WO2024042134A1 - Aqueous herbicide formulations - Google Patents
Aqueous herbicide formulations Download PDFInfo
- Publication number
- WO2024042134A1 WO2024042134A1 PCT/EP2023/073159 EP2023073159W WO2024042134A1 WO 2024042134 A1 WO2024042134 A1 WO 2024042134A1 EP 2023073159 W EP2023073159 W EP 2023073159W WO 2024042134 A1 WO2024042134 A1 WO 2024042134A1
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- WO
- WIPO (PCT)
- Prior art keywords
- formulation
- dispersant
- poly
- range
- saflufenacil
- Prior art date
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- 239000003021 water soluble solvent Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
Definitions
- the present invention relates to a liquid aqueous co-formulation of pyroxasulfone, saflufenacil, and dimethenamid-P.
- the present invention also relates to a process for producing such a co-formulation and to the use of the co-formulation for combating undesired plant growth.
- the present invention further relates to a ternary combination of pyroxasulfone, saflufenacil and dimethenamid-P and to the use of such a combination for controlling undesired plant growth, in particular in corn.
- Pyroxasulfone is a pre-emergence herbicide belonging to the group of VLCFA inhibitors, i.e. it inhibits the production of very long chain fatty acids in plants (HRAC/WSSA code 15). Pyroxasulfone is the ISO common name of 3- ⁇ [5- (difluoromethoxy)-l -methyl-3-[(trifluoromethyl)-1 H-pyrazol-4-yl] methanesulfonyl ⁇ -5,5- dimethyl-4,5-dihydro-1 ,2-oxacole (IUPAC).
- Pyroxasulfone is a solid crystalline material having a melting point of 130-132°C and a water solubility in deionized water at 20°C of below 0.1 g/l. Pyroxasulfone and its production are described e.g. in EP 1364946 and US 2005/0256004. Since pyroxasulfone is a crystalline solid, it is usually formulated as an aqueous suspension concentrate formulation (SC) or as wettable granules. Examples of such formulations are Zidua® SC and Zidua® WG, both of BASF Corp.
- SC aqueous suspension concentrate formulation
- Saflufenacil (ISO common name of 2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)-3,6-dihydropyrimidin-1 (2H)-yl]-N-[methyl(propan-2- yl)sulfamoyl]benzamide (IUPAC)) is a herbicide compound which acts by inhibiting the enzyme protoporphyrinogen oxidase (PPO inhibitor: HRAC/WSSA code 14). It is a crystalline solid whose anhydrate form has a melting point of 185-195°C. It has a solubility in deionized water at 20°C of about 2 g/l.
- Saflufenacil can be used for controlling broad leaf weeds in crops including soy bean and corn but also as a burndown herbicide. It has been disclosed in WO 01/083459. Further processes for its preparation are described in WO 2003/097589, WO 2005/054208, WO 2006/097589 and WO 2006/125746.
- Saflufenacil is frequently formulated as an aqueous suspension concentrate or as wettable granules. Formulations of saflufenacil are commercially available e.g. as Sharpen® or Treevix®, both of BASF Corp.
- Dimethenamid-P is a further herbicide of the group of VLCFA-inhibitors. Dimethenamid-P is a common name of (S)2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2- methoxy-1-methylethyl)acetamide. Dimethenamid-P is a yellowish-brown, clear liquid having a melting point of ⁇ -50°C and a solubility in water at 25°C of about 1.45 g/l . Dimethenamid-P is typically formulated as an emulsifiable concentrate (EC) which is commercially available under the BASF SE brands Frontier® and Outlook®.
- EC emulsifiable concentrate
- Combined application of different herbicides may be of interest for many reasons.
- combined application of different herbicides usually broadens the spectrum of application towards the harmful plants to be controlled and may reduce the risk of crop damage or other undesirable side effects.
- combined application allows for a better control of difficult to control weeds.
- an increase in efficacy is achieved that exceeds what would have been expected from the individual application of the herbicides (synergism).
- combined application may be required for resistance management, since the application rates of the individual herbicides can be reduced by combined application.
- WO 2009/115433 discloses the combined application of pyroxasulfone and dimethenamid P.
- WO 2009/115490 discloses the combined application of pyroxasulfone and saflufenacil. Both WO 2009/115433 and WO 2009/115499 suggest co-formulating the herbicide combinations.
- dimethenamid-P is a water-insoluble liquid while saflufenacil and pyroxasulfone are crystalline solids, it is difficult to incorporate these three compounds in a single formulation, in particular in an acceptable amount required for efficient application.
- a first aspect of the present invention relates to an aqueous herbicide formulation containing a) 2 to 10 wt.-%, in particular 3 to 8 wt.-% and especially 4 to 7 wt.-% based on the total weight of the formulation, of saflufenacil, b) 2 to 10 wt.-%, in particular 2.5 to 7.5 wt.-% and especially 3 to 6 wt.-% based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, in particular 24 to 35 wt.-% and especially 28 to 35 wt.-% based on the total weight of the formulation, of dimethenamid-P, d) 0.3 to 3 wt.-%, in particular 0.4 to 2.8 wt.-% and especially 0.5 to 2.5 wt.-%, based on the total weight of the formulation, of at least one dispersant D, selected from non-ionic polymeric
- a second aspect of the present invention relates to a ternary combination of herbicide compounds consisting of pyroxasulfone, saflufenacil and dimethenamid P wherein the weight ratio of pyroxasulfone to saflufenacil is in the range of 3:1 to 1 :3, in particular in the range of 2: 1 to 1 :2 and especially in the range of 1.5: 1 to 1 : 1 .5, the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :8 to 1 :1 , in particular in the range of 1 :7 to 1 :2 and especially in the range of 1 :6.5 to 1 :3; where the weight ratio of pyroxasulfone to dimethenamid P is in the range of 1 :10 to 1 :1 , in particular in the range of 1 :9 to 1 :2 and especially in the range of 1 :8 to 1 :3.
- a third aspect of the present invention relates to a process for producing the aqueous formulation of the invention:
- step (iv) Mixing the component (i) with the emulsion provided in step (iii); where the component (i) and/or the emulsion provided in step (iii) contains at least one thickener.
- the invention also relates to the use of a formulation as disclosed herein for controlling undesired plant growth. Yet, the invention also relates to the use of a combination as disclosed herein for controlling undesired plant growth.
- a further aspect of the invention relates to method for controlling undesired plant growth which comprises applying a formulation as disclosed herein or a herbicide combination as disclosed herein to the undesired plants or to an area where the undesired plants will grow.
- aqueous herbicide formulations of the present invention and the combination of herbicide compounds has several benefits:
- both the aqueous herbicide formulation and the herbicide combination of the present invention provide good and long-lasting control of undesired vegetation, in particular control of numerous difficult to control broadleaf weeds and does not result in crop injury, as long it is applied before the emergence of the crops.
- crops selected from corn including field corn, popcorn and sweet corn, soybean, chickpea, edible pea, field pea, lentil, perennial grass for seed production, alfalfa, and others, but it can also be applied in fallow, for pre-plant burndown, for post harvest burndown and in non-crop land area.
- the aqueous herbicide formulation of the present invention is storage stable, even if it is stored for a prolonged time at increased temperatures and/or with cycling temperatures. In particular, even after storage for 26 weeks, the formulation does not form sediment, and only little separation with small amount of layer formation occurs. The pH value increases only slightly upon prolonged storage, and no degradation of the active ingredients is observed.
- the aqueous herbicide formulation of the present invention has a beneficial viscosity profile, i. e. it has a high zero-shear viscosity and a high storage module and a comparatively low viscosity at a shear rate of 100 S’ 1 .
- a beneficial viscosity profile i. e. it has a high zero-shear viscosity and a high storage module and a comparatively low viscosity at a shear rate of 100 S’ 1 .
