WO2024133245A1 - Combinaison de tensioactifs pour formulations agrochimiques aqueuses en suspension (protection des cultures) d'un herbicide hppd combiné à une concentration élevée d'un principe actif présent sous la forme d'un sel - Google Patents

Combinaison de tensioactifs pour formulations agrochimiques aqueuses en suspension (protection des cultures) d'un herbicide hppd combiné à une concentration élevée d'un principe actif présent sous la forme d'un sel Download PDF

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WO2024133245A1
WO2024133245A1 PCT/EP2023/086623 EP2023086623W WO2024133245A1 WO 2024133245 A1 WO2024133245 A1 WO 2024133245A1 EP 2023086623 W EP2023086623 W EP 2023086623W WO 2024133245 A1 WO2024133245 A1 WO 2024133245A1
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weight
surfactant
aqueous dispersion
aqueous
ammonium
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PCT/EP2023/086623
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Arianna Martelletti
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Bayer Aktiengesellschaft
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  • the invention relates to the technical field of herbicidal compositions and surfactant combinations for crop protection formulations with high salt like active ingredient content, as well as methods for producing said compositions and formulations.
  • the present invention further relates to aqueous formulations of water-soluble active ingredients, in particular aqueous formulations of salt-like active ingredients, and in particular to formulations containing glufosinate as an agrochemically acceptable salt thereof, preferably ammonium, in combination with at least one further HPPD active ingredient, in particular selected from the triketone family, and at least one safener, wherein at least the HPPD active ingredient is suspended in the formulation.
  • the high salt like active ingredient may be preferably glufosinate-ammonium.
  • the present invention relates to a herbicidal composition in form of aqueous dispersions comprising
  • the herbicidal composition of the present invention is a “suspension concentrate” (SC), wherein the HPPD -inhibiting herbicide and safener components are present as suspension in a water and glufosinate (e.g. ammonium salt) solution.
  • SC suspension concentrate
  • Herbicidally active compounds are generally not employed in their pure form. Depending on the area of use and the type of application, and on physical, chemical and biological parameters, the active compounds are employed as an active compound formulation in a mixture with customary auxiliaries and additives. Combinations with further active substances for widening the spectrum of action are also known.
  • Safeners are compounds which, fully or predominantly, prevent the phytotoxic side-effects of herbicides in useful plants thus protecting the crop plants.
  • Various formulations for water soluble active ingredients are known, in particular for herbicides like glufosinate in its salt form.
  • SC formulation active ingredient in dispersion
  • a HPPD inhibitor in particular a triketone herbicide like tembotrione
  • chemical stability of the formulation is not attained.
  • compositions comprising HPPD-inhibiting herbicides are known in the art. Suspension concentrates or water-dispersible granules are already known as formulations of these active substances, see, for example, “The Pesticide Manual” 13th edition (2003), The British Crop Protection Council.
  • WO 08/135854A2 relates to oil dispersions comprising a 2-benzoyl- 1,3-cyclohexanedione herbicide.
  • EP2193712A1 relates to dispersions containing herbicidal active compounds which are known as inhibitors of hydroxyphenylpyruvate dioxygenase (HPPD).
  • HPPD hydroxyphenylpyruvate dioxygenase
  • WO 02/091831 relates to herbicidal compositions comprising certain benzoylcyclohexanediones in combination with nitrogen fertilizers and adjuvants, which are useful for the selective control of weeds and weed grasses in important plant crops.
  • WO 09/103455 relates to a herbicide formulation comprising a 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor, a chloroacetamide herbicide or an isoxazoline herbicide and glyphosate and/or glufosinate.
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • WO 20/025652 Al relates to the technical field of thickener combinations for crop protection formulations with high salt content, in particular herbicidal formulations, and formulations containing said adjuvant combinations, as well as methods for producing said formulations.
  • W02007006415 A2 relates to herbicidal compositions containing as active ingredient tembotrione as a herbicide from the group of benzoylcyclohexanediones in combination with at least one other herbicide and a safener.
  • Herbicides are widely used in crop protection. Most of them are used as sole actives in agrochemical compositions, but it has been discovered that some of them may increase their activity when used in association. For practical reasons, it is desirable for the end user to have a single composition to apply to its crop, i.e. a combination formulation.
  • Formulations of herbicidal active ingredients should generally have high chemical and physical stability, good applicability and user-friendliness and a broad biological action with high selectivity.
  • compositions comprising at least two active ingredients selected from the group of glufosinate as ammonium salt and HPPD inhibitors, in particular triketone HPPD inhibitors, as well as at least one safener.
  • Another object of the instant invention is to provide a surfactant combination for aqueous herbicidal formulations which does not show the disadvantages of the chemical instability known in the art for low loaded suspension formulations in water of HPPD inhibitors, in particular triketone HPPD inhibitors, containing high salt content.
  • an agrochemical composition comprising: a herbicidal mixture as a combination of a salt-like herbicide, a triketone, and a safener; more specifically glufosinate-ammonium salt, tembotrione, and a safener; a stabilizing surfactant/adjuvant system comprising an alkylpoly glycoside alone used between 5 and 25%, preferred 8 to 24%, and even more preferred 10-22%, optionally with an adjuvant based on choline chloride.
  • the present invention also provides a process for the preparation of said agrochemical composition, wherein all the components are mixed together in a specific order.
