , HCIO 4 , HC10 2 , HCIO, HONC, HOCN, HNCO, HI0 3 , HIO (or IOH, HIO 4 ), H 5 I0 6 , H 4 I 2 0 9 , HN0 3 , HN0 2 , H 3 P0 4 , 3 ⁇ 4P0 5 , HP0 3 , H 3 P0 3 , H 4 P 2 0 5 , HP0 2 , H 3 P0 2 , H 4 P 2 0 6 , H 4 P 2 0 7 , H 2 S0 4 , H 2 S0 3 , H 2 S 2 0 3 , H 2 S 2 0 7 , H 2 S0 2 , H 2 S x 0 6 (x 2-6), H 6 S0 6 , H 2 S 2 0 4 , H 2 S0 5 , H 2 S 2 0 8 , HSO 3 CI, HS0 3 F,
- Lithium salts that are envisioned for use in the present invention include, by way of example, the following compounds: lithium acetate, lithium acetate dihydrate, lithium acetoacetate, lithium acetylacetonate, lithium iodoacetate, lithium 2-hydroxybutanoate, lithium molybdate, lithium titanate, lithium manganese oxide, lithium manganese dioxide, lithium iron phosphate, lithium zirconate, lithium iron oxide, lithium D-gluconate, lithium pentaborate, lithium bromide, lithium iodide, lithium chloride, lithium calcium chloride, lithium hydrogen carbonate, lithium carbonate, lithium citrate, lithium hydroxide, lithium manganate, lithium methionate, lithium oxalate, lithium monoxide, lithium oxide, lithium mono-orthophosphate, lithium orthophosphite, lithium silicate, lithium disilicate, lithium metasilicate, lithium sodium carbonate, lithium salt (E,E)-2,4- hexadienoic acid, dilithium fluorophosphate,
- dihydrogenphosphate monolithium L-aspartic acid, lithium bromate, lithium periodate, monlithium salt D-saccharic acid, D-asparatic lithium salt, (R)-alpha-hyroxymethylaspartic acid lithium salt, lithium salt ethyl malonate, lithium salt lactic acid, dilithium thiosulfate, lithium dichloroacetate, lithium dimethylacetate, lithium diethylacetate, lithium dipropyl-acetate, lithium metaborate, lithium laurate, lithium caprate, lithium caprylate, lithium caproate, lithium tetraborate, lithium difluoride, lithium bismuthate, lithium borate, lithium chlorite, lithium hexametaphosphate, lithium hydrogenphosphite, lithium hydrogenselenite, lithium
- hydro gensulfite lithium hydrosulfite, lithium hypochlorite, lithium polyphosphate, lithium polyphosphite, lithium propionate, lithium pyrophosphate, lithium selenate, lithium thiosulfate, lithium thiosulfide, and lithium thiosulfite.
- the above list includes analogues, homologues, isomers, enantiomers, hydrates and derivatives thereof. Both the anhydrous and hydrated forms of the lithium salts can be used for the purpose of this invention but the anhydrous form is most preferred in view of improving chemical stability of the sulfonylurea.
- lithium formate, lithium acetate, lithium citrate, lithium benzoate, lithium octanoate, lithium salicylate, lithium carbonate, lithium phosphate, lithium chloride and lithium sulphate provide for a sulfonylurea with superior chemical stability than many of the other salts mentioned herein, particularly with respect to those sulfonylureas that are more prone to hydrolysis in liquid compositions.
- iodosulfuron-methyl, halosulfuron-methyl, metsulfuron-methyl, pyrazosulfuron-ethyl, and amidosulfuron were found to have excellent chemical stability in the presence of lithium acetate.
- iodosulfuron-methyl was found to have excellent chemical stability in the presence of lithium acetate, lithium formate, lithium benzoate, lithium octanoate, lithium salicylate, lithium citrate, lithium carbonate, lithium phosphate, lithium chloride and lithium sulphate. Superior chemical stability has also been observed where:
- the at least one lithium salt is lithium acetate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof, halosulfuron-methyl or salts thereof, metsulfuron-methyl or salts thereof, pyrazosulfuron-ethyl or salts thereof or amidosulfuron or salts thereof; or
- the at least one lithium salt is lithium carbonate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof, or halosulfuron-methyl or salts thereof; or
- the at least one lithium salt is lithium formate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof; or the at least one lithium salt is lithium phosphate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof; or
- the at least one lithium salt is lithium chloride and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof; or
- the at least one lithium salt is lithium sulphate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof;
- the at least one lithium salt is lithium benzoate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof;
- the at least one lithium salt is lithium octanoate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof, halosulfuron-methyl or salts thereof, pyrazosulfuron-ethyl or salts thereof, amidosulfuron or salts thereof, or foramsulfuron or salts thereof, or chlorsulfuron or salts thereof; or
- the at least one lithium salt is lithium citrate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof.
- the invention also relates to formulations, as described herein, comprising the above preferred combination of salt and sulfonylurea.
- the invention also relates to the use of a lithium salt to improve chemical stabilisation of a sulfonylurea herbicide, wherein the at least one lithium salt is lithium acetate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof, halosulfuron-methyl or salts thereof, metsulfuron-methyl or salts thereof, pyrazosulfuron-ethyl or salts thereof or amidosulfuron or salts thereof; or the at least one lithium salt is lithium carbonate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof, or halosulfuron-methyl or salts thereof; or the at least one lithium salt is lithium formate and the sulfonylurea is selected from iodosulfuron-methyl or salt
- the at least one lithium salt is lithium citrate or lithium benzoate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof; or the at least one lithium salt is lithium octanoate and the sulfonylurea is selected from iodosulfuron-methyl or salts thereof, halosulfuron-methyl or salts thereof, pyrazosulfuron-ethyl or salts thereof, amidosulfuron or salts thereof, or foramsulfuron or salts thereof, or chlorsulfuron or salts thereof.
- the lithium salt is preferably comprised in the liquid composition of the invention in an amount of at least 0.01 wt.% based on the total weight of the liquid composition. More preferably, the lithium salt is comprised in an amount of at least 0.03 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, at least 0.2 wt.%, at least 0.5 wt.%, at least 1 wt.%, at least 2 wt.%.
- the lithium salt is preferably comprised in the composition in an amount of 30 wt.% or less to reduce physical stability problems of the formulation and to reduce interference with the function of any surfactants that are optionally present.
- the lithium salt is comprised in an amount of 25 wt.% or less, 20 wt.% or less, 15 wt.% or less, 10 wt.% or less, 8 wt.% or less, 6 wt.% or less, 5 wt.% or less, 2 wt.% or less, 1 wt.% or less, or 0.7 wt.% or less.
- Any of the preferred lower wt.% limits for the amount of lithium salt can be combined with any of the preferred upper wt.% limits to define further suitable wt.% ranges for the present invention.
- further exemplary ranges for the amount of lithium salt in the liquid composition include 0.01 to 30 wt.%, 0.1 to 25 wt.%, 1 to 20 wt.%, 1 to 10 wt.%, 0.5 to 10 wt.%, 1 to 5 wt.%, 0.5 to 5 wt.%, 0.1 to 2 wt.%, 0.2 to 2 wt.%, 0.2 to 1 wt.%, and 0.2 to 0.7 wt.%.