- the tendency of the sold actives saflufenacil and pyroxasulfone to segregate upon storage is low and, on the other hand, the formulation can be easily poured into water.
- the aqueous herbicide formulation of the present invention can be easily diluted and does not tend to cream or form sediment. Moreover, no persistent foam is formed upon dilution.
- the formulation is highly compatible with formulations of other herbicides in tank mix applications, in particular with formulations of water soluble herbicides, such as glufosinate, glyphosate, 2,4-D, dicamba or imidazolinones.
- ternary herbicide combination refers to combinations or compositions of three different herbicide compounds, namely saflufenacil, pyroxasulfone and dimethenamid P which are co-applied and which do not comprise a further herbicide compound. Different salts of the same herbicide compound are considered as the same herbicide compound.
- co-applied refers to the simultaneous or sequential application of the three herbicide compounds to the same locus in a timely context.
- the “ternary herbicide combination” includes tank mix of the three herbicide compounds, single formulation of the three herbicide compounds, 2 or 3 separate formulations of the three herbicide compounds and also the combined application of the three herbicide compounds.
- controlling and combating are synonyms, referring to inhibition of growth, control of growth, reduction of growth or complete destruction of the undesired plants.
- the growth of the undesired plant(s) is essentially diminished (60-79%), more preferably the growth of the undesired plant(s) is largely or fully suppressed (80-100%), and in particular the growth of the undesired plant(s) is almost fully or fully suppressed (90-100%).
- undesirable vegetation As used herein, the terms “undesirable vegetation”, “undesirable species”, “undesirable plants”, “harmful plants”, “undesirable weeds”, “volunteer plants” or “harmful weeds” are used synonymously
- C n -C m used in connection with compounds or molecular moieties each indicate a range for the number of possible carbon atoms that a molecular moiety or a compound can have.
- alkyl refers to a monovalent, linear or branched saturated hydrocarbon radical, which has e. g. 1 to 30 carbon atoms (C1-C30 alkyl) or 1 to 4 carbon atoms (Ci- 04 alkyl).
- alkyl include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1 .1 -dimethylethyl (tert-butyl), pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
- Ci-C4-alkyl are for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl.
- alkyl also includes saturated hydrocarbon radicals resulting from the oligomerization of C2-C4 olefins such as ethane, propene, 1 -butene and isobutene. These radicals will usually have 6 to 30 carbon atoms and are a mixture of different isomers.
- sucspoemulsion refers to a liquid aqueous formulation, which contains a liquid disperse phase emulsified in an aqueous phase, which is a coherent phase, and a solid phase in the form of fine particles which are suspended in the liquid phase and/or the aqueous phase.
- the dispersed solid phase may be present suspended in the droplets of the emulsified liquid phase or adhere to the droplets but they may also be present as particles suspended in the aqueous phase.
- the liquid dimethenamid P forms the liquid disperse phase, which is emulsified in the aqueous phase, while pyroxasulfone and saflufenacil are present in the form of particles, which are dispersed in the aqueous phase and/or in the liquid emulsified dimethenamid P phase.
- concentrations of the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the aqueous formulation is as described above.
- the concentrations of the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the aqueous formulation are as follows: a) the concentration of saflufenacil is in the range of 3 to 8 wt.-%, based on the total weight of the formulation, b) the concentration of pyroxasulfone is in the range of 2.5 to 7.5 wt.-%, based on the total weight of the formulation, and c) the concentration of dimethenamid-P is in the range of 24 to 35 wt.-%, based on the total weight of the formulation.
- the concentrations of the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the aqueous formulation are as follows: a) the concentration of saflufenacil is in the range of 4 to 7 wt.-% based on the total weight of the formulation, b) the concentration of pyroxasulfone is in the range of 3 to 6 wt.-% based on the total weight of the formulation, and c) the concentration of dimethenamid-P is in the range of 28 to 35 wt.-% based on the total weight of the formulation.
- the formulation of the invention contains the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the following relative amounts: the weight ratio of pyroxasulfone to saflufenacil is in the range of 3:1 to 1 :3, in particular in the range of 2:1 to 1 :1.5 and especially in the range of 1.5:1 to 1 :1 , the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :8 to 1 :1 , in particular in the range of 1 :7 to 1 :2 and especially in the range of 1 :6.5 to 1 :3; where the weight ratio of pyroxasulfone to dimethenamid P is in the range of 1 :10 to 1 :1 , in particular in the range of 1 :9 to 1 :2 and especially in the range of 1 :8 to 1 :3.
- the active ingredients contained in the formulations according to the invention i. e. saflufenacil, pyroxasulfone and dimethenamid P usually have the purities and qualities required for formulations of plant protection products. In particular, their chemical purity is at least 97% by weight. While different crystalline forms are known both of saflufenacil and pyroxasulfone it is possible to use any crystalline form of them.
- saflufenacil it is beneficial both for production and for stability of the formulation, if it is present as its crystalline anhydrate form.
- the crystalline anhydrate form of saflufenacil refers to the saflufenacil modification that has been disclosed in WO 2008/043835. Accordingly, the crystalline anhydrate form is an essentially solvent-free crystalline form of saflufenacil.
- the term "essentially solvent-free" means that the crystalline anhydrate form comprises no detectable amounts of solvents incorporated into the crystal lattice, i.e. the amount of solvent in the crystal lattice is less than 10 mol%, in particular not more than 5 mol%, based on saflufenacil.
- the crystalline anhydrate form of saflufenacil can be identified by means of X-ray powder diffractometry on the basis of its diffraction diagram.
- an X-ray powder diffractogram recorded at 25°C using Cu-Ka radiation (1.54178 A) shows at least 2, as a rule at least 4, frequently at least 6, in particular at least 8 and specifically all of the reflexes detailed in Table 1 hereinbelow as 20values, or as interplanar spacings d:
- differential scanning calorimetry can also be employed for identifying the anhydrate form.
- the anhydrate form shows a thermogram with a characteristic melting peak in the range between 170 and 200°C.
- the peak maximum is typically in the range of approximately 180°C to 190°C.
- the melting points indicated herein refer to data determined by means of differential scanning calorimetry (DSC, crucible material aluminum, heating rate 5 K/min).
- the crystalline anhydrate form of saflufenacil may be prepared by controlled crystallization from a solution of saflufenacil in an organic solvent which is essentially free from water as described in WO 2008/043835.
- the suspoemulsion of the present invention is stabilized against segregation and phase separation by a combination of d) at least one dispersant D which selected from non-ionic polymeric dispersants and carboxylated polymeric dispersants and combinations thereof and e) at least one anionic dispersant E which bears at least one anionic group selected from sulfonate, sulfate, phosphonate and phosphate groups.
- concentration of the total amount of dispersants D in the formulation is in the range of 0.2 to 5 wt.-%, in particular in the range of 0.4 to 2.8 wt.-% and especially in the range of 0.5 to 2.5 wt.-%, based on the total weight of the formulation.
- the polymeric dispersant D is preferably a non-ionic dispersant.
- N on-ionic dispersants usually comprise at least one poly(oxy-C2-C3-alkylene) moiety, which imparts hydrophilicity to the polymeric dispersant.
- poly(oxy-C2-C3- alkylene) includes poly(oxyethylene) and poly(oxypropylene) and poly(oxyethylene-co- oxypropylene), where in the latter, the oxy-1 ,2-ethylene and oxy-1 ,2-propylene repeating units may be arranged randomly or blockwise.
- the polymeric dispersants D typically have a molecular weight, which is higher than that of emulsifiers. Frequently, the polymeric dispersants D have a number average molecular weight M n of at least 1500, in particular at least 2000 Dalton. In particular, the polymeric dispersants D have a number average molecular weight M n in the range of 1500 to 100000 Dalton, especially in the range of 2000 to 50000 Dalton.