  • the ability to provide these herbicides as a stable "ready-mix" composition has several significant advantages.
  • the herbicidal compositions of the present invention also provide comparable or improved biological function compared to tank-mixed compositions, both in terms of efficacy and selectivity.
  • a surfactant system refers to a compound or a mixture of compounds that lowers the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid.
  • a specific surfactant or surfactant combination can significantly chemically stabilize HPPD-inhibiting herbicides, in particular tembotrione, in particular at low loading of max. 4 to 5% w/w, in herbicidal compositions, and in particular suspension concentrates in water in the presence of a high salt content.
  • a surfactant from the group of alkylpolyglucoside surfactants or the combination of an alkylpolyglucoside surfactant and an adjuvant based on choline chloride, can stabilize low loaded high salt content formulations of active ingredients formulated as suspension concentrates in water, in particular herbicides, preferably an HPPD active ingredient from the triketone class, present as at low loading as of 4 to 5% w/w.
  • the storage stability of these formulations using a combination of a HPPD inhibitor, in particular a triketone HPPD inhibitor, in particular at low loading of max. 4 to 5% w/w, glufosinate-ammonium salt, and a safener may be markedly improved by using a specific surfactant combination from the class of alkylpolyglycosides alone or in combination with an adjuvant based on choline chloride.
  • the biological efficacy of such all-in-one combination of herbicides is at least, if not better, comparable to the use of the herbicides alone as a tank-mix application.
  • the particle size diameter of the herbicides and the safener in the liquid herbicidal composition (defined as D90) is between 6 pm and 12 pm, as compositions comprising particles of this size have been shown to exhibit improved physical stability.
  • the particle size is determined as follows:
  • a herbicidal composition in form of a water-based suspension concentrate comprising:
  • a surfactant or a surfactant combination comprising at least one alkylpolyglycoside surfactant DI) or one alkylpolyglycoside surfactant DI) and one adjuvant based on choline chloride D2), and further optionally an alkoxylated phosphate ester surfactant D3),
  • a pH adjuster preferably citric acid anhydrous
  • adjuvant based on choline chloride refers to an adjuvant comprising choline chloride in a mixture of water and glycol solvent.
  • the adjuvant based on choline chloride comprises 50% to 90% by weight of choline chloride in mixture in a glycol solvent, such as glycerine or polyethylene glycol ether. Glycerine is further preferred.
  • a glycol solvent such as glycerine or polyethylene glycol ether.
  • Glycerine is further preferred.
  • Such adjuvants are described, for example, in WO2012113830.
  • the composition does not comprise a surfactant based on glucamides, in particular alkyl glucamides, even further particular N-alkenoyl-N-alkylglucamide, such as Synergen ® GA (Clariant), or a surfactant based on an alkyl ether sulfate, in particular C12-C14 alkyl ether sulfate sodium salt, such as Genapol ® LRO paste (Clariant).
  • a surfactant based on glucamides in particular alkyl glucamides, even further particular N-alkenoyl-N-alkylglucamide, such as Synergen ® GA (Clariant)
  • a surfactant based on an alkyl ether sulfate in particular C12-C14 alkyl ether sulfate sodium salt, such as Genapol ® LRO paste (Clariant).
  • Component A) is a HPPD inhibitor, preferably a triketone.
  • the triketone is a 2-benzoyl-l,3-cyclohexanedione of formula (I), wherein:
  • R 8 is selected from the group consisting of halogen, nitro, Ci-4 alkyl, CH haloalkyl, Ci-6 alkoxy, Ci-6 alkoxy-Ci-6 alkyl, Ci-6 alkoxy-Cz 6 alkoxy, Ci-6 alkoxy-C -6-alkoxy-Ci-6 alkyl, Ci-4 haloalkoxy and Ci-4 haloalkoxy-Cinalkyl.
  • R 8 is chloro or nitro.
  • R 2 ) a is preferably selected from the group consisting of - SO2CH3, CF3 and 2,2,2 trifluoroethoxymethyl.
  • Preferred compounds of formula (I) are 2-(2’ -nitro-4 ‘-methylsulphonylbenzoyl)-l,3-cyclohexanedione (mesotrione), 2-(2 ‘-nitro-4 ‘ -methylsulphonyloxybenzoyl)-l,3-cyclohexanedione, 2-(2 ‘-chloro-4’ - methylsulphonylbenzoyl)- 1,3 -cyclohexanedione (sulcotrione), 2-[2-chloro-4-(methylsuphonyl)-3-(2,2,2- trifluoroethoxy] methyl] benzoyl ]- 1,3 -cyclohexanedione (tembotrione), 4,4-dimethyl-2-( 4- methanesulphonyl-2-nitrobenzoyl)-l,3-cyclohexanedione, 2-(2-chloro-3-ethoxy-4- methanesulphonylbenz
  • the HPPD-inhibiting herbicide is selected from the group consisting of mesotrione, sulcotrione, tembotrione, 4-Hydroxy-3-(2-(2-methoxyethoxymethyl)- 6-trifluoromethylpyridine-3-carbonyl]-bicyclo[3.2.1] oct-3-en-2-one) [Bicyclopyrone].
  • the HPPD-inhibiting herbicide is selected from the group consisting of tembotrione, mesotrione and sulcotrione.
  • HPPD-inhibiting herbicide is tembotrione.