- the weight ranges above refer to the total amount of inorganic lithium salt and organic lithium salt wherein the organic lithium salt is selected from the C1-C12 organic carboxylic acid salts of lithium.
- the weight ranges above do not refer to the lithium salt of a sulfonylurea or lithium salt of a non-sulfonylurea herbicide should these be present in the composition.
- the amounts described herein refer to the sum amount of all the inorganic and organic lithium salts that are present in the composition, wherein the organic lithium salt refers to the C1-C12 organic carboxylic acid salts of lithium.
- the weight ratio of the lithium salt to sulfonylurea is 0.1 or greater.
- the weight ratio of the lithium salt to sulfonylurea is 0.2 or greater, 0.3 or greater, 0.5 or greater, 0.7 or greater, or 1 or greater.
- the weight ratio of the lithium salt to sulfonylurea is preferably 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.
- the preferred weight ratios refer to the total amount of the inorganic lithium salt and C1-C12 organic acid lithium salt with respect to the total amount of sulfonylurea compounds in the liquid composition.
- any of the preferred lower weight ratio limits can be combined with any of the preferred upper weight ratio limits to define further suitable weight ratio ranges for the present invention.
- further exemplary ranges for the weight ratio of the lithium salt to sulfonylurea include 0.1 to 5, 0.2 to 4, 0.3 to 3, 0.3 to 1, 0.5 to 2, 0.7 to 2, 0.1 to 2, 1 to 2 and 1 to 5.
- At least one sulfonylurea herbicide wherein the total amount of sulfonylurea compounds is 1 to 50 wt.% of the composition
- At least one inorganic or C1-C12 organic lithium salt wherein the total amount of said lithium salt is 0.1 to 20 wt.%;
- the weight ratio of said lithium salt to sulfonylurea is in the range of from 0.1 to 10.
- the total amount of sulfonylurea compounds is 2 to 20 wt.%
- the total amount of inorganic or C1-C12 organic lithium salt is 1 to 20 wt.%
- the weight ratio of said lithium salt to sulfonylurea is in the range of from 0.1 to 10.
- the total amount of sulfonylurea compounds is 2 to 20 wt.%
- the total amount of inorganic or C1-C12 organic lithium salt is 1 to 20 wt.%
- the weight ratio of said lithium salt to sulfonylurea is in the range of from 0.5 to 2.5, preferably 0.7 to 2.0.
- the lithium salt can be a C1-C3 organic carboxylic acid salt.
- the liquid herbicidal composition may comprise iodosulfuron methyl (optionally as the sodium salt), halosulfuron-methyl, metsulfuron-methyl, pyrazosulfuron- ethyl or amidosulfuron.
- the liquid herbicidal composition may contain only one sulfonylurea selected from iodosulfuron methyl (optionally as the sodium salt), halosulfuron- methyl, metsulfuron-methyl, pyrazosulfuron-ethyl and amidosulfuron.
- sulfonylurea selected from iodosulfuron methyl (optionally as the sodium salt), halosulfuron- methyl, metsulfuron-methyl, pyrazosulfuron-ethyl and amidosulfuron.
- the salt includes lithium acetate, lithium formate, lithium carbonate, lithium chloride, lithium sulphate, lithium octanoate, lithium benzoate or lithium citrate
- the weight ratio of these salts (individually, or collectively if more than one is present) to the total amount of sulfonylurea is preferably in the range of from 0.1 to 10, more preferably in the range of from 0.5 to 2.
- the particle size (D50) of the lithium salt is preferably at least 100 nm or more, at least 200 nm or more, at least 500 nm or more, at least 1 ⁇ or more, at least 1.5 ⁇ or more, or at least 2 ⁇ or more.
- the particle size (D50) of the lithium salt is preferably 30 ⁇ or less, 15 ⁇ or less, 10 ⁇ or less, 5 ⁇ or less, 3 ⁇ or less, 1 ⁇ or less, or 500 nm or less to improve chemical stability of the sulfonylurea in the composition.
- any of the preferred lower limits for the lithium salt particle size can be combined with any of the preferred upper limits to define further suitable salt particle size ranges for the present invention.
- further exemplary ranges for the particle size of the lithium salt include 0.1-30 ⁇ , 0.2-15 ⁇ , 0.5-10 ⁇ , 0.1-0.5 ⁇ , 0.2-1 ⁇ , 0.5-3 ⁇ , 1-15 ⁇ , 1-10 ⁇ , 1-5 ⁇ , 1-3 ⁇ , 1.5-15 ⁇ , 2-15 ⁇ , 2-10 ⁇ , 2-5 ⁇ , and 2-3 ⁇ .
- D50 refers to the volume median particle size and can be determined by laser light scattering using the method described in CIPAC MT187.
- the composition of the present invention comprises a non-aqueous solvent system.
- non-aqueous solvent system means that one or more solvents other than water (e.g. organic solvents) are used as the liquid carrier in the liquid composition. This does not mean to say that the solvent system must necessarily be completely free of water. Trace amounts of water may be present in the components that are used to prepare the non-aqueous solvent system. For instance, trace amounts of water may be introduced into the solvent system by organic solvents, surfactants or salts that are used to prepare the liquid herbicidal composition. While the term “non-aqueous solvent system” is clear in this technical field (e.g.
- ODs, ECs and SLs employ a non-aqueous solvent system
- the term can be taken to mean that the liquid composition comprises water in an amount of 5 wt.% or less of the composition, preferably 3 wt.% or less, more preferably 2 wt.% and most preferably 1 wt.% or less.
- the sulfonylurea and lithium salt are dissolved, dispersed, suspended or otherwise contained in the non-aqueous solvent system. Typical solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
- the non-aqueous solvent system preferably contains one or more aprotic organic solvents as the major constituent of the solvent system.
- the amount of aprotic solvent in the solvent system is 50 wt.% or more, the ability of the lithium salt to chemically stabilise the sulfonylurea is greatly improved.
- the one or more aprotic solvents make up 60 wt.% or more, 70 wt.% or more, 80 wt.% or more and most preferably 90 wt.% or more of the solvent system.