- the number average molecular weight M n polymeric dispersants D can be determined by well known techniques, e. g. by gel permeation chromatography (GPC), which is also termed size exclusion chromatography.
- the polymeric dispersant D is selected from block copolymers having a poly(C2-C3-alkylene oxide) moiety and graft polymers having a poly(C2-C3-alkylene oxide) moiety and combinations of such dispersants.
- the polymeric dispersant comprises at least one block copolymer having a poly(C2-C3-alkylene oxide) moiety and at least one graft polymer having a poly(C2-C3-alkylene oxide) moiety.
- block copolymer refers to copolymers, where one type of monomer forms a at least one polymer block A, which is covalently bound to at least one second polymer block B.
- the block copolymers may have also one or more further polymer blocks C, D etc., which are attached to A or B. Typical arrangements of these blocks are A-B, A-B-A, B-A-B, A-B-A-B, A-B-C or A-B-A-C etc. Preference is given to diblock copolymers A-B and triblock copolymers A-B-A and B-A-B.
- the end groups of the block copolymers may be capped by non- polymeric radicals, such as Ci-C2o-alkyl.
- non- polymeric radicals such as Ci-C2o-alkyl.
- graft polymer and comb polymer are used synonymously and refer to polymers having a polymer backbone formed by one or more first monomers and side chains formed by one or more second monomers and attached to the polymer backbone.
- a first subgroup D-i) in the group of dispersants D are block copolymers which are selected from Ci-C2o-alkyl-poly(C2-C3-alkylene oxides), i. e. mono-Ci-C20-alkyl ethers of poly(C2-C3-alkylene oxides). These dispersants are referred to as dispersants D-i). These block copolymers are in particular selected from C1-C20 alkyl poly(ethylene oxide-co-propylene oxide), in particular C2-C10 alkyl poly(ethylene oxide-co-propylene oxide), where the oxyethylene and oxypropylene repeating units are arranged blockwise, in particular in two blocks.
- a particular example of a D-i) block copolymer is a poly(ethylene oxide-co-propylene oxide) monobutyl ether.
- Block copolymers of the group of dispersants D-i) are commercially available as Atlas® G-5000 and Atlas® G- 5002L, both of Croda.
- a further subgroup D-ii) in the group of dispersants D are block copolymers having at least one block formed by a poly(C -C2o hydroxyalkanoic acid), in particular by polyhydroxystearic acid, and at least one block formed by poly(C2-C3-alkylene oxide), in particular by polyethylene oxide. These dispersants are referred to as dispersants D-ii).
- A-B-A block copolymers are preferred where A refers to the blocks formed by a poly(C -C2o hydroxyalkanoic acid), in particular by polyhydroxystearic acid, and B refers to a central block formed by poly(C2-C3-alkylene oxide), in particular by polyethylene oxide.
- block polymers are preferred which have at least one block formed by polyhydroxystearic acid and at least one block formed by polyethylene oxide with particular preference given to the A-B-A block copolymers.
- Block copolymers of group of dispersants D-ii) are commercially available as Atlox® 4912 of Croda.
- a further subgroup D-iii) in the group of dispersants D are graft copolymers having a polymer backbone, which is formed by polymerized ethylenically unsaturated monomers and side chains grafted to the polymer backbone, where the side chains are polyethylene oxide radicals and/or Ci-C4-alkyl-polyethylene oxide radicals.
- These dispersants are referred to as dispersants D-iii).
- the polyethylene oxide radicals and the Ci-C4-alkyl-polyethylene oxide radicals have a number average molecular weight in the range of 200 to 2000 Dalton.
- the polyethylene oxide part of the polyethylene oxide radicals and the Ci-C4-alkyl-polyethylene oxide radicals contribute 20 to 90%, especially 30 to 80% of the total weight of the graft copolymers.
- the ethylenically unsaturated monomers which form the backbone are typically non-ionic monoethylenically unsaturated monomers.
- the monomers forming the backbone are selected from Ci-C4-alkyl esters of a C3-C5 monoethylenically unsaturated carboxylic acid, such as Ci-C4-alkyl esters of acrylic acid or methacrylic acid (hereinafter also referred to as Ci-C4-alkyl (meth)acrylates, and combinations thereof with (meth)acrylic acid.
- Ci-C4-alkyl esters of acrylic acid or methacrylic acid hereinafter also referred to as Ci-C4-alkyl (meth)acrylates, and combinations thereof with (meth)acrylic acid.
- (meth)acrylic acid refers to both acrylic acid and methacrylic acid.
- the polymer backbone is formed by methylmethacrylate or combinations thereof with methacrylic acid.
- the backbone contains polymerized units of a monoethylenically unsaturated carboxylic acid, such as (meth)acrylic acid, their carboxyl group is typically esterified with polyethylene oxide radicals and/or Ci-C4-alkyl-polyethylene oxide radicals.
- the graft copolymers of the group of dispersants D-iii) are obtainable by copolymerization of one or more non-ionic monoethylenically unsaturated monomers, such as Ci-C4-alkyl (meth)acrylates, in particular methyl methacrylate, with an ester of polyethylene oxide or polyethylene oxide mono-Ci-C4-alkyl ether with (meth)acrylic acid, or by polymer analogue esterification or transesterification of a polymer formed by Ci-C4-alkyl (meth)acrylate, or by a combination of at least one Ci-C4-alkyl (meth)acrylate with (meth)acrylic acid, with polyethylene oxide or polyethylene oxide mono-Ci-C4-alkyl ether.
- non-ionic monoethylenically unsaturated monomers such as Ci-C4-alkyl (meth)acrylates, in particular methyl methacrylate
- Copolymers of group of dispersants D-iii) are well known and commercially available as Tersperse® 2500 of Indorama (CAS-No. 1000934-04-1) or as Atlox® 4913 of Croda (CAS-No. 119724-54-8).
- the dispersant D in the formulation is a combination of at least one dispersant D-i) and at least one further dispersant D, which is selected from dispersant D-ii), dispersant D-iii) and combinations of dispersants D-ii) and D-iii).
- the weight ratio of dispersant D-i) to the total amount of dispersants D-ii) to D-iii) is in the range of 5:1 to 1 :5, in particular in the range of 2:1 to 1 :2.
- the concentration of the dispersant D-i) is in the range of 0.15 to 2.5% wt.-%, especially in the range of 0.2 to 2.0 wt.-%, based on the total weight of the formulation.
- the total concentration of the dispersants D-ii) and D-iii) is in the range of 0.15 to 2.5% wt.-%, especially in the range of 0.2 to 2.0 wt.-%, based on the total weight of the formulation.
- the polymeric dispersants D have a hydrophilic-lipophilic balance, i. e. a HLB value in the range of 3 to 18, in particular in the range of 5 to 17.
- HLB values refer to the HLB values according to Griffin (W. C. Griffin, J. Soc. Cosmet. Chem. 1 (1950), p. 311 , and J. Soc. Cosmet. Chem. 5 (1954), p. 249).
- the formulation of the present invention comprises at least one dispersant D having a HLB value of in the range of 3 to 8, in particular in the range of 3 to 7 and at least one dispersant D which has a HLB value of at least 9, in particular a HLB in the range of 9 to 18, especially in the range of 10 to 17.
- Dispersants having a HLB of at least 9, in particular in the range of 9 to 18, especially in the range of 10 to 17 are in particular the dispersants D-i) and D-iii).
- Dispersants having a HLB in the range of 3 to 8, especially in the range of 4 to 7 are in particular the dispersants D-ii).
- the weight ratio of the total amount of dispersant D having a HLB in the range of 3 to 8 to the total amount of dispersant D having a HLB of at least 9 is in the range of 1 :1 to 1 :10, in particular in the range of 1 :2 to 1 :4.