  • the component A) is typically in the free acid form having the molecular structure depicted as formula (I), rather than as a salt (e.g., wherein the triketone is deprotonated).
  • HPPD inhibitors have an acidic proton which may be removed by means of a base. It should be understood that reference to the herbicides above also includes, for example, reference to tautomers and agriculturally acceptable salts thereof.
  • the invention also relates to agriculturally acceptable salts of the compounds of formula (I).
  • Such salts include those which may form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • agriculturally acceptable salts means salts the cations of which are known and accepted in the art for the formation of salts for agricultural or horticultural use.
  • the salts are water-soluble.
  • alkali metal and alkaline earth metal hydroxides oxides, alkoxides and hydrogen carbonates and carbonates used as salt formers
  • the corresponding trimethylsulfonium salt may also be used.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • metal complexes means compounds one or more of the oxygen atoms of the 2-benzoyl derivatives of formula (I) (or a tautomer thereof) act as chelating agents to a metal cation. Examples of such cations include zinc, manganese, cupric, cuprous, ferric, ferrous, titanium and aluminum.
  • the present invention also includes agronomically acceptable salts that the compounds of Formula (I) may form with amines (for example ammonia, dimethylamine and triethylamine, diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine), alkali metal (eg. sodium and potassium) and alkaline earth metal bases (eg. calcium and magnesium), or quaternary ammonium bases.
  • amines for example ammonia, dimethylamine and triethylamine, diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine
  • alkali metal eg. sodium and potassium
  • alkaline earth metal bases eg. calcium and magnesium
  • quaternary ammonium bases quaternary ammonium bases.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C1-C4 alkylamines, C1-C4 hydroxy alkylamines and C2-C4 alkoxy alkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbuty
  • compounds of formula (I) may exist in different isomeric forms.
  • G is hydrogen, for example, compounds of formula (I) may exist in different tautomeric forms.
  • the salts of the HPPD inhibitors which can thus be obtained are also suitable as salt building ion in component A) in the dispersions according to the invention.
  • suitable bases are ammonia, the hydroxides, carbonates and hydrogen carbonates of zinc, alkali metals and alkaline earth metals such as sodium, potassium, calcium and magnesium, and organic bases of the formula NR'R 2 R 3 where R 1 , R 2 and R 3 are in each case (Ci-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl, and R 2 and R 3 can additionally also be hydrogen.
  • the potassium, sodium and ammonium salts are preferred.
  • the herbicide may also be provided as a metal chelate. Metal ions which may be useful in forming the metal chelate include di- and trivalent transition metal ions such as Cu 2+ , Zn 2+ , Co 2+ , Fe 2+ , Ni 2+ and Fe 3+ .
  • Component B) is at least one safener selected from the group of compounds of the formula (II) [(component Bl)], in which R 5 is isopropyl or cyclopropyl and R 6 is hydrogen or chlorine, and of a 2-isoxazoline-3-carboxylic acid type safener [(component B2)], embracing compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3- carboxylic acid type, or the 5.5-diphenyl-2-isoxazoline-3-carboxylic acid, preferably compounds such as 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylic acid ethyl ester or 5-phenyl-2-isoxazoline-3- carboxylic acid ethyl ester and related compounds, as described in WO 91/08202, or 5.5-Diphenyl-2- isoxazoline-3-carboxylic acid ethyl ester ("isoxadifen
  • Component Bl is preferably selected with R5 being cyclopropyl and R6 being hydrogen. This corresponds to cyprosulfamide (CAS 221667-31-8).
  • Component B2) is preferably selected to be 5.5-Diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester, which corresponds to isoxadifen-ethyl (CAS 163520-33-0).
  • components A) and B) can be applied as ready to use aqueous suspension, a TK (technical concentrate).
  • a TK technical concentrate
  • the premix used is tembotrione + cyprosulfamide TK 38.03 (28.31+9.73) (% by weight) as shown below.
  • Component C) is glufosinate in form of a salt. For easiness of use and mixing it can be used as a TK (technical concentrate) of 50% by weight.
  • component C) is glufosinate in form of its ammonium salt.
  • the weight ratio of HPPD inhibitor, in particular tembotrione, to safener in the agrochemical composition may be selected from 5:1 to 2:1, preferably from 2.5:1.
  • Component A) and component Bl) are preferably present in a weight ratio of 5 : 1 to 1 : 1 , further preferably 4:1 to 2:1, and even further preferably approximately 3:1.
  • Component A) and component B2) are preferably present in a weight ratio of 5 : 1 to 1 : 1 , further preferably 4:1 to 2 : 1 , and even further preferably approximately 2.5:1.
  • component A) and component C) may be present in a weight ratio of 6:1 to 3:1, preferably 5:1 to 4:1, and even further preferably in weight ratio of approximately 4.5:1.
  • Component D) are surface-active compounds comprising at least one dispersant selected from the group consisting of alkyl poly glycosides, preferably alkylpolyglucosides, or at least one dispersant selected from the group consisting of alkyl polyglycosides and at least one adjuvant based on choline chloride.
  • choline chloride adjuvant is mandatory.
  • Component DI is defined as at least one other dispersant selected from the group consisting of alkylpolyglycosides (CAS Number 68515-73-1; 132778-08-6).
  • Component D2) is at least one adjuvant comprising choline chloride in a mixture of water and glycol solvent, in particular choline chloride in a mixture of water and glycerine, as described above (e.g. Geronol® CF/82-CC, Solvay).