- Suitable aprotic organic solvents for use in the present invention include, for example, those listed under "Component (C)" in US 2005/01 13254 (Bayer CropScience GmbH):
- hydrocarbons which may be unsubstituted or substituted, for example
- aromatic hydrocarbons for example mono- or polyalkyl-substituted benzenes, such as toluene, xylenes, mesitylene, ethylbenzene, or mono- or polyalkyl-substituted naphthalenes, such as 1 -methylnaphthalene, 2-methylnaphthalene or dimethylnaphthalene, or other benzene- derived aromatic hydrocarbons, such as indane or Tetralin ® , or mixtures thereof,
- (lb) aliphatic hydrocarbons for example straight-chain or branched aliphatics, for example of the formula C n H 2n +2, such as pentane, hexane, octane, 2-methylbutane or 2,2,4- trimethylpentane, or cyclic, optionally alkyl-substituted aliphatics, such as cyclohexane or methylcyclopentane, or mixtures thereof, such as solvents of the Exxsol ® D series, Isopar ® series or Bayol ® series, for example Bayol ® 82 (ExxonMobil Chemicals), or the Isane ® IP series or Hydroseal ® G series (TotalFinaElf), as well as straight-chain, branched or cyclic unsaturated aliphatics including terpenes such as turpentine and its constituents (e.g. pinene, camphene) as well as compounds derivable therefrom
- halogenated hydrocarbons such as halogenated aromatic and aliphatic
- hydrocarbons such as chlorobenzene or methylene chloride
- aprotic polar solvents such as ethers, esters of Ci-Ccralkanoic acids which may be mono-, di- or polyfunctional, such as their mono-, di- or triesters, for example with Ci-Cis-alkyl alcohols, ketones with a low tendency to tautomerize, phosphoric acid esters, amides, nitriles or sulfones, for example tris-2-ethylhexyl phosphate, diisobutyl adipate, Rhodiasolv ® RPDE (Rhodia), cyclohexanone, Jeffsol ® PC (Huntsman), ⁇ -butyrolactone, pyrrolidone -based solvents such as N- methylpyrrolidone or N-butylpyrrolidone, dimethyl sulfoxide, acetonitrile, tributylphosphatam or the Hostarex ® PO series (Clariant);
- fatty acid esters for example of natural origin, for example natural oils, such as animal oils or vegetable oils, or of synthetic origin, for example the Edenor ® series, for example Edenor ® MEPa or Edenor ® MESU, or the Agnique ® ME series or Agnique ® AE series (Cognis), the Salim ® ME series (Salim), the Radia ® series, for example Radia ® 30167 (ICI), the Prilube ® series, for example Prilube ® 1530 (Petrofina), the Stepan ® C series (Stepan) or the Witconol ® 23 series (Witco).
- natural origin for example natural oils, such as animal oils or vegetable oils
- synthetic origin for example the Edenor ® series, for example Edenor ® MEPa or Edenor ® MESU, or the Agnique ® ME series or Agnique ® AE series (Cognis)
- the Salim ® ME series for example Radia ® 30167 (ICI)
- the fatty acid esters are preferably esters of C 10 -C 22 -, with preference Ci2-C2o-fatty acids.
- the Cio-C22-fatty acid esters are, for example, esters of unsaturated or saturated C10-C22- fatty acids, in particular those having an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid, and in particular Cis-fatty acids, such as stearic acid, oleic acid, linoleic acid or linolenic acid.
- fatty acid esters such as Cio-C22-fatty acid esters are glycerol and glycol esters of fatty acids such as Cio-C22-fatty acids, or transesterification products thereof, for example fatty acid alkyl esters such as Cio-C22-fatty acid Ci-C2o-alkyl esters, which can be obtained, for example, by transesterification of the abovementioned glycerol or glycol fatty acid esters such as C 10 -C 22 -fatty acid esters with Ci-C2o-alcohols (for example methanol, ethanol, propanol or butanol).
- Ci-C22-fatty acid esters are glycerol and glycol esters of fatty acids such as Cio-C22-fatty acids, or transesterification products thereof, for example fatty acid alkyl esters such as Cio-C22-fatty acid Ci-C2o-alkyl esters, which can be obtained, for example, by transesterification of the above
- Cio-C22-fatty acid Ci-C2o-alkyl esters are methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters and dodecyl esters.
- Preferred glycol and glycerol fatty acid esters such as Cio-C22-fatty acid esters are the uniform or mixed glycol esters and glycerol esters of Cio-C22-fatty acids, in particular of such fatty acids having an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular Cis-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.
- Animal oils and vegetable oils are generally known and commercially available.
- animal oils is to be understood as meaning oils of animal origin such as whale oil, cod-liver oil, musk oil or mink oil
- vegetable oils is to be understood as meaning oils of oleaginous plant species, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, arachis oil, olive oil or castor oil, in particular rapeseed oil, where the vegetable oils also include their transesterification products, for example alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester.
- the vegetable oils are preferably esters of Cio-C22-fatty acids, preferably Ci2-C2o-fatty acids.
- the Cio-C22-fatty acid esters are, for example, esters of unsaturated or saturated Cio-C22-fatty acids having, in particular, an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular Cis-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.
- Examples of vegetable oils are Cio-C22-fatty acid esters of glycerol or glycol with Cio-C22-fatty acids, or Cio-C22-fatty acid Ci-C2o-alkyl esters which can be obtained, for example, by transesterification of the glycerol or glycol Cio-C22-fatty acid esters mentioned above with Ci- C2o-alcohols (for example methanol, ethanol, propanol or butanol).
- Ci- C2o-alcohols for example methanol, ethanol, propanol or butanol
- the vegetable oils can be contained in the mixtures for example in the form of commercially available vegetable oils, in particular rapeseed oils, such as rapeseed oil methyl ester, for example Phytorob ® B ( ovance, France), Edenor ® MESU and the Agnique ® ME series (Cognis, Germany) the Radia ® series (ICI), the Prilube ® series (Petrofina), or biodiesel or in the form of commercially available plant-oil- containing formulation additives, in particular those based on rapeseed oils, such as rapeseed oil methyl esters, for example Hasten ® (Victoria Chemical Company, Australia), Actirob ® B
- Examples of synthetic acid esters are, for example, those derived from fatty acids having an odd number of carbon atoms, such as Cn-C2i-fatty acid esters.
- Preferred organic solvents are hydrocarbons, in particular aromatic hydrocarbons and/or aliphatic hydrocarbons and fatty acid esters, such as vegetable oils, such as triglycerides of fatty acids having 10 to 22 carbon atoms, which may be saturated or else unsaturated, straight-chain or branched and which may or may not carry further functional groups, such as corn oil, rapeseed oil, sunflower oil, cottonseed oil, linseed oil, soybean oil, coconut oil, palm oil, thistle oil or castor oil, and their trans-esterification products, such as fatty acid alkyl esters, and mixtures thereof.
- Preferred solvents for use in the present invention include: linear or branched C6 to C30 paraffin oils, for example hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, their mixtures, or mixtures thereof with higher boiling homologs, such as hepta-, octa-, nona-decane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and the branched chain isomers thereof; aromatic or cycloaliphatic solvents, which may be unsubstituted or substituted, C7- to C18-hydrocarbon compounds such as mono- or polyalkyl-substituted benzenes, or mono- or polyalkyl-substituted
- vegetable oils such as liquid triglycerides, for example olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, walnut oil, coconut oil, cotton seed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, or also transesterification products thereof, e.g.
- alkyl esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester; animal oil, such as whale oil, cod-liver oil, or mink oil; liquid esters of CI to C 12 monoalcohols or polyols, for example butanol, n-octanol, i-octanol, dodecanol, cyclopentanol, cyclohexanol, cyclooctanol, ethylene glycol, propylene glycol or benzyl alcohol, with C2 to CIO carboxylic or polycarboxylic acids, such as caproic acid, capric acid, caprylic acid, pelargonic acid, succinic acid and glutaric acid; or with aromatic carboxylic acids such as benzoic acid, toluic acid, salicylic acid and phthalic acid.
- animal oil such as whale oil, cod-liver oil, or mink oil
- Esters which can be used in the composition of the invention are thus, for example, benzyl acetate, caproic acid ethyl ester, isobornyl acetate, pelargonic acid ethyl ester, benzoic acid methyl or ethyl ester, salicylic acid methyl, propyl, or butyl ester, diesters of phthalic acid with saturated aliphatic or ali cyclic CI to CI 2 alcohols, such as phthalic acid dimethyl ester, dibutyl ester, diisooctyl ester; liquid amides of C1-C3 amines, alkylamines or alkanolamines with C6 to CI 8 carboxylic acids; or mixtures thereof.