- the concentration of the total amount dispersant D having a HLB of at least 9 is in the range of 0.25 to 2.9% wt.-%, especially in the range of 0.3 to 2.5 wt.-%, based on the total weight of the formulation.
- the concentration of the total amount dispersant D having a HLB in the range of 3 to 8 is in the range of 0.05 to 1% wt.-%, especially in the range of 0.1 to 0.8 wt.-%, based on the total weight of the formulation.
- the formulation of the present invention further contains at least one anionic dispersant E which has an anionic group selected from the group consisting of sulfonate, sulfate, phosphonate and phosphate.
- Suitable anionic dispersants E include, but are not limited to, the following groups E.1 to E.4 of dispersants, including combinations thereof.
- aryl- and Ci-Ci6-alkylarylsulfonates such as naphthylsulfonate, mono-, di- and tri- Ci-Ci6-alkylnaphthylsulfonates such as dibutylnaphtylsulfonate; dodecyldiphenylether sulfonate, mono-, di- and tri-Ci-Ci6-alkylphenylsulfonates such as cumylsulfonate, octylbenzene sulfoanate, nonylbenzenesulfonate, dodecylbenzene sulfonate and tridecylbenzene sulfonate;
- aryl ether sulfates in particular aryl poly(C2-C3-alkylene oxide) ether sulfates, e.g. the sulfates of (poly)ethoxylated di- or tristyrylphenols and the sulfates of (poly)ethoxylated-co-propoxylated di- or tristyrylphenols;
- aryl ether phosphates in particular aryl poly(C2-C3-alkylene oxide) ether phosphates, e.g. the phosphate esters of (poly)ethoxylated di- or tristyrylphenols and the phosphate esters of (poly)ethoxylated-co-propoxylated di- or tristyrylphenols;
- E.4 condensates of arylsulfonic acid, such as naphthalenesulfonic acid or phenolsulfonic acid, with formaldehyde and condensates of arylsulfonic acid, such as naphthalenesulfonic acid or phenolsulfonic acid, with formaldehyde and urea.
- the anionic dispersants are usually present in the formulation of the invention as their salts, in particular the ammonium salts, the alkaline metal salts, such as the sodium or potassium salt, and the earth alkaline metal salts, in particular the calcium salts.
- Preferred anionic dispersants E are those of the groups E.2 and E.3, in particular the aryl poly(C2-C3-alkylene oxide) ether sulfates the and aryl poly(C2-C3-alkylene oxide) ether phosphates, especially the aryl poly(C2-C3-alkylene oxide) ether sulfates of the group E.2.
- the group of surfactants E.1 preference is given to mono- or di-C4-Cs-alkyl- naphthalene sulfonic acid and mono- or di-C4-Ci6-alkylbenzesulfonic acid and the ammonium salts, the alkaline metal salts, such as the sodium or potassium salt, and the earth alkaline metal salts, in particular the calcium salts thereof.
- Particularly suitable examples are Morwet® EFW (Akzo Nobel), and the like.
- ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols preference is given to the ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 70, in particular 10 to 60 or 15 to 50 ethylenoxide repeating units.
- Particularly suitable examples of sulfates of (poly)ethoxylated di- or tristyrylphenols are Soprophor® 4D384 of Solvay and the like.
- ammonium salts and alkaline metal salts of phosphates of (poly)ethoxylated di- or tristyrylphenols preference is given to the ammonium salts and alkaline metal salts of phosphates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 50, in particular 10 to 50 or 15 to 50 ethylenoxide repeating units.
- the formulation of the present invention is an aqueous suspoemulsion which contains: a) 2 to 10 wt.-%, in particular 3 to 8 wt.-% and especially 4 to 7 wt.-% based on the total weight of the formulation, of saflufenacil, b) 2 to 10 wt.-%, in particular 2.5 to 7.5 wt.-% and especially 3 to 6 wt.-% based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, in particular 24 to 35 wt.-% and especially 28 to 35 wt.-% based on the total weight of the formulation, of dimethenamid-P, d) 0.3 to 3 wt.-%, in particular 0.4 to 2.8 wt.-% and especially 0.5 to 2.5 wt.-%, based on the total weight of the formulation, of at least one dispersant
- anionic dispersant E is in particular selected from aryl poly(C2-C3-alkylene oxide) ether sulfates and aryl poly(C2-C3-alkylene oxide) ether phosphates, and especially from tristyrylphenol poly(C2-C3-alkylene oxide) ether sulfates, with particular preference given to the ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 70, in particular 10 to 60 or 15 to 50 ethylenoxide repeating units; f) at least one thickener F, and g) water.
- the polymeric dispersant D is preferably a combination of at least one dispersant D-i) and at least one further dispersant D, which is selected from dispersants D-ii) and combinations of at least one dispersant D-ii) and at least one dispersant D-iii).
- the dispersant D comprises at least one dispersant D having a HLB value in the range of 3 to 8, in particular in the range of 3 to 7, which is preferably selected from dispersants D-ii), and at least one dispersant D which has a HLB value of at least 9, in particular a HLB in the range of 9 to 18, especially in the range of 10 to 17, which is selected from dispersants D-i) and combinations of at least one dispersant D-i) and at least one dispersant D-iii).
- the weight ratio of the total amount of dispersant D having a HLB in the range of 3 to 8 to the total amount of dispersant D having a HLB of at least 9 is in the range of 1 :1 to 1 : 10, in particular in the range of 1 :2 to 1 :4.
- the concentration of the total amount dispersant D having a HLB of at least 9 is in the range of 0.25 to 2.9% wt.-%, especially in the range of 0.3 to 2.5 wt.- %, based on the total weight of the formulation.
- the concentration of the total amount dispersant D having a HLB in the range of 3 to 8 is in the range of 0.05 to 1 % wt.-%, especially in the range of 0.1 to 0.8 wt.-%, based on the total weight of the formulation.
- the formulation of the present invention is an aqueous suspoemulsion which contains: a) 2 to 10 wt.-%, in particular 3 to 8 wt.-% and especially 4 to 7 wt.-% based on the total weight of the formulation, of saflufenacil, b) 2 to 10 wt.-%, in particular 2.5 to 7.5 wt.-% and especially 3 to 6 wt.-% based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, in particular 24 to 35 wt.-% and especially 28 to 35 wt.-% based on the total weight of the formulation, of dimethenamid-P, d) 0.3 to 3 wt.-%, in particular 0.4 to 2.8 wt.-% and especially 0.5 to 2.5 wt.-%, based on the total weight of the formulation, of at least one dispers
- anionic dispersant E is in particular selected from aryl poly(C2-C3-alkylene oxide) ether sulfates and aryl poly(C2-C3-alkylene oxide) ether phosphates, and especially from tristyrylphenol poly(C2-C3-alkylene oxide) ether sulfates, with particular preference given to the ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 70, in particular 10 to 60 or 15 to 50 ethylenoxide repeating units; f) at least one thickener F, and g) water.
- the weight ratio of the total amount of dispersant D having a HLB in the range of 3 to 8 to the total amount of dispersant D having a HLB of at least 9 is preferably in the range of 1 :1 to 1 :10, in particular in the range of 1 :2 to 1 :4.
- the concentration of the total amount dispersant D having a HLB of at least 9 is preferably in the range of 0.25 to 2.9% wt.-%, especially in the range of 0.3 to 2.5 wt.-%, based on the total weight of the formulation and the concentration of the total amount dispersant D having a HLB in the range of 3 to 8 is preferably in the range of 0.05 to 1 % wt.-%, especially in the range of 0.1 to 0.8 wt.-%, based on the total weight of the formulation.
- the formulations of the invention contain at least one thickener as a component F.
- the following observations regarding the thickener likewise apply to the formulations according to the preferred groups (1) of embodiments and the particularly preferred group (2) of embodiments.