  • Component D3) is at least one wetting agent selected from the group consisting of alkoxylated phosphate esters (CAS no 68130-47-2), most preferably Multitrope® 1214 from CRODA.
  • DI is an alkylpoly glycoside as defined below.
  • Alkyl polyglucosides are used in agrochemical formulations for various reasons, such as surfactants for wetting, and they are known to have stabilizing effects when used in high-salt content formulations of actives or simply fertilizers. These stabilizing effects allow more biological activity to be gained from the application of a agrochemical to a plant or crop, since the active is chemically more stable.
  • the fundamental performance of APGs as chemical stability enhancing surfactants alone is however rather poor and does not work with all active classes. Examples in the literature indicate that there are many better surfactants which could be used instead.
  • the literature does not provide any direction about mixtures of APG surfactants with other better stabilizers. Examples of recipes using APGs with other surfactants are known, however there is nothing to indicate that these mixtures are better when sued with herbicide combinations as depicted in the present invention.
  • component DI is an alkylpoly glycoside (APG) with following composition of formula (III): where n is a mean value and is from 7 to 11; and m is a mean value and is from 1 to 3.
  • n + 1 is the mean number of carbon atoms in the hydrophobic tail of the APG; and m is the mean number of sugar rings on the hydrophilic head group of the APG.
  • APG a mixture of an APG with another stabilizer.
  • the inclusion of the APG can reduce the overall cost of the formulation, it can alter its aqueous dilution properties and it can alter the toxicology of the formulation.
  • n + 1 is the mean number of carbon atoms in the hydrophobic tail of the surfactant.
  • n is from 7 to 15; more preferably n is from 7 to 13; and even more preferably it is from 7 to 11.
  • m is the mean number of sugar rings on the hydrophilic head group of the APG.
  • m is from 1 to 3; more preferably m is from 1 to 2; most preferably m is from 1.4 to 1.8.
  • Component DI may in particular refer to an alkylpolyglycoside having a C8-C10 or C9-C11 backbone, e.g. Agnique® PG 8105 (BASF) or Multitrope® 1620 (CRODA), Agnique®PG 8107 (BASF), Agnique®PG 8116 (BASF).
  • BASF Agnique® PG 8105
  • CRODA Multitrope® 1620
  • BASF Agnique®PG 8107
  • BASF Agnique®PG 8116
  • an alkylpolyglycoside having a C8-C10 backbone e.g. Agnique® PG 8105 from BASF or Multitrope® 1620 from CRODA.
  • the total proportion of compounds D) in the suspension concentrates according to the invention comprising at least one alkylpolyglucoside surfactant is generally between 5 and 25 % by weight. If the surfactants, in addition to their dispersing properties, are also used for increasing the biological effectiveness, for example as penetrants or tackifiers, their proportion in the suspension concentrates according to the invention may increase to up to 20% by weight.
  • the weight ratio of DI) and D2) is preferably between 3:1 and 1:3, further preferably 2:1 and 1:2, and even preferably 0.8:1 to 1:0.8 by weight, and most preferably approximately 1:1 by weight.
  • aqueous suspension concentrates according to the invention may additionally comprise further auxiliaries and additives customary in crop protection, in particular other surfactants [component D3] , citric acid in its anhydrous form as pH adjuster [component E)] and antifreeze agents, preservatives, thickeners and defoamers [component F)] and water as a filler.
  • citric acid anhydrous as pH adjuster as component E).
  • the water content is between 27% and 41% by weight.
  • crop protection compositions in the instant application have a water content on top of the one combined with the glufosinate-ammonium technical concentrate [TK] of at least 27% by weight.
  • the water content is between 27% and 41% by weight.
  • they may also comprise further substances (F), such as colorants and fragrances, tackifiers and penetrants, evaporation inhibitors, and viscosity modifiers (rheological modifiers).
  • F further substances
  • colorants and fragrances such as tackifiers and penetrants, evaporation inhibitors, and viscosity modifiers (rheological modifiers).
  • Preferred rheological additives / thickeners and thixotropic agents are, for example, modified phyllosilicates and natural and synthetic silicates.
  • the proportion of thickeners and thixotropic agents in the suspension concentrates according to the invention is, if present, between 0.1 and 5% by weight, in particular between 0.1 and 2 % by weight.
  • the rheological modifiers are selected from the group of xanthan gums, more preferably selected from the group consisting of Rhodopol® G, and Rhodopol® 23 [Solvay] and Satiaxane® CX911 [Cargill].
  • the listed class of thickeners can be used alone or in combination; a suitable combination thereof is for example described in WO 20/025652A1.
  • Suitable antifreeze agents are those from the group of the ureas, diols and polyols, such as ethylene glycol and propylene glycol.
  • crop protectant compositions according to the instant application have a glycerine content between 1 % and 2% by weight.
  • Suitable preservatives are those from the group of the isothiazoles, such as 2-methyl-2H- isothiazol-3-one or l,2-benzisothiazol-3(2H)-one.
  • the proportion of preservatives in the suspension concentrates according to the invention is generally between 0.05 and 1 % by weight, in particular between 0.08 and 0.2% by weight.
  • Suitable defoamers are, for example, those based on silicones, in particular poly dimethylsiloxanes, preferably Silcolapse® 454 from Bluestar silicones and SAG® 1572 from Momentive.