- the non-aqueous solvent system is present in an amount such that it can act as a liquid carrier for the other components that are present in the composition.
- the non-aqueous solvent system comprises an organic solvent in an amount of at least 5 wt.% based on the weight of the composition.
- a low amount of organic solvent is possible when other components in the composition are also liquids (e.g. liquid herbicide and/or liquid emulsifier).
- the non-aqueous solvent system comprises an organic solvent in an amount of at least 10 wt.%, at least 15 wt.%, at least 20 wt%, at least 25 wt%, at least 30 wt.%, or at least 40 wt.% of the composition.
- the non-aqueous solvent system comprises an organic solvent in an amount of 95 wt.% or less of the composition. More preferably the non-aqueous solvent system comprises an organic solvent in an amount of 90 wt.% or less, 85 wt.% or less, 80 wt.% or less, 75 wt.% or less, or 60 wt.% or less of the composition. Any of the disclosed wt.% lower limits for the amount of the organic solvent in the non-aqueous solvent system can be combined with any of the disclosed wt.% upper limits to define further suitable wt.% ranges for the purpose of this invention.
- exemplary ranges for the amount of the organic solvent in the composition include 5 to 95 wt.%, 10 to 90 wt.%, 20 to 80 wt.%, 30 to 60 wt.%, 40 to 60 wt.%, 10 to 75 wt.% and 20 to 60 wt.%.
- the amounts described herein refer to the sum amount of all the organic solvents present in the composition.
- the total amount of protic organic solvent such as alcohols, amines and carboxylic acids is preferably kept to 20 wt.% or less based on the weight of the liquid composition. More preferably, the total amount of protic organic solvent is 15 wt.% or less, 10 wt.% or less, 5 wt.% or less, 2 wt.% or less, or 1 wt.% or less of the composition.
- the amounts described herein refer to the sum amount of all the protic solvents present in the composition. 4.6 Additional active agents
- composition of the present invention may comprise one or more herbicides in addition to the sulfonylurea herbicide(s).
- additional non-sulfonylurea herbicides may be liquids, waxy solids or powders and may be dissolved, dispersed, suspended or otherwise contained in the composition.
- the additional herbicidal compound is not particularly limited and can be any herbicidal compound known in the art.
- the compound may be selected from the herbicidal compounds listed in the 16 th Edition of "The Pesticide Manual" (ISBN- 10:
- herbicidal compounds include:
- 2,4-D e.g. ester or amine
- 2,4-DB 2,3,6-TBA
- acetochlor acifluorfen, acifluorfen-sodium, aclonifen, alachlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, aminopyralid, amitrole, anilofos, asulam, atrazine, azafenidin, beflubutamid, benazolin,-benazolin-ethyl, benfuresate, bentazone, benzfendizone, benzobicyclon, benzofenap, bifenox, bilanafos, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide
- the additional non-sulfonylurea herbicide is preferably comprised in the liquid composition of the invention in an amount of at least 0.1 wt.%. More preferably, the non-sulfonylurea herbicide is comprised in an amount of at least 0.2 wt.%, at least 0.5 wt.%, at least 0.7 wt.%, at least 1 wt.%, at least 2 wt.%, at least 5 wt.%, at least 10 wt.%, at least 15 wt.%, at least 20 wt.% or at least 25 wt.%. The non-sulfonylurea herbicide is preferably comprised in the composition an amount of 95 wt.% or less.
- non-sulfonylurea herbicide is itself a liquid. More preferably, the non-sulfonylurea herbicide is comprised in an amount of 60 wt.% or less, 50 wt.% or less, 40 wt.% or less, 35 wt.% or less, 30 wt.% or less or 25 wt.% or less. Any of the disclosed wt.% lower limits for the amount of non- sulfonylurea herbicide can be combined with any of the disclosed wt.% upper limits to define further suitable wt.% ranges for the purposes of this invention.
- further exemplary ranges for the amount of non-sulfonylurea herbicide in the liquid composition include 0.1 to 95 wt.%, 1 to 60 wt.%, 2 to 50 wt.%, 5 to 40 wt.%, 10 to 30 wt.%, 15 to 25 wt.%, 25 to 35 wt.% and 10 to 50 wt.%.
- the wt.% amounts that are described herein refer to the weight of the salt or derivative.
- the amounts described herein refer to the sum amount of all of the non-sulfonylurea herbicides present in the composition.
- one or more of the non-sulfonylurea herbicides may be partially or wholly encapsulated (e.g. microcapsules) such as is described in WO 2008/061721 A2 (GAT Microencapsulation AG).
- the wt.% amounts that are described herein refer to the weight of the non-sulfonylurea herbicides without the encapsulating material.
- the liquid composition of the invention may comprise any of the sulfonylureas described herein with any of the non-sulfonylurea herbicides described herein.
- the liquid composition may comprise tribenuron-methyl and any of the other non- sulfonylurea herbicides described herein.
- Exemplary combinations with tribenuron-methyl include: tribenuron-methyl and 2,4-D (e.g. as ester or amine or choline salt); tribenuron methyl and MCPA (e.g.
- tribenuron-methyl and bromoxynil tribenuron-methyl and glyphosate; tribenuron-methyl and fluroxypyr; tribenuron-methyl and dicamba (e.g. as the sodium salt or diglycolamine salt or ester); tribenuron-methyl and mecoprop-P; tribenuron- methyl and MCPB; tribenuron-methyl, fluroxypyr and clopyralid; tribenuron-methyl and carfentrazone ethyl; tribenuron-methyl and clopyralid (e.g.
- the liquid composition may comprise nicosulfuron and any of the other non-sulfonylurea herbicides described herein.
- nicosulfuron examples include: nicosulfuron and dicamba (optionally as the sodium salt or ester); nicosulfuron and atrazine; nicosulfuron and flumetsulam; nicosulfuron and clopyralid (optionally as the potassium salt or ester); nicosulfuron and diflupenzopyr (optionally as the sodium salt or ester); nicosulfuron and metolachlor;
- the liquid composition may comprise metsulfuron-methyl and any of the other non-sulfonylurea herbicides described herein. Exemplary combinations with metsulfuron-methyl include:
- metsulfuron-methyl and acetochlor metsulfuron-methyl and carfentrazone ethyl; metsulfuron- methyl and imazapyr; metsulfuron-methyl and aminopyralid; metsulfuron-methyl and fluroxypyr; metsulfuron-methyl and mecoprop-p; metsulfuron-methyl and picloram; metsulfuron-methyl and pyraflufen ethyl; metsulfuron-methyl and propanil; metsulfuron-methyl and glyphosate- ammonium; metsulfuron-methyl and dicamba (optionally as the sodium, dimethylammonium or diglycolamine salt or as an ester); metsulfuron-methyl and 2,4-D (optionally as the
- dimethylammonium salt, choline salt, or an ester dimethylammonium salt, choline salt, or an ester
- metsulfuron-methyl, dicamba optionally as the sodium, dimethylammonium or diglycolamine salt or as an ester
- 2,4-D optionally as the dimethylammonium salt, choline salt, or an ester
- sulfonylureas and non-sulfonylureas for use in the present invention include: bensulfuron-methyl and acetochlor; bensulfuron-methyl and indanofan;
- pyrazosulfuron-ethyl and pretilachlor pyrazosulfuron-ethyl and pyriftalid; pyrazosulfuron-ethyl and mefenacet; pyrazosulfuron-ethyl and esprocarb; pyrazosulfuron-ethyl and dimethametryn; pyrazosulfuron-ethyl and
- oxaziclomefone pyrazosulfuron-ethyl and benzobicyclon; pyrazosulfuron-ethyl and cyhalo fop- butyl; pyrazosulfuron-ethyl and penoxsulam; pyrazosulfuron-ethyl, cyhalofop-butyl, pretilachlor, and dimethametryn; pyrazosulfuron-ethyl, benzobicyclon and penoxsulam; pyrazosulfuron-ethyl, benzobicyclon, dimethametryn and oxaziclomefone; pyrazosulfuron-ethyl, pretilachlor, dimethametryn, and esprocarb; pyrazosulfuron-ethyl, benzobicyclon, butachlor and pyraclonil; pyrazosulfuron-ethyl, benzobicyclon and
- composition of the present invention may comprise one or more safeners that may be dissolved, dispersed, suspended or otherwise contained in the composition.