- Suitable thickeners are compounds which affect the flow behavior of the suspoemulsion and may assist in stabilizing the suspoemulsion against phase separation and/or segregation of solids. Mention may be made, for example, of F.1 polysaccharide thickeners, such as methylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxypropylcellulose (e. g. Klucel® grades), Xanthan Gum (commercially available e.g. as Kelzan® grades from Kelco or Rhodopol® grades from Rhodia) and guar gum,
- F.2 synthetic polymers such as acrylic acid polymers (Carbopol® grades), polyvinyl alcohol (e.g. Mowiol® and Poval® grades from Kuraray) or polyvinyl pyrrolones, F.3 inorganic thickeners, such as silicic acid or phyllosilicates such as montmorillonite, hectorite, smectites and bentonites, which may be hydrophobized, (commercially available as Attaclay® grades and Attaflow® grades from BASF SE; or as Veegum® grades and Van Gel® grades from R.T. Vanderbilt).
- Acrylic acid polymers Carbopol® grades
- polyvinyl alcohol e.g. Mowiol® and Poval® grades from Kuraray
- polyvinyl pyrrolones e.g. Mowiol® and Poval® grades from Kuraray
- F.3 inorganic thickeners such as silicic acid or phyllosi
- the concentration of thickener in the final formulations of the invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments will generally not exceed 2 wt.-%, based on the total weight of the final suspoemulsion, and is preferably in the range of 0.01 to 2 wt.-%, in particular in the range of 0.02 to 1 .5 % by weight and especially from 0.1 to 1 wt.-%, based on the total weight of the final suspoemulsion.
- the kind and amount of thickener is chosen such that the formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments have a zero shear viscosity, determined at 20°C of at least 30 Pa-s, in particular at least 100 Pa-s, e. g. in the range of 30 to 1000 Pa-s, in particular in the range of 100 to 600 Pa- s.
- Zero-shear viscosity can be determined by measuring the dynamic viscosity of a liquid with a rotational viscometer at very low shear rates.
- aqueous formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments are typically shear thinning, i. e. their dynamic viscosity decreases with increasing shear rates.
- the dynamic viscosity of the formulation of the present invention determined at 20°C at a shear rate of 100 s- 1 does not exceed 1000 mPa-s in particular 500 mPa-s and is typically in the range of 20 to 500 mPa-s.
- the aqueous formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments contain preferably at least one polysaccharide thickener F.1. Preference is given to formulations, where the polysaccharide thickener comprises or consists of a Xanthan gum.
- thickener comprises at least one polysaccharide thickener of group F.1 , in particular xanthan gum and at least one inorganic thickener F.3, which preferably comprises or in particular is a phyllosilicate.
- phyllosilicates of the group of smectite minerals are particularly preferred.
- the formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments may contain a water-immiscible organic solvent.
- water-immiscible solvent refers to organic solvents which have a solubility in deionized water at 20°C and 1 bar of not more than 1 g/L.
- Suitable water-immiscible organic solvents include but are not limited to plant oils, aromatic hydrocarbons, fatty acid alkyl esters, in particular Ci-Cs-alkyl esters of Cs-C26-fatty acids, such as methyl or ethyl esters, fatty acid amides, in particular di-Ci-C4-alkyl amides of Cs-C26-fatty acids and mixtures thereof.
- plant oil refers to any vegetable oil, including e. g. sunflower oil, corn oil, rapeseed oil, including also canola oil, coconut oil, cottonseed oil, olive oil, peanut oil, palm oil, palm kernel oil, safflower oil, soybean oil, sesame oil, and mixtures thereof.
- Cs-C26-fatty acid refers to a fatty acid having from 8 to 26 carbon atoms.
- Examples for Cs-C26-fatty acids are the saturated fatty acids caprylic acid, caprinic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid; the mono-unsaturated fatty acids undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenic acid, cetoleic acid, erucic acid and nervonic acid; and the poly-unsaturated fatty acids linoleic acid, a- linolenic acid, y-linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid.
- the formulations of the invention and likewise the formulations according to the preferred groups (1) of embodiments and the particularly preferred group (2) of embodiments contain not more than 1 wt.-%, based on the total weight of the formulation, of water-immiscible solvents having a boiling point of less than 150°C at 1 bar.
- the formulation of the invention contains not more than 1 wt.-%, based on the total weight of the formulation, of aromatic hydrocarbons.
- the total amount of water-immiscible solvent may vary and, if present, is typically in the range of 0.1 to 5 wt.-%, based on the total weight of the formulation.
- the formulations of the present invention and likewise the formulations according to the preferred groups (1) of embodiments and the particularly preferred group (2) of embodiments may contain one or more additives which may usually contained in aqueous formulations of organic pesticide compounds.
- additives include, but are not limited to, anti-freeze agents, anti-foam agents, dyes, pigments and preservatives to prevent microbial spoiling.
- the formulation includes at least one anti-freeze.
- Suitable anti-freeze agents are typically water-soluble solvents, including alcohols, such as ethanol, ethylene glycol, propylene glycol and glycerol.
- the amount of such anti-freeze may depend on the type of anti-freeze and, if present, is typically in the range of 0.5 to 10 wt.-%, based on the total weight of the formulation.
- Antifoam agents suitable for the formulations according to the invention are, for example, silicone emulsions (such as, for example, Silicone SRE-PFL from Wacker or Rhodorsil® from Bluestar Silicones), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
- the amount of such antifoam may depend on the type of antifoam and, if present, is typically in the range of 0.01 to 0.5 wt.-%, based on the total weight of the formulation.
- Suitable preservatives to prevent microbial spoiling of the compositions of the invention include formaldehyde, alkyl esters of p-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1 ,3-diol, o-phenylphenol, thiazolinones, such as 1 ,2-benzisothiazol-3(2H)-one, 5-chloro-2-methyl-4-isothiazolinone (CIT), methylisothiazolinon (MIT) pentachlorophenol, 2,4-dichlorobenzyl alcohol and mixtures thereof.
- formaldehyde alkyl esters of p-hydroxybenzoic acid
- sodium benzoate 2-bromo-2-nitropropane-1 ,3-diol
- o-phenylphenol thiazolinones
- thiazolinones such as 1 ,2-benzisothiazol-3(2H)-one, 5-chloro-2
- the formulation of the present invention comprises water.
- the amount of water may vary and is generally in the range of 35 to 75 wt.-%, in particular in the range of 38 to 69 wt.-%, especially in the range of 40 to 63 wt.-%, based on the total weight of the formulation.
- the suspoemulsions of the present invention have a continuous aqueous phase, a liquid phase containing dimethenamid P and a solid phase formed by saflufenacil and pyroxasulfone.
- the liquid phase is present emulsified as small droplets, while the solid phase is present as finely dispersed particles.
- the size of the droplets and the solid particles is characterized by a size distribution, which can be determined by laser light scattering of dilute samples of the suspoemulsion.
- the mean diameter of the droplets/particles, i.e. the D[v, 0.5] value of the size distribution is typically in the range of 0.5 to 10 pm, in particular in the range of 1 to 5 pm.
- the D[v, 0.9] value of the size distribution does not exceed 50 pm and is typically at most 40 pm and may be as low as 2 or 3 pm.
- the D[v, 0.1] value means that 10% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v, 01]
- the D[v, 0.5] value means that 50% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v, 0.5]
- the D[v, 0.9] value means that 90% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v, 0.9]
- aqueous formulations are preferably produced by a process comprising the aforementioned steps (i) to (iv). It is clear to a skilled person that steps (i) and (ii) may be carried out in an arbitrary order.
- an aqueous suspension of pyroxasulfone and saflufenacil is provided.
- the suspension contains at least one of the dispersants D, in particular at least one dispersant D-i) and/or D-iii) in order to stabilize the suspension during production and storage.