  • the proportion of defoamers in the suspension concentrates according to the invention is generally between 0.05 and 1 % by weight, in particular between 0.1 and 0.3% by weight.
  • the agrochemical composition according to the invention also comprises a carrier, in this case water.
  • the herbicide composition further comprising one or more additional components selected from the group comprising biocides, antioxidants, chemical stabilizers, adhesives, fertilizers, perfumes, colorants, liquid carriers, solid carriers, surface-active agents, crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, foaming agents, light-blocking agents, compatibility agents, antifoam agents, sequestering agents, neutralizing agents and buffers, wetting and dispersing agents, preservatives, thickening agents, corrosion inhibitors, freezing point depressants, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, sticking agents and humectants.
  • additional components selected from the group comprising biocides, antioxidants, chemical stabilizers, adhesives, fertilizers, perfumes, colorants, liquid carriers, solid carriers, surface-active agents, crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, foaming agents, light
  • the aqueous suspension concentrates according to the invention also comprise a further agrochemically active compound, preferably from the group of the herbicides.
  • This further herbicidally active compound may both be present in the aqueous suspension concentrate according to the invention as a ready formulation and be applied as a tank mix by joint dilution of the separately formulated or partially separately formulated components.
  • the aqueous suspension concentrates or herbicidal compositions according to the invention can be diluted in a customary manner, for example with water or with aqueous solutions of fertilizers, such as ammonium sulfate.
  • agrochemically active compounds for example components for tank mixes in the form of suitable formulations
  • customary auxiliaries and additives conventionally used for application and/or fertilizers. It has been found to be advantageous to dilute the aqueous suspension concentrates or herbicidal compositions according to the invention with aqueous solutions of fertilizers, for example urea ammonium nitrate and ammonium sulfate.
  • Component A) is preferably present from 2 to 12 % by weight, preferably 3 to 10% by weight, and even further preferably from 4 to 5% by weight.
  • Component Bl is preferably present from 0.8 to 4 % by weight, further preferably from 1 to 3.3% by weight, and even further preferably from 1.3 to 2% by weight.
  • Component C) as pure substance is preferably present from 10 to 35 % by weight, preferably 14 to 30 % by weight, even further preferably from 15 to 25 % by weight, and most preferably from 18 to 22 % by weight.
  • Component D) is preferably present in 5 to 25 % by weight, more preferably 8 to 24 % by weight and most preferably 10 to 22 % by weight.
  • Component E) is preferably present in 0.1 to 2 % by weight, more preferably from 0.5 to 1.5 % by weight, and most preferably from 0.8 to 1.2% by weight.
  • Component F is preferably present in 0 to 10 weight % by weight, more preferably from 0.65 to 4% by weight, most preferably from 2.2 to 2.4% by weight.
  • the aqueous dispersion herbicidal composition is preferred as: A) 3 to 10% by weight of a triketone HPPD inhibitor,
  • surfactant comprising at least one alkylpoly glycoside surfactant DI) and optionally an alkoxylated phosphate ester surfactant D3), or comprising at least one alkylpolyglycoside surfactant DI), optionally an alkoxylated phosphate ester surfactant D3), and at least one adjuvant based on choline chloride surfactant D2),
  • formulation auxiliaries biocides, antifoam, antifreeze
  • the safener is preferably selected from the group consisting of cyprosulf amide Bl) or isoxadifen-ethyl B2).
  • aqueous dispersion herbicidal composition is preferred as:
  • a surfactant comprising at least one alkylpoly glycoside surfactant DI) and optionally an alkoxylated phosphate ester surfactant D3), or comprising at least one alkylpolyglycoside surfactant DI), optionally an alkoxylated phosphate ester surfactant D3), and at least one adjuvant based on choline chloride surfactant D2),
  • a surfactant comprising at least one alkylpoly glycoside surfactant DI) and optionally an alkoxylated phosphate ester surfactant D3), or comprising at least one alkylpolyglycoside surfactant DI), optionally an alkoxylated phosphate ester surfactant D3), and at least one adjuvant based on choline chloride surfactant D2),0.8 to 1.2% by weight of citric acid anhydrous,
  • Component C) is preferably present from 14 to 27%, most preferably from 18 to 24%, even most preferably from 20 to 22%.
  • component DI is preferably present from 8 to 12%, most preferably from 10% by weight, and D2) is preferably present from 8 to 12% by weight.
  • the preferred weight ratio between component DI) and D2) is 0.8:1 to 1:0.8.
  • the combinations according to the invention may comprise further surfactants, in particular an alkoxylated phosphate ester (D3), in particular a CIO phosphate ester, such as Multitrope 1214 from CRODA (CAS no 68130-47-2).
  • D3 alkoxylated phosphate ester
  • CIO phosphate ester such as Multitrope 1214 from CRODA (CAS no 68130-47-2).
  • Such surfactant is preferably comprised in an amount of 0 to 5 % by weight, preferably 0 to 2 % by weight, and further preferably 0.03 to 1 % by weight.
  • a range of active substances can exist in different crystalline but also in amorphous modifications.
  • Polymorphism is the term used in these cases.
  • a polymorph is a solid, crystalline phase of a compound which is characterized by a specific, uniform packing and arrangement of the molecules in the solid.