- Suitable safeners are those listed in the "The Pesticide Manual” (ISBN- 10: 190139686X), as well as those listed in paragraphs [0113] to [0129] of US 2006/0276337 Al, which paragraphs are incorporated herein by reference.
- Exemplary safeners include:
- dichlorophenylpyrazolecarboxylic acid preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate, ethyl l-(2,4-dichlorophenyl)-5- isopropylpyrazole-3-carboxylate, ethyl l-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)pyrazole-3- carboxylate, ethyl l-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate and related compounds, as described in EP-A-333 131 and EP-A-269 806;
- active compounds of the type of the phenoxyacetic or -propionic acid derivatives or the aromatic carboxylic acids such as, for example, 2,4-dichlorophenoxyacetic acid (esters), 4- chloro-2-methylphenoxy-propionic esters, MCPA or 3,6-dichloro-2-methoxybenzoic acid (esters);
- active compounds of the type of the oxyimino compounds such as, for example, “oxabetrinil” ((Z)-l,3-dioxolan-2-ylmethoxyimino-(phenyl)acetonitrile), “fluxofenim” (l-(4- chlorophenyl)-2,2,2-trifluoro-l-ethanone 0-(l ,3-dioxolan-2-ylmethyl) oxime, and "cyometrinil” or "CGA43089” ((Z)-cyanomethoxyimino-(phenyl)acetonitrile);
- active compounds of the type of the thiazolecarboxylic esters which are known as seed dressings, such as, for example, "flurazole” (benzyl 2-chloro-4-trifluoromethyl-l,3-thiazole- 5-carboxylate);
- active compounds of the type of the naphthalenedicarboxylic acid derivatives such as, for example, "naphthalic anhydride” (1 ,8-naphthalenedicarboxylic anhydride);
- active compounds of the type of the chromanacetic acid derivatives such as, for example, "CL 304415” (CAS-Reg. No. 31541-57-8) (2-(4-carboxychroman4-yl)acetic acid from American Cyanamid);
- active compounds which, in addition to a herbicidal action against harmful plants, also have safener action on crop plants such as, for example, "dimepiperate” or "MY-93" (-S-1- methyl- 1 -phenylethyl piperidine-l-thiocarboxylate), “daimuron” or “SK 23” ( 1-(1 -methyl- 1- phenylethyl)-3-p-tolyl-urea), “cumyluron” or "JC-940" (3-(2-chlorophenylmethyl)-l-(l-methyl- l-phenyl-ethyl)urea, see JP-A-60087254), "methoxyphenone” or “NK 049” (3,3'-dimethyl-4- methoxybenzophenone), “CSB” (l-bromo-4-(chloromethylsulfonyl)benzene) (CAS-Reg No. 54091-06-4 from Kumiai).
- Preferred herbicide safeners for use in the present invention include benoxacor, BCS (l-bromo-4- [(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, 2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), dietholate, fenchlorazole- ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, jiecaowan, jiecaoxi, mefenpyr, mefenpyrethyl, methoxyphenone ((4-methoxy-3-methylphenyl)(3- methylphenyl)methanone), mephenate, naphthalic anhydride and oxabetrinil.
- the liquid composition of the invention may comprise any of the sulfonylureas described herein with any suitable safener described herein.
- exemplary combinations of sulfonylurea and safener include: iodosulfuron-methyl (optionally as the sodium salt) and mefenpyr-diethyl; mesosulfuron (and/or as the methyl ester) and mefenpyr-di-ethyl; mesosulfuron (and/or as the methyl ester) and propoxycarbazone (e.g. sodium salt) and mefenpyr-di-ethyl. 4.6.3 Other salts
- the liquid composition of the invention may comprise further salts such as those disclosed in PCT/EP2015/080844.
- the liquid composition of the invention may comprise an inorganic salt selected from the metal carbonates and metal phosphates.
- Preferred additional salts include those where the inorganic salt is selected from alkali metal phosphates and alkali metal carbonates or where the inorganic salt comprises a metal selected from Na, K, Ca, Mg or Al.
- Particularly preferred are those salts selected from Na 3 P0 4 , K 3 P0 4 , Mg 3 (P0 4 ) 2 , A1P0 4 , and Na 2 C0 3 . 4.7 Co-formulants
- the composition of the invention may comprise one or more additional co-formulants such as surfactants (e.g. emulsifiers and/or dispersants), thickeners and thixotropic agents, wetting agents, anti-drift agents, adhesives, penetrants, preservatives, antifreeze agents, antioxidants, solubilizers, fillers, carriers, colorants, antifoams, fertilizers, evaporation inhibitors and agents which modify pH and viscosity.
- surfactants e.g. emulsifiers and/or dispersants
- thickeners and thixotropic agents wetting agents, anti-drift agents, adhesives, penetrants, preservatives, antifreeze agents, antioxidants, solubilizers, fillers, carriers, colorants, antifoams, fertilizers, evaporation inhibitors and agents which modify pH and viscosity.
- additional co-formulants such as surfactants (e.g. emulsifiers and/or dis
- composition comprises at least one co-formulant that is an adjuvant, such as one of those listed in the Compendium of Herbicide Adjuvants, 12th Edition, Southern Illinois University, 2014, or any earlier edition thereof.
- adjuvants include, but are not limited to, paraffin oil, horticultural spray oils (e.g., summer oil), methylated rape seed oil, methylated soybean oil, highly refined vegetable oil and the like, polyol fatty acid esters, polyethoxylated esters, ethoxylated alcohols, alkyl polysaccharides and blends, amine ethoxylates, sorbitan fatty acid ester ethoxylates, polyethylene glycol esters, alkylpolyglucosides and their derivatives (e.g.
- the liquid composition of the invention includes one or more surfactants, for example, to enable the forming an emulsion if the compositions are to be diluted with water.
- surfactants can be cationic, anionic or non-ionic, but are preferably anionic or non-ionic.