- the suspension may also contain a portion of the thickener, in particular a portion or the total amount of the inorganic thickener, in particular the phyllosilicate.
- the suspension may also contain antifoam to avoid foaming during production.
- the sequence in which the individual components of the suspension are combined is not critical.
- step (i) it may be advantageous to carry out step (i) out by firstly mixing the water and a portion of the dispersant D and optionally a portion of the thickener until a homogenous mixture is obtained, and then adding the saflufenacil and pyroxasulfone with shear to said homogenous mixture.
- the mixture is then usually subjected to suitable means for reducing the particle size of the saflufenacil and pyroxasulfone particles present in the mixture typically to a mean particle size D[v, 0.5] below 10 pm, preferably to below 7 pm and in particular to below 5 pm.
- This step may be carried out by any physical attrition method, such as grinding, crushing or milling, in particular by wet grinding or wet milling, including e.g. bead milling, hammer milling, jet milling, air classifying milling, pin milling, cryogenic grinding processes and the like.
- Mixing and reducing particle size are usually performed subsequently. However it is also possible to perform these steps together.
- Step (i) is usually carried out at temperatures in the range of 10 to 60°C.
- an aqueous solution of the anionic dispersant is provided as a component (ii).
- the aqueous solution may contain one or more dispersants D, in particular a dispersant of group D-i).
- the aqueous solution contains at least a portion of the thickener, in particular a polysaccharide based thickener.
- the aqueous solution may also contain a portion or the total amount of inorganic thickener, in particular the phyllosilicate.
- the aqueous solution may also contain one or more bactericides and/or antifreeze. However, it is also possible to blend the final suspoemulsion with one or more bactericides and/or antifreeze.
- the aqueous solution may also contain antifoam to avoid foaming during production of the emulsion in step (iii).
- the aqueous solution can be prepared simply by mixing the components of the aqueous solution in an arbitrary order. However, it may be beneficial to predissolve the carbohydrate thickener, if present, in water and or a mixture of water and anti-freeze.
- Step (ii) is usually carried out at temperatures in the range of 10 to 70°C and preferably in the range of 15 to 60°C.
- step (iii) of the process of the invention the dimethenamid-P is emulsified in the aqueous solution provided in step (ii). If the final suspoemulsion contains a surfactant D-ii) it is preferred to dissolve the dispersant D-ii) in the dimethenamid prior to emulsification.
- the dimethenamid may also be blended with a water-immiscible solvent, in particular with at least one plant oil prior to emulsification in order to reduce the viscosity and/or for increasing the compatibility with the dispersant D-ii), if present.
- the amount of organic solvent, if present, is typically in the range of 0.1 to 10%, based on the total weight of dimethenamid-P and solvent.
- the dimethenamid-P, which is optionally blended with the further ingredients is then emulsified in the aqueous phase obtained in step (ii).
- the aqueous phase and the dimethenamid, which optionally has previously been blended with further ingredients are mixed and optionally homogenized.
- homogenization is carried out to a mean droplet size D[v, 0.5] below 7 pm, preferably to below 5 pm and in particular to below 2 pm.
- Step (iii) is usually carried out at temperatures in the range of 10 to 70°C and preferably in the range of 15 to 60°C.
- step (iv) of the process of the invention the thus obtained emulsion is then mixed with the aqueous suspension of pyroxasulfone and saflufenacil provided in step (i) to obtain a suspoemulsion.
- the further ingredients such as a defoamer, an antifreeze, bacterizides and/or water, are added at this stage.
- Mixing can be done by any conventional means for mixing liquids. Typically, the mixing is carried out in in a stirred tank.
- the aqueous formulation of the present invention i. e. the suspoemulsion of saflufenacil, pyroxasulfone and dimethenamid P, as well as the herbicide combination of saflufenacil, pyroxasulfone and dimethenamid P of the present invention are suitable for controlling undesired plant growth, in particular undesired plant growth in crop.
- the aqueous formulation is applied to the undesired plants or to an area where the undesired plants will grow.
- the terms “synergistic effect” and “synergism” are used synonymously and mean that the application of the combination of herbicidal components demonstrates a greater herbicidal effect than expected from the effect of the application of the individual herbicidal components when applied singly.
- Synergism can be determined by the Colby method (Colby, S.R., Weeds, 1967(15), p. 20-22), i.e. the expected (or predicted) response of the combination is calculated by taking the product of the observed response for each individual component of the combination when applied alone divided by 100 and subtracting this value from the sum of the observed response for each component when applied alone. Synergism of the combination is then determined by comparing the observed response of the combination to the expected (or predicted) 10 response as calculated from the observed responses of each individual component alone. If the observed response of the combination is significantly greater than the expected (or predicted) response as determined by Fisher's protected 15 Least Significant Difference (LSD) test using significance level 0.05, than the combination is said to be synergistic.
- Colby equation is as follows:
- Y effect in percent using herbicide B, here pyroxasulfone, at an application rate b;
- Synergism (Obs. — Exp. ) > LSD, wherein a combination is composed of components X, Y and Z, and Obs. designates the observed response of this combination.
- the formulation of the invention and the combinations of the invention can be applied in numerous crops.
- the crops include in particular field corn, including field corn grown for producing grain, seed or silage, popcorn, sweet corn, soybean, chickpea, edible pea, field pea, lentils, including green and red type, perennial grasses, in particular when grown for seed production, alfalfa, in particular in established stands of dormant alfalfa, in cereals, legume and oilseed cover crops.
- the formulations are active against broad-leaved weeds and grass weeds without inflicting substantial damage to the crop plants.
- the formulations and the combinations of the invention are preferably applied pre-emergently, i. e. before the undesired plants emerge.
- Pre-emergent application in crops may be carried out shortly before or shortly after the crop has been planted but preferably before the crop plants emerge.
- the formulation of the invention and the combinations of the invention can be applied in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
- Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome.
- Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
- Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination.
- one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants.
- the process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
- genetically modified crops in which the formulations and combinations can be used include in particular corn and soybean:
- Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
- Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN 10211 , BXN 10215, BXN 10222, BXN 10224, MON 1445, MON 1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
- the formulations and the combinations of the invention provide a very good control of vegetation during the fallow period, i. e. the period following harvest and before the following crop is planted.
- the formulations and the combinations of the invention provide a very good control of vegetation also in non-crop areas, especially at high application rates.
- the formulations and the combinations of the invention provide a very good control of the following plants, including broadleaf weeds, such as Amaranth, Palmer ⁇ Amaranthus palmeri), Amaranth, Powell ⁇ Amaranthus powellii), Bedstraw, catchweed ⁇ Gaiium aparine), Beggarticks, hairy ⁇ Bidens piiosa), Beggarweed, Florida ⁇ Desmodium tortuosum), Bindweed, field ⁇ Convolvulus arvensis , Buckwheat, wild Polygonum convolvulus), Buffalobur ⁇ Solanum rostratum) C.
- broadleaf weeds such as Amaranth, Palmer ⁇ Amaranthus palmeri), Amaranth, Powell ⁇ Amaranthus powellii), Bedstraw, catchweed ⁇ Gaiium aparine), Beggarticks, hairy ⁇ Bidens piiosa), Beggarweed, Florida ⁇ Desmodium tortuo
- Burcucumber ⁇ S icy os angulatus S, Canola, volunteer (rapeseed), all types ⁇ Brassica spp.), Carpetweed ⁇ Mollugo verticillata), Chamomile, mayweed ⁇ Anthemis cotula), Chickweed, common ⁇ Stellaria media), Cocklebur, common ⁇ Xanthium strumarium), Copperleaf, Virginia ⁇ Acalypha virginica), Cotton, volunteer ⁇ Gossypium hirsutum), Cowcockle ⁇ Vaccaria pyramidata), Dandelion ( Taraxacum officinale), Devil’s-claw ⁇ Proboscidea Louisiana), Eclipta ⁇ Edipta prostrata , Eveningprimrose, cutleaf ⁇ Oenothera laciniata), Galinsoga, smallflower ⁇ Gah'nsoga parviflora), Falseflax, smallseed ⁇ Cameh'na macrocarpa
- the application of the formulation of the invention may vary depending on the rate may depend on the kind of ground to which the suspoemulsion is applied is typically in the range of 1 to 100 kg/h, in particular in the range of 5 to 50 kg/ha.