  • the instant invention also covers the suitable use of the active ingredient of e.g. formula (I) also in its especially preferred solid forms as crystalline form which may contain only one polymorph.
  • composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made.
  • the final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • Examples of agriculturally acceptable salts include alkali metal salts such as sodium or potassium, alkaline earth metal salts such as magnesium or calcium, amine salts such as a monomethyl amine, dimethylamine, triethylamine, ammonium salts or dimethyl ammonium salts.
  • the herbicide may also be provided as a metal chelate.
  • Metal ions which may be useful in forming the metal chelate include di- and trivalent transition metal ions such as Cu2+, Zn2+, Co2+, Fe2+, Ni2+ and Fe3+.
  • the present invention accordingly also provides those suspension concentrates or herbicidal compositions comprising the agrochemically active compounds, auxiliaries and additives and/or fertilizers mentioned in the above section.
  • aqueous suspension concentrates and herbicidal compositions according to the invention have outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. They even effect good control of perennial problem weeds which emerge from rhizomes, root stocks or other perennial organs.
  • aqueous suspension concentrates and herbicidal compositions according to the invention have prolonged herbicidal activity with prompt onset.
  • aqueous suspension concentrates and herbicidal compositions according to the invention have an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops such as soybeans, cotton, oilseed rape, sugar beet, or graminaceous crops such as wheat, barley, rye, oats and millet, sugar cane, coffee, tea, cocoa, coconut, bananas or com only suffer minor damage, if any.
  • dicotyledonous crops such as soybeans, cotton, oilseed rape, sugar beet, or graminaceous crops such as wheat, barley, rye, oats and millet
  • sugar cane coffee, tea, cocoa, coconut, bananas or com only suffer minor damage, if any.
  • the aqueous suspension concentrates and herbicidal compositions according to the invention are highly suitable for the selective control of unwanted vegeta-tion in plantations of agriculturally useful crops
  • the aqueous suspension concentrates and herbicidal compositions according to the invention can also be employed for controlling harmful plants in crops of genetically modified plants which are known or yet to be developed.
  • the transgenic plants have specific advantageous properties, for example resistances to certain pesticides, especially certain herbicides, resistances to plant diseases or pathogens causing plant dis-eases, such as certain insects or microorganisms, such as fungi, bacteria or viruses.
  • Other specific properties relate, for example, to quantity, quality, storability, composition and specific constituents of the harvested material.
  • trans-genic plants having an increased starch content or modified starch quality or else having a different fatty acid composition of the harvested material are known.
  • aqueous suspension concentrates and herbicidal compositions according to the invention in economically important transgenic crops of useful plants and ornamentals, for example graminaceous crops, such as wheat, barley, rye, oats, millet, rice and com, in particular com, or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, pea and other vegetables.
  • the aqueous suspension concentrates and herbicidal compositions according to the invention can be employed as herbicides in crops of useful plants which are resistant, or which have been made resistant by means of genetic engineering, to the phytotoxic effects of the herbicidally active compounds.
  • aqueous suspension concentrates and herbicidal compositions according to the invention are applied in transgenic crops, effects are frequently observed which are specific for the application in the transgenic crop in question, for example a modified, or specifically broadened, spectrum of weeds which can be controlled, modified application rates which can be employed for the application, preferably good combining ability with the herbicides to which the transgenic crop is resistant, and an effect on the growth and yield of the transgenic crop plants, in addition to the effects, against harmful plants, which can be observed in the other crops.
  • the present invention furthermore also provides a method for controlling unwanted vegetation, preferably in crop plants such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, oilseed rape, cotton and soybeans, particularly preferably in monocotyledonous crops, such as cereals, for example wheat, barley, rye, oats, their hybridization products, such as triticale, rice, com and millet, one or more aqueous suspension concentrates or herbicidal compositions according to the invention being applied to the harmful plants, parts of plants, plant seeds or the area in which the plants grow, for example the area under cultivation.
  • cereals for example wheat, barley, rye, oats, rice, corn, millet
  • sugar beet sugar cane
  • oilseed rape cotton and soybeans
  • monocotyledonous crops such as cereals, for example wheat, barley, rye, oats
  • their hybridization products
  • the plant crops can also have been genetically modified or have been obtained by mutation selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors.
  • ALS acetolactate synthase
  • the aqueous suspension concentrates according to the invention are prepared in a manner known to the person skilled in the art, for example by mixing the individual constituents; see, in this context, Winnacker-Kiichler, “Chemische Technologic”, volume 7, C. Hauser Verlag Kunststoff, 4th Ed. 1986, Wade van Valkenburg, "Pesticide Formula-tions", Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
  • the herbicide composition of the present invention can also be used as a mixture together with or in combination with other agricultural chemicals, tank-mix adjuvants, crop oil concentrates, fertilizers and/or safeners.
  • the herbicidal composition of the present invention is preferably a liquid “ready-mix” formulation - that will be diluted prior to use. Dilution of the herbicidal composition of the present invention will typically result in a suspension.
  • the dispersions according to the invention show significantly improved application behavior, and manifests itself in markedly reduced sieve residues or clogging of sieves or nozzles.
  • the application rate of the dispersions according to the invention per hectare generally varies between 0.5 and 5 liters, preferably between 1.0 and 4.0 liters.