- Preferred non-ionic surfactants for use in this invention include: polyalkoxylated, preferably polyethoxylated, saturated and unsaturated aliphatic alcohols having 8 to 24 carbon atoms in the alkyl radical, which is derived from the corresponding fatty acids or from petrochemical products, and having 1 to 100, preferably 2 to 50, ethylene oxide units (EO), it being possible for the free hydroxyl group to be alkoxylated, which are commercially available, for example, as Genapol ® X and Genapol ® O series (Clariant), Crovol ® M series (Croda) or as Lutensol series (BASF); polyalkoxylated, preferably polyethoxylated, arylalkylphenols, such as, for example, 2,4,6-tris(l-phenylethyl)phenol (tristyrylphenol) having an average degree of ethoxylation of between 10 and 80, preferably from 16 to 40, such as, for example, Soprophor
- Preferred ionic surfactants for use in this invention include: polyalkoxylated, preferably polyethoxylated, surfactants which are ionically modified, for example by conversion of the terminal free hydroxyl function of the polyethylene oxide block into a sulfate or phosphate ester (for example as alkali metal and alkaline earth metal salts), such as, for example, Genapol ® LRO or dispersant 3618 (Clariant), Emulphor ® (BASF) or Crafol ® AP (Cognis); alkali metal and alkaline earth metal salts of alkylarylsulfonic acids having a straight-chain or branched alkyl chain, such as phenylsulfonate CA or phenylsulfonate CAL (Clariant), Atlox ® 3377BM (ICI), or the Empiphos ® TM series (Huntsman); polyelectrolytes, such as ligno sulfonates
- OMS organo-modified siloxanes
- GET Microencapsulation examples include those disclosed in the Compendium of Herbicide Adjuvants, 12th Edition, Southern Illinois University, 2014, or any earlier edition thereof, as well as those disclosed in WO 2008/155108 A2 (GAT Microencapsulation), as well as the polyether-polysiloxane copolymers described in GB 2496643 (Rotam Agrochem), including those available from Evonik Industries under the trade names Break-Thru 9902TM, Break-Thru 9903TM, Break-Thru 5503TM, Break-Thru 9907TM and Break-Thru 9908TM.
- OMS organo-modified siloxanes
- the surfactant is preferably included in an amount of at least 1 wt.% with respect to the total weight of the composition. More preferably, the surfactant is comprised in an amount of at least 2 wt.%, at least 5 wt.%, at least 10 wt.%, at least 15 wt.%, or at least 20 wt.%. The surfactant is preferably comprised in the composition an amount of 60 wt.% or less. More preferably, the surfactant is comprised in an amount of 50 wt.% or less, 40 wt.% or less, or 30 wt.% or less.
- any of the disclosed wt.% lower limits for the amount of surfactant can be combined with any of the disclosed wt.% upper limits to define further suitable wt.% ranges for the purposes of this invention.
- further exemplary ranges for the amount of surfactant in the liquid composition include 1 to 60 wt.%, 2 to 50 wt.%, 5 to 40 wt.%, 10 to 30 wt.%, 5 to 50 wt.% and 2 to 40 wt.%. Where more than one surfactant is used the preferred ranges refer to the total amount of surfactant present in the liquid composition.
- composition of the invention can be prepared by known processes, for example by mixing the components and milling the suspended solids or dissolving the solids.
- Any soluble agrochemically active compounds used can also be dissolved in the premix.
- solid sulfonylurea, any other insoluble agrochemically active compounds used and the lithium salts can be suspended in the mixture.
- the coarse suspension is, if appropriate after pregrinding, subjected to fine grinding.
- solid sulfonylurea and, if appropriate, any insoluble components used are suspended in the non-aqueous solvent system and subjected to grinding. Any soluble active compounds used and any auxiliaries and additives which do not require grinding or are not required for the grinding process can be added after grinding.
- the invention is concerned with improving chemical stability of a sulfonylurea herbicide in liquid composition comprising a non-aqueous solvent system. Improved chemical stability may be achieved by including, in the liquid composition, at least one inorganic or C1-C12 organic lithium salt as discussed herein.
- the sulfonyl urea, the lithium salt and the non-aqueous solvent system can be selected to meet desired needs such as to ensure that the liquid composition conforms with one or more local regulatory requirements.
- the sulfonyl urea, the lithium salt and the non-aqueous solvent system are selected such that the sulfonyl urea exhibits at least 85% chemical stability.
- the sulfonyl urea exhibits at least 90% chemical stability, more preferably at least 95% chemical stability, and still more preferably at least 98% chemical stability.
- Chemical stability can be determined as a percentage of the sulfonyl urea remaining (e.g. as determined by HPLC) when the liquid composition (e.g. a 50 ml sample of the liquid composition in a 60 ml hermetically sealed Winchester bottle) has been stored at 54°C for two weeks relative to a corresponding control sample that has been stored at -10°C for two weeks.
- the liquid composition is one where chemical stability of the sulfonyl urea is improved by at least 2% compared to a corresponding liquid composition that does not contain a lithium salt according to the invention (instead of salt, an equivalent extra wt.% of solvent is used).
- Chemical stability of the sulfonylurea for each of the salt-containing liquid composition and the non-salt control composition can be determined as described immediately above. The difference in chemical stability can then be calculated to determine that an improvement of at least 2% is achieved.
- the sulfonyl urea exhibits at least a 5% improvement, more preferably at least a 10% improvement, and even more preferably at least a 50% improvement in chemical stability.
- the liquid composition is one where the sulfonyl urea exhibits at least 85% chemical stability (as described above), and is one where the chemical stability of the sulfonyl urea is improved by at least 10% compared to a
- the sulfonyl urea exhibits at least 90% chemical stability, more preferably at least 95% chemical stability, and even more preferably at least 98% chemical stability.
- the chemical stability, or improvement thereon is determined based on the total amount of sulfonylurea herbicide in the composition.
- composition of the invention can be applied directly or can be diluted with water and then applied to plant foliage and/or soil by methods commonly employed in the art, such as conventional high-volume hydraulic sprays, low-volume sprays, air-blast, and aerial sprays.
- the diluted composition may be applied to the plant foliage or to the soil or area adjacent to the plant.
- the selection of the specific herbicidal compounds in the composition both sulfonylureas and non-sulfonylureas
- rates and mode of application are determined by the selectivity of the herbicidal compounds to specific crops and by the prevalent weed species to be controlled and are known to those skilled in the art (e.g. see "The Pesticide Manual" (ISBN- 10:
- liquid compositions of the invention are as follows:
- An oil dispersion (OD) comprising a suspension of lithium acetate and at least one
- sulfonylurea in a non-aqueous solvent system, wherein the at least one sulfonylurea is selected from metsulfuron, halosulfuron, iodosulfuron, pyrazosulfuron, amidosulfuron, or esters and/or salts thereof.
- An oil dispersion (OD) comprising a suspension of lithium carbonate and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An oil dispersion (OD) comprising a suspension of lithium formate and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An oil dispersion (OD) comprising a suspension of lithium chloride and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An oil dispersion (OD) comprising a suspension of lithium citrate and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An emulsifiable concentrate comprising lithium acetate and at least one sulfonylurea in a non-aqueous solvent system, wherein the at least one sulfonylurea is selected from metsulfuron, halosulfuron, iodosulfuron, pyrazosulfuron, amidosulfuron, or esters and/or salts thereof.