- the individual application rates of saflufenacil is typically in the range of 5 to 250 g/ha, in particular in the range of 15 to 120 g/ha.
- the individual application rates of pyroxasulfone is typically in the range of 5 to 250 g/ha, in particular in the range of 15 to 120 g/ha.
- the individual application rates of dimethenamid P is typically in the range of 50 to 1500 g/ha, in particular in the range of 120 to 750 g/ha.
- the formulations and the combinations of the present invention may be applied preplant, preemergence, or as burndown application, in particular in the fall. Preplant application may be done to the surface or by incorporating the formulation or the individual herbicides of the combination into the ground.
- Preplant surface application is typically carried out by applying a uniform broadcast to the soil surface. Preplant surface application is usually carried out within 30 days of planting and before crop emergence.
- Preplant surface application is usually carried out within 30 days of planting and before crop emergence.
- the formulation or the individual herbicides of the combination are usually incorporated into the upper soil surface, e. g. into a depth of 2 to 6 cm, preferably within 14 days of planting.
- Incorporation may be carried out by shallow incorporation, including a field cultivator, harrow, rolling cultivator, or finishing disc.
- the application of the formulation of the invention or formulations or co-formulations of the individual herbicides of the combination of the invention may be carried out using water or a fluid nitrogen fertilizer as a spray carrier.
- the respective formulations are diluted with water or the liquid nitrogen fertilizer to obtain a liquid spray liquor.
- the amount of water used is at least 20 L/ha, in particular at least 25 L/ha and may be as high as 1000 L/ha.
- the components of the combination are typically formulated separately or as co-formulations of two components of the herbicide combination of the invention.
- pyraxasulfone is commercially available in the form of suspension concentrates and as wettable granules, e. g. under the brands Zidua® SC and Zidua® WG.
- saflufenacil is commercially available in the form of suspension concentrates and as wettable granules, e. g. under the brands Sharpen® or Treevix®, both of BASF Corp. Saflufenacil may be also be formulated as an oil dispersion as described in WO 2011/070051.
- Dimethenamid P is commercially available as an emulsion concentrate, e.g. under the BASF SE brands Frontier® and Outlook®.
- the components of the combination of the invention may also be formulated as co-formulations e. g. as co-formulations of saflufenacil and pyroxasulfone as suggested in WO 2009/115490 or as a co-formulation of pyroxasulfone and dimethenamid P as suggested in WO 2009/115433.
- the combination of the invention may also be in the form of a two package formulation, wherein one package is a formulation of pyroxasulfone while the other package contains a co-formulation of saflufenacil and dimethenamid-P, wherein all formulations contain at least one carrier material, if desired, one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.
- the combination of the invention may also be in the form of a three package formulation, wherein one package is a formulation of pyroxasulfone while the other two packages contain separate formulations of saflufenacil and dimethenamid-P, wherein all formulations contain at least one carrier material, if desired, one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.
- the individual formulations of the herbicides comprised in the combination of the present invention are usually mixed prior to application in the desired ratios and applied as a spray liquor containing the herbicide combination of the present invention.
- the mixing is performed as a tank mix, i.e. the formulations are mixed immediately prior or upon dilution with water or aqueous fertilizer. It is also possible to apply the individual formulations of the present invention as separate spray liquors which may be applied simultaneously or successively.
- the spray liquors can be applied in conventional manner by using techniques as skilled person is familiar with. Suitable techniques include spraying, atomizing, dusting, spreading or watering. The type of application depends on the intended purpose in a well-known manner; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
- formulations or combinations of the present invention in the form of fertilizer granules which have been impregnated with the formulations of the present invention or with formulations of the individual components.
- the formulation of the present invention and the combination of the present invention may be applied together with an adjuvant as action improver.
- a particular preferred adjuvant is described in WO 00/53014 and in WO2010/037734.
- Said adjuvant is a combination of a Ci-Cs-alkyl C5-C22-alkanoate, a Cio-C2o-carboxylic acid, a partial phosphoric or sulfuric acid ester of a monohydroxy-functional polyalkyl ether and an alkyl polyoxyalkylene polyether.
- Preferred Ci-Cs-alkyl C5-C22-alkanoates are methyl oleate, methyl palmitate and ethyl oleate and mixtures thereof.
- the C1-C5- alkyl Cs-C22-alkanoate comprises at least 70% by weight of methyl oleate or of a mixture of methyl oleate and methyl palmitate.
- Such action improver systems are commercially available under the name DASH®, e.g. DASH® HC, from BASF Corporation, USA.
- Further action improvers include but are not limited to those adjuvants conventionally used in combination with glyphosate, such as non-ionic surfactants (NIS), ammonium sulfate, alkyl sulfates of Ce-is alkanols such as sodium dodecyl sulfate, alkyl ether sulfates of Ce-is alkanols, methylated soybean oil (MSO) and crop oil concentrate (COC).
- NIS non-ionic surfactants
- MSO methylated soybean oil
- COC crop oil concentrate
- Particle sizes were determined by laser diffraction with a Malvern Mastersizer 2000 system at 23°C using the Fraunhofer model.
- Viscosity was determined by Brookfield method (using spindle no. 2 at 30 rpm) and with an Anton Paar Rheometer.
- the herbicide content was analysed by common HPLC methods.
- Surfactant 1 monobutyl ether of poly(ethylene oxide)-poly(propylene oxide) block copolymer (HLB: 17) - AtlasTM G 5000 (Croda);
- Surfactant 2 monoether of polyethylene oxide)-poly(propylene oxide) block copolymer - AtlasTM G 5002L (Croda);
- Surfactant 3 block copolymer of polyethylene glycol and 12-hydroxystearic acid (HLB: 6) - AtloxTM 4912 (Croda);
- Surfactant 4 polymethyl methacrylate-polyethylene glycol graft copolymer (HLB: 11-12) - AtloxTM 4913 (Croda);
- Surfactant 5 polyethylene glycol mono(tristyryl phenyl) ether sulfate ammonium salt - Soprophor® 4D/384 (Solvay);
- Thickener 1 xanthan gum - Rhodopol® 23 (Solvay);
- Thickener 2 magnesium aluminum silicate which is a phyllosilicate of the smectite group - Van Gel® ES (Vanderbilt Minerals);
- Antifoam 1 polydimethylsiloxane - SAGTM 1572 (Momentive);
- Biocide 1 1 ,2-benzisothiazol-3(2H)-one - Acticide® B 20 (Thor GmbH);
- Biocide 2 2-bromo-2-nitro-1 ,3-propandiol - Acticide® L 30 (Thor GmbH);
- Biocide 3 mixture of 5-chloro-2-methyl-4-isothiazolin-3-one (1.11 %) and 2- methyl-4-isothiazolin-3-one (0.37%) - Acticide® MV (Thor GmbH);
- Biocide 4 mixture of 1 ,2-benzisothiazol-3(2H)-one (2.5%) and 2-methyl-4- isothiazolin-3-one (2.5%) - Acticide® MBS (Thor GmbH);
- the three components for preparing the suspoemulsion namely an aqueous millbase, an aqueous phase and an oil phase, were prepared separately.
- the oil phase was then slowly poured into the aqueous phase with mixing and mixing was continued for 5 minutes. Afterwards a median particle diameter D50 of 0.77 pm was measured.