  • the dispersions according to the invention may be diluted in a customary manner, for example to give suspensions, for example by means of water. It may be advantageous to add, to the spray mixtures obtained, further agrochemical active substances (for example partners for tank mixers in the form of suitable formulations) and/or adjuvants and additives conventionally used for application, for example self-emulsifying oils such as vegetable oils or liquid paraffin and/or further fertilizers.
  • agrochemical active substances for example partners for tank mixers in the form of suitable formulations
  • adjuvants and additives conventionally used for application, for example self-emulsifying oils such as vegetable oils or liquid paraffin and/or further fertilizers.
  • the present invention therefore also relates to the herbicidal compositions prepared in this manner.
  • the ratio of dispersion according to the invention to water amounts to from 1:500 to 1:50.
  • the spray mixture per ha is usually 50 to 500 liters, preferably 75 to 350 liters of water. In some cases, the concentrations may also fall short of, or exceed, the limits detailed herein.
  • the dispersions are also suitable for aerial application. To this end, dispersions according to the invention are applied either in undiluted form or diluted with water or with organic solvents. In this context, the volume of additional carrier liquid will, as a rule, vary from 0.5 to 50 liters per hectare. The present invention therefore also relates to such herbicidal compositions based on the dispersions according to the invention.
  • the invention also comprises a method of controlling undesirable vegetation in the presence of a crop, particularly a corn crop, by applying to the locus of the crop or undesired vegetation a diluted herbicidal composition comprising a herbicidally effective amount of the HPPD, in mixture with glufosinate- ammonium and optionally in mixture with safeners according to the present invention.
  • crop is to be understood as also including a crop which has been genetically modified and in particular one which has been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD -inhibitors).
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO- and HPPD -inhibitors.
  • the dispersions or herbicidal compositions according to the invention have an outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants.
  • the activity also extends to weeds which sprout from rhizomes, root stocks or other perennial organs and which are difficult to control.
  • the compositions may be applied for example before sowing, pre-emergence or post-emergence.
  • some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the herbicidal compositions according to the invention may be mentioned by way of example, without the mention being intended as a restriction to certain species: among the monocotyledonous weed species, good activity is effected on, for example, Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. and Bromus spp.
  • Bromus catharticus such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus and Cyperus species from among the annuals, and, among the perennial species, Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species.
  • the spectrum of action extends to species such as, for example, Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp.
  • Galium aparine such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp. among the annuals and Convolvulus, Cirsium, Rumex and Artemisia among the perennial weeds.
  • compositions according to the invention also effect outstanding control of harmful plants which are found under the specific culture conditions in rice, such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.
  • the herbicidal compositions have an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds
  • crop plants of economically important crops for example dicotyledonous crops such as soybean, cotton, oilseed rape, sugar beet, or Gramineae crops such as wheat, barley, rye, oats, sorghum/millet, rice or maize are only damaged to a negligible extent, or not at all. This is why the herbicidal compositions according to the invention are highly suitable for the selective control of undesired vegetation in stands of agriculturally useful plants or in stands of ornamentals.
  • the herbicidal compositions according to the invention have outstanding growth-regulatory properties in crop plants. They engage in the plants’ metabolism in a regulatory fashion and can therefore be employed for the targeted control of plant constituents and for facilitating harvesting such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting undesired vegetative growth without killing the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since lodging can thereby be reduced or prevented completely.
  • the herbicidal compositions according to the invention can also be used for controlling harmful plants in crops of genetically modified plants which are known or yet to be developed.
  • the transgenic plants are distinguished by special advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate for example to the harvested material with regard to quantity, quality, storability, composition and specific constituents.
  • transgenic plants are known to have an increased starch content or a modified starch quality, or those which have different fatty acid composition of the harvested material.
  • the herbicidal compositions according to the invention in economically important transgenic crops of useful plants and ornamentals, for example Gramineae crops such as wheat, barley, rye, oats, sorghum/millet, rice and maize, or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, pea and other vegetables.
  • the compositions according to the invention can be employed as herbicides in crops of useful plants which are resistant, or have been made resistant by means of genetic engineering, to the phytotoxic effects of the herbicides.
  • the liquid formulations from the present invention are low-foam formulations with good storage properties. In many cases they have very favorable technical properties on application.
  • the formulations are distinguished by a low tendency to aggregate or forming a supernatant, e.g. during storage.
  • formulations of the invention are especially suitable for use in crop protection where the formulations are applied to the plants, to parts of plants or to the area under cultivation.
  • herbicidal ingredients A) and C) are very suitable for controlling unwanted plant growth both on uncultivated land and in tolerant crops.
  • GLUFOSINATE-AMMONIUM IUPAC name 2-amino-4-[hydroxy(methyl)phosphoryl] butanoic acid ammoniate
  • ISOXADIFEN-ETHYL IUPAC name ethyl 4,5-dihydro-5,5-diphenyl-l,2-oxazole-3- carboxylate (Bayer AG)
  • CYPROSULFAMIDE IUPAC name N-[4-(cyclopropylcarbamoyl)phenylsulfonyl]-o- anisamide (Bayer AG)
  • ACTICIDE® B 20 Aqueous dipropylene glycol solution of approx. 20 % 1,2- Benzisothiazolin-3-on as sodium salt (Thor GmbH)
  • SILCOLAPSE® 454 Polydimethylsiloxanes and silica (Elkem Silicones)
  • Component C) was received from production directly as a TK 50 (50% aqueous solution (w/w)). Water and component C) are added into a vessel. Components F) and D) are added, followed by A) and B) in form of an aqueous-based mill base. At the end the pH is adjusted with component E).