- An emulsifiable concentrate comprising lithium carbonate and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An emulsifiable concentrate comprising lithium formate and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An emulsifiable concentrate comprising lithium chloride and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An emulsifiable concentrate comprising lithium citrate and iodosulfuron or esters and/or salts thereof in a non-aqueous solvent system.
- An soluble concentrate (SL) comprising lithium acetate and at least one sulfonylurea in a non-aqueous solvent system, wherein the at least one sulfonylurea is selected from metsulfuron, halosulfuron, iodosulfuron, pyrazosulfuron, amidosulfuron, or esters and/or salts thereof.
- SL soluble concentrate
- SL soluble concentrate
- metsulfuron-methyl (optionally as the sodium salt) or halosulfuron- methyl or iodosulfuron-methyl (optionally as the sodium salt) or pyrazosulfuron-ethyl or amidosulfuron; and
- liquid composition according to any one of embodiments (ii), (vii), (xii) comprising: 5 to 15 wt.% of iodosulfuron-methyl (optionally as the sodium salt); and
- any of the exemplary embodiments (i) to (xxiv) as listed above can be further modified in line with the general description provided herein.
- the sulfonylurea can be replaced with any other sulfonylurea disclosed herein and the salt can be replaced with any other salt disclosed herein in accordance with the invention.
- the sulfonylurea can be replaced with iodosulfuron methyl (optionally as the sodium salt) and the salt can be replaced with lithium acetate, or lithium benzoate, or lithium octanoate, or lithium salicylate.
- the lithium salt can be replaced with lithium octanoate and the sulfonylurea can be replaced with foramsulfuron, or chlorsulfuron, or pyrazosulfuron-ethyl, or amidosulfuron, or halosulfuron-methyl, or iodosulfuron-methyl (optionally as the sodium salt).
- embodiments (i) to (xxiv) can be set from 1 to 50wt.%, 2 to 40 wt.%, 5 to 30 wt.%, 0.5 to 20 wt.%, 7 to 30 wt.%, and 5 to 10 wt.%.
- the total amount of lithium salt that is present in the exemplary embodiments (i) to (xxiv) can be from 0.1 to 25 wt.%, 1 to 20 wt.%, 1 to 10 wt.%, 0.5 to 10 wt.%, 1 to 5 wt.% and 0.5 to 5 wt.%.
- the weight ratio of the total amount of lithium salt recited in the embodiments above to the total amount of recited sulfonylurea can be from 0.2 to 4, 0.3 to 3, 0.5 to 2, 0.7 to 2, 0.1 to 2, 1 to 2 and 1 to 5.
- any of the exemplary embodiments including metsulfuron or metsulfuron-methyl (in both cases, optionally as the sodium salt) can further comprise fluroxypyr-meptyl as a non-sulfonylurea.
- the lithium salt in any of the above embodiments (i) to (xxiv) can be replaced with another lithium salt as described herein, for example, lithium octanoate or lithium benzoate.
- Any of the exemplary embodiments (i) to (xxiv) or as described herein can further comprise a surfactant and/or a safener.
- Sulfonylurea was added to a solvent in an amount of 25 wt.%.
- the mixture was placed in a mill (Eiger Torrance Mini Mill) containing glass beads (1.0-1.25 mm).
- the suspension was then milled to provide a 25 wt.% sulfonylurea millbase having a particle size (D50) between 2 and 3 ⁇ .
- Lithium salt was added to solvent in an amount of 25 wt.% and milled as described above to provide a 25 wt.% lithium salt millbase having a particle size (D50) between 2 and 3 ⁇ .
- Oil dispersions of iodosulfuron-methyl sodium salt (IMS) with or without added acetate salt were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 1 below.
- Oil dispersions of iodosulfuron-methyl sodium (IMS) with or without added lithium and sodium salts were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 2-1 and Table 2-2 below.
- a sulfonylurea-containing oil dispersions comprising a lithium salt (OD6-OD10; OD16-OD18) is superior to an oil dispersion with the corresponding sodium salt (OD11-OD15; OD19-OD21), irrespective if the salt is an organic salt (Table 2-1) or an inorganic salt (Table 2-2). Stability without any salt after storage at 54°C for two weeks is 74.1% (see OD5 in Table 1). Thus, while sodium salts can improve stability of the sulfonylurea, the corresponding lithium salt improves stability to an even greater extent.
- Oil dispersions of various sulfonylureas with or without added lithium acetate salt were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 3 below.
- sulfonylurea-containing oil dispersions comprising an inorganic acid salt of lithium (OD22-OD26) were found to be superior to corresponding oil dispersions with no co-formulated lithium salt (OD27-OD31). Improved stability is achieved for different amounts of sulfonylurea, different amounts of lithium salt, and different surfactant systems.
- Oil dispersions of iodosulfuron-methyl sodium salt or halosulfuron-methyl with or without added lithium carbonate salt were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 4 below.
- Example 5 Comparison of a Li C8-organic acid salt and a Li C16-organic acid salt for various sulfonylureas
- Oil dispersions of various sulfonylureas with or without added lithium octanoate and lithium 12- hydroxystearate were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 5-1 (with salt) and Table 5-2 (no salt) below.
- Example 6 Comparison of a Li C8-organic acid salt and a Li C16-organic acid salt at various concentrations
- Oil dispersions of halosulfuron-methyl with or without added lithium octanoate and lithium 12- hydroxystearate at various concentrations were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 6-1 and Table 6-2 below.
- Example 7 Comparison of various Li organic acid salts for stabilising low-concentration iodosulfuron-methyl sodium salt
- Oil dispersions having a low concentration (1 wt.%) iodosulfuron-methyl sodium salt (IMS) with or without added lithium salts were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks. The results are summarised in Table 7 below.
- sulfonylurea-containing oil dispersions comprising a lithium salt according to the invention (OD65-OD68) were found to be superior to corresponding oil dispersions with the CI 6 organic acid salt of lithium (OD69) as well as a corresponding oil dispersion with no salt (OD70).
- Example 8 Comparison of various Li organic acid salts for stabilising low-concentration iodosulfuron-methyl sodium salt in a Solvesso liquid system
- Oil dispersions having a low concentration (0.5 wt.%) iodosulfuron-methyl sodium salt (IMS) with or without added lithium salts were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks.
- IMS iodosulfuron-methyl sodium salt
- Table 8 The results are summarised in Table 8 below.
- Oil dispersions having a mixture of sulfonylureas with or without an added lithium salt were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks.
- the results are summarised in Table 9 below.
- the sulfonylureas are numbered 1 -4 and their respective stabilities are reported using the same numbering.
- Example 10 Comparison of various Li organic acid salts for stabilising a mixture of a sulfonylurea and a non-sulfonyizi ea
- Oil dispersions having a mixture of a sulfonylurea and a non-sulfonylurea with or without an added lithium salt were prepared and tested to determine the chemical stability of the sulfonylurea after storage at 54°C for two weeks.
- the results are summarised in Tables 10-1 and 10-2 below.
- the sulfonylureas and the non-sulfonylureas are numbered and their respective stabilities are reported using the same numbering.
- a liquid composition comprising a sulfonyl urea in a non-aqueous solvent system (N-butyl pyrrolidone) was prepared with and without an added salt and tested.
- the sulfonylurea was dissolved in the N-butyl pyrrolidone and the salt (milled) was dispersed as solid particles.