  • tembotrione and cyprosulfamide were prepared first as a TK (technical concentrate in water, as in Examples 1 and 2) where following process is used for the preparation of the mill base TBT+CSA TK 38.03 (28.31+9.73) as depicted in Table 2:
  • the resulting suspension according to the invention is storage-stable over a prolonged period. Even upon prolonged storage at high temperatures the active substance A) shows only a very low degree of decomposition.
  • the suspension according to the invention can be diluted with water to give a homogeneous suspension and has outstanding activity against harmful plants while simultaneously being very well tolerated in crops of useful plants.
  • Decomposition after 2W54 storage The storage was performed after CIPAC MT 46.3 at 2 weeks 54°C.
  • 2W54 Result of the fast storage (2 weeks 54°C) to check the long-term storage stability of a formulation.
  • the test for determining the storage stability is carried out by storing 0.2-10 g samples of the formulations according to the invention at the temperatures and storage conditions of 2W54. After this storage, the active compound analysis is carried out by HPLC methods known to the person skilled in the art. The decomposition amount of the active ingredient is given in %. pH of the formulation: measured 100% directly in the suspension.
  • Table 4 Storage stability as decomposition of tembotrione at 2W54 in %, and pH of the formulation:
  • the storage stability of the formulation not according to the invention manifests itself for example in the form of a massive degree of decomposition of the active substance A) upon storage at high temperatures.
  • a first experiment involved preparing the abovementioned formulation according to the invention in accordance with the above-described method and storing the products for 2 weeks at 54°C.
  • the results in Table 4 show that the comparative formulation shows a high decomposition of the active substance A).
  • Genapol® LRO paste is considered the adjuvant for glufosinate-ammonium, in this case it destabilizes chemically tembotrione at an unacceptable level.
  • Table 6 Storage stability as decomposition of tembotrione at 2W54 in %, and pH of the formulation:
  • the storage stability of the Comparative Examples 4 to 6 manifests itself for example in the form of a lesser degree of decomposition of the active substance A) upon storage at different temperatures.
  • a first experiment involved preparing the abovementioned formulation according to the invention in accordance with the above-described method and storing the products for 2 weeks at 54°C.
  • the results in Table 4 show that the Comparative Examples 4 to 6 show a lower decomposition of the active substance A) compared when using other surfactants in the recipe, eg Comparative Examples 1 to 3.
  • tembotrione is pH sensitive - the pH of the formulation should not be close to the pKa (eg max 4 - 4.5) to allow tembotrione to be stable.
  • the pKa of tembotrione being 3,2, a pH of 4-4.5 gives good conditions for tembotrione full stability.
  • a pH of 4-4.5 gives good conditions for tembotrione full stability.
  • the data from table 6 show a degradation at 2W54 ranging from 10.66% to 15.28%. This is far above what is required for a formulation stability of at least two years at room temperature - 2W54 being a prediction for this storage time period.
  • Table 7 Example 1 to 3 show tembotrione formulations with a water-soluble herbicide such as glufosinate-ammonium, where the surfactant system has been modified, examples according to the invention:
  • Table 8 Storage stability as decomposition of tembotrione at 2W54 in %, and pH of the formulation:
  • Examples 1 to 3 are according to the invention using an alkylpolyglucoside alone or with an adjuvant based on choline chloride, Geronol® CF/82-CC.
  • Table 8 shows the better storage stability of tembotrione which is not due to a lowering of pH, but more on the choice of a completely new surfactant system.
  • the use of an alkylpoly glucoside Agnique® PG 8105 as in Comparative Example 5 coupled with Synergen® GA does not allow to reach a tembotrione stability which is low enough to be able to register and market the product.
  • Multitrope® 1620 or Agnique® PG 8105 alone, or either of Multitrope® 1620 or Agnique® PG 8105 in combination with Geronol® CF/82-CC, a clean tembotrione stability is reached, in particular in a pH independent manner, and allows for the preparation of a formulation that can be registered and marketed.

Abstract

L'invention appartient au domaine technique des compositions herbicides et des combinaisons de tensioactifs pour des formulations de protection des cultures ayant une teneur élevée en principe actif de type sel, en particulier des formulations herbicides, et des formulations contenant lesdites combinaisons d'adjuvants, ainsi que des procédés de production desdites formulations. Selon un mode de réalisation préféré, la présente invention concerne des formulations aqueuses de principes actifs hydrosolubles, en particulier des formulations aqueuses de principes actifs de type sel, et en particulier des formulations contenant du glufosinate sous la forme de son sel d'ammonium, en combinaison avec au moins un autre principe actif HPPD, en particulier de la famille des tricétones et au moins un phytoprotecteur, au moins le principe actif HPPD étant en suspension dans la formulation, le principe actif de type à forte teneur en sel étant le glufosinate-ammonium.
PCT/EP2023/086623 2022-12-22 2023-12-19 Combinaison de tensioactifs pour formulations agrochimiques aqueuses en suspension (protection des cultures) d'un herbicide hppd combiné à une concentration élevée d'un principe actif présent sous la forme d'un sel WO2024133245A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP22216258.8 2022-12-22

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WO2024133245A1 true WO2024133245A1 (fr) 2024-06-27

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