- the stability of the sulfonylurea after storage at 54°C for two weeks is reported in Table 11 below.
- liquid herbicidal compositions comprising a non-aqueous solvent system; at least one
- the at least one lithium salt is not a lithium carbonate or a lithium phosphate.
- This proviso that the at least one lithium salt is not a lithium carbonate or a lithium phosphate may be applied to all disclosures herein, including the appended claims, unless of course a disclosure expressly calls for the presence of lithium carbonate and/or lithium phosphate.
Landscapes
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- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
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Abstract
Description
Claims
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BR112018071885-8A BR112018071885B1 (en) | 2016-06-21 | 2017-06-21 | LIQUID HERBICIDAL COMPOSITIONS CONTAINING SULFONYL UREA AND LITHIUM SALT AND USE OF THESE SALTS |
PL17733415T PL3416486T3 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
CN201780024577.8A CN110035657B (en) | 2016-06-21 | 2017-06-21 | Liquid herbicidal composition containing sulfonylurea and Li salt |
EA201891997A EA033330B1 (en) | 2016-06-21 | 2017-06-21 | LIQUID SULFONYLUREA- AND Li-SALT CONTAINING HERBICIDAL COMPOSITIONS |
JP2018551392A JP6811784B6 (en) | 2016-06-21 | 2017-06-21 | Herbicidal composition containing liquid sulfonylurea and Li salt |
KR1020187029826A KR102163883B1 (en) | 2016-06-21 | 2017-06-21 | Herbicide composition containing liquid sulfonylurea- and LI- salts |
US16/087,576 US11464225B2 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
LTEP17733415.8T LT3416486T (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
CA3018651A CA3018651C (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea-and li-salt containing herbicidal compositions |
MYPI2018001608A MY198487A (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea-and l1-salt containing herbicidal compositions |
MX2018012367A MX2018012367A (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions. |
ES17733415T ES2732049T3 (en) | 2016-06-21 | 2017-06-21 | Herbicidal compositions containing Li salt and liquid sulfonylurea |
EP17733415.8A EP3416486B1 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
EP19175100.7A EP3549443A1 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
AU2017281579A AU2017281579B2 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and Li-salt containing herbicidal compositions |
UAA201809618A UA120736C2 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
RS20190768A RS58885B1 (en) | 2016-06-21 | 2017-06-21 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
CONC2018/0011196A CO2018011196A2 (en) | 2016-06-21 | 2018-10-19 | Liquid herbicidal compositions containing li and sulfonylurea salt |
HRP20190979TT HRP20190979T1 (en) | 2016-06-21 | 2019-05-29 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
US17/873,854 US20220378040A1 (en) | 2016-06-21 | 2022-07-26 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
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US17/873,854 Continuation US20220378040A1 (en) | 2016-06-21 | 2022-07-26 | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
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US (2) | US11464225B2 (en) |
EP (2) | EP3549443A1 (en) |
JP (1) | JP6811784B6 (en) |
KR (1) | KR102163883B1 (en) |
CN (1) | CN110035657B (en) |
AU (1) | AU2017281579B2 (en) |
CA (1) | CA3018651C (en) |
CO (1) | CO2018011196A2 (en) |
EA (1) | EA033330B1 (en) |
ES (1) | ES2732049T3 (en) |
HU (1) | HUE043981T2 (en) |
LT (1) | LT3416486T (en) |
MX (1) | MX2018012367A (en) |
MY (1) | MY198487A (en) |
PL (1) | PL3416486T3 (en) |
PT (1) | PT3416486T (en) |
RS (1) | RS58885B1 (en) |
UA (1) | UA120736C2 (en) |
WO (1) | WO2017220680A1 (en) |
Cited By (6)
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WO2020234175A1 (en) | 2019-05-21 | 2020-11-26 | Syngenta Crop Protection Ag | Improved herbicidal oil dispersion compositions |
US11109588B2 (en) | 2019-02-19 | 2021-09-07 | Gowan Company, L.L.C. | Stable liquid formulations and methods of using the same |
EP3900535A1 (en) | 2020-04-24 | 2021-10-27 | Battelle UK Limited | Liquid sulfonylurea herbicide composition |
RU2767999C1 (en) * | 2021-08-05 | 2022-03-22 | ООО "Агро Эксперт Груп" | Liquid herbicide composition |
US20220151229A1 (en) * | 2019-02-25 | 2022-05-19 | Clariant International Ltd. | Synergistic Herbicidal Combinations |
RU2810478C1 (en) * | 2023-05-03 | 2023-12-27 | Акционерное общество "Щелково Агрохим" | Herbicidal composition for corn crops |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107427010B (en) * | 2014-12-22 | 2020-07-17 | 三井农业化学国际有限公司 | Liquid sulfonylurea-containing herbicidal compositions |
EP3549443A1 (en) * | 2016-06-21 | 2019-10-09 | Battelle UK Limited | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
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Cited By (7)
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US11109588B2 (en) | 2019-02-19 | 2021-09-07 | Gowan Company, L.L.C. | Stable liquid formulations and methods of using the same |
US20220151229A1 (en) * | 2019-02-25 | 2022-05-19 | Clariant International Ltd. | Synergistic Herbicidal Combinations |
WO2020234175A1 (en) | 2019-05-21 | 2020-11-26 | Syngenta Crop Protection Ag | Improved herbicidal oil dispersion compositions |
EP3900535A1 (en) | 2020-04-24 | 2021-10-27 | Battelle UK Limited | Liquid sulfonylurea herbicide composition |
WO2021214316A1 (en) | 2020-04-24 | 2021-10-28 | Battelle Uk Limited | Liquid sulfonylurea herbicide composition |
RU2767999C1 (en) * | 2021-08-05 | 2022-03-22 | ООО "Агро Эксперт Груп" | Liquid herbicide composition |
RU2810478C1 (en) * | 2023-05-03 | 2023-12-27 | Акционерное общество "Щелково Агрохим" | Herbicidal composition for corn crops |
Also Published As
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UA120736C2 (en) | 2020-01-27 |
AU2017281579B2 (en) | 2019-02-28 |
EP3549443A1 (en) | 2019-10-09 |
JP6811784B6 (en) | 2023-03-22 |
MX2018012367A (en) | 2019-03-07 |
CN110035657B (en) | 2020-03-24 |
ES2732049T3 (en) | 2019-11-20 |
AU2017281579A1 (en) | 2018-10-11 |
CO2018011196A2 (en) | 2019-02-08 |
KR102163883B1 (en) | 2020-10-13 |
PT3416486T (en) | 2019-06-25 |
JP2019518717A (en) | 2019-07-04 |
EP3416486A1 (en) | 2018-12-26 |
KR20190019906A (en) | 2019-02-27 |
CA3018651A1 (en) | 2017-12-28 |
US20190110468A1 (en) | 2019-04-18 |
US20220378040A1 (en) | 2022-12-01 |
EA201891997A1 (en) | 2019-02-28 |
EA033330B1 (en) | 2019-09-30 |
PL3416486T3 (en) | 2019-11-29 |
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JP6811784B2 (en) | 2021-01-13 |
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CA3018651C (en) | 2019-06-04 |
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US11464225B2 (en) | 2022-10-11 |
LT3416486T (en) | 2019-07-10 |
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