- the resulting emulsion was then mixed with the millbase and further components listed in Table 4 in the indicated weight ratio using an overhead stirrer fitted with a sawthooth blade until a homogeneous suspoemulsion was obtained.
- the obtained aqueous suspoemulsion 1 had the composition shown in Table 5.
- Table 5 The obtained aqueous suspoemulsion 1 had the composition shown in Table 5.
- the chemical stability of the suspoemulsion 1 was monitored by measuring the weight percentages of saflufenacil, pyroxasulfone and dimethenamid-P before and after different storage conditions by HPLC. The results are given in weight percentages [% (w/w)] in Table 6 below. The additionally given numbers in brackets are the percentages of the respective initial weight percentage.
- suspoemulsion 1 was an opaque, off-white, mobile liquid with medium viscosity. Over a period of 12 weeks at a temperature of 20°C, the appearance remained unchanged.
- the particle size distribution of the suspoemulsion 1 was monitored by determining the Dio, D50 and D90 by laser diffraction before and after different storage conditions. The results are listed in Table 8 below.
- the foam persistences were measured in accordance to the standard procedure CIPAC MT 47.2. The measurements were carried out on 5 % (v/v) dilutions of the suspoemulsion 1 in CIPAC D water. The dilutions were made of samples taken from the suspoemulsion before and after it was exposed to various storage conditions. The foam layers remaining in each case after 10 seconds, 1 minute, 3 minutes and 12 minutes were determined in mm. The results are listed in Table 10 below.
- the particle size distribution of the suspoemulsion 1 was examined according to the standard procedure CIPAC MT 185 using stacked sieves having mesh sizes of 75 and 150 pm before and after different storage conditions. The respective residues obtained are listed in weight percent relative to the total weight in Table 11.
- the stability of dilutions of the suspoemulsion 1 were examined in accordance to the standard procedure CIPAC MT 180. The measurements were carried out on 5 % (v/v) dilutions of the suspoemulsion that were prepared with CIPAC D water at a temperature of 30°C. The dilutions were made of samples taken from the suspoemulsion before and after it was exposed to various storage conditions. The volumes of cream and sediment formed in the dilutions after 30 minutes and 24.5 hours are given in Table 12 below.
- the Brookfield viscosity of the suspoemulsion 1 was measured by using spindle no. 2 at 30 rpm at 20°C before and after different storage conditions. The results are listed in Table 13 below.
- the viscosity of the suspoemulsion 1 was determined with a rheometer at different shear rates at 20°C before and after different storage conditions.
- the measured viscosities in mPa-s at shear rates of- 10 s- 1 and 100-s- 1 are given in Table 14 below.
- the three components for preparing the suspoemulsion namely an aqueous millbase, an aqueous phase and an oil phase, were prepared separately.
- the oil phase and the aqueous phase were mixed with a Silverson® high shear mixer with a emulsion head in a ratio so that an emulsion consisting of 49.17 %(w/w) oil phase and 50.83%(w/w) aqueous phase was obtained.
- the obtained aqueous suspoemulsion 2 had the composition shown in Table 19.
- the chemical stability of the suspoemulsion 2 was monitored by measuring the weight percentages of saflufenacil, pyroxasulfone and dimethenamid-P before and after different storage conditions as described above for suspoemulsion 1 .
- suspoemulsion 2 was an opaque, off-white, mobile liquid with medium viscosity. Over a period of 12 weeks at a temperature of 20°C, the appearance remained unchanged.
- the particle size distribution of the suspoemulsion 2 was monitored by determining the Dio, D50 and D90 as described for suspoemulsion 1. The results are summarized in Table 22 below.
- the particle size distribution of the suspoemulsion 2 was examined according to the standard procedure CIPAC MT 185 as described for suspoemulsion 1. The respective residues obtained are listed in weight percent relative to the total weight in Table 25.
- the viscosity of the suspoemulsion 2 was determined with a rheometer at different shear rates before and after different storage conditions.
- the measured viscosities in mPa-s at shear rates of- 10 s- 1 and 100-s- 1 are given in Table 28 below.
- Suspoemulsion 3 was prepared by the protocol of suspoemulsion 2, where the rapeseed oil was replaced by same amount of canola oil. Thus, the composition of suspoemulsion 3 is the same as of suspoemulsion 2, except for containing canola oil instead of rapeseed oil. The suspoemulsion 3 had the same properties as suspoemulsion 2 regarding viscosity, chemical stability, formulation stability and foam persistence.
- suspoemulsion 1 provided strong long-season residual control of several broadleaf and grass weed species.
- Table 29 Preemergence efficacy profile of suspoemulsoin 1 on various broadleaf and grass weed species based on weed efficacy studies conducted at multiple US locations over two years.
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Abstract
The present invention relates to a liquid aqueous co-formulation of pyroxasulfone, saflufenacil, and dimethenamid-P. The present invention also relates to a process for producing such a co-formulation and to the use of the co-formulation for combating undesired plant growth. The present invention further relates to a ternary combination of pyroxasulfone, saflufenacil and dimethenamid-P and to the use of such a combination for controlling undesired plant growth, in particular in corn.
Description
Aqueous herbicide formulations
The present invention relates to a liquid aqueous co-formulation of pyroxasulfone, saflufenacil, and dimethenamid-P. The present invention also relates to a process for producing such a co-formulation and to the use of the co-formulation for combating undesired plant growth. The present invention further relates to a ternary combination of pyroxasulfone, saflufenacil and dimethenamid-P and to the use of such a combination for controlling undesired plant growth, in particular in corn.
Pyroxasulfone is a pre-emergence herbicide belonging to the group of VLCFA inhibitors, i.e. it inhibits the production of very long chain fatty acids in plants (HRAC/WSSA code 15). Pyroxasulfone is the ISO common name of 3-{[5- (difluoromethoxy)-l -methyl-3-[(trifluoromethyl)-1 H-pyrazol-4-yl] methanesulfonyl}-5,5- dimethyl-4,5-dihydro-1 ,2-oxacole (IUPAC). Pyroxasulfone is a solid crystalline material having a melting point of 130-132°C and a water solubility in deionized water at 20°C of below 0.1 g/l. Pyroxasulfone and its production are described e.g. in EP 1364946 and US 2005/0256004. Since pyroxasulfone is a crystalline solid, it is usually formulated as an aqueous suspension concentrate formulation (SC) or as wettable granules. Examples of such formulations are Zidua® SC and Zidua® WG, both of BASF Corp.
Saflufenacil (ISO common name of 2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)-3,6-dihydropyrimidin-1 (2H)-yl]-N-[methyl(propan-2- yl)sulfamoyl]benzamide (IUPAC)) is a herbicide compound which acts by inhibiting the enzyme protoporphyrinogen oxidase (PPO inhibitor: HRAC/WSSA code 14). It is a crystalline solid whose anhydrate form has a melting point of 185-195°C. It has a solubility in deionized water at 20°C of about 2 g/l. Saflufenacil can be used for controlling broad leaf weeds in crops including soy bean and corn but also as a burndown herbicide. It has been disclosed in WO 01/083459. Further processes for its preparation are described in WO 2003/097589, WO 2005/054208, WO 2006/097589 and WO 2006/125746. A crystalline and essentially solvent-free form of saflufenacil, herein after also referred to as the crystalline anhydrate form, is disclosed in WO 2008/043835. Saflufenacil is frequently formulated as an aqueous suspension concentrate or as wettable granules. Formulations of saflufenacil are commercially available e.g. as Sharpen® or Treevix®, both of BASF Corp.
Dimethenamid-P is a further herbicide of the group of VLCFA-inhibitors. Dimethenamid-P is a common name of (S)2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2- methoxy-1-methylethyl)acetamide. Dimethenamid-P is a yellowish-brown, clear liquid
having a melting point of <-50°C and a solubility in water at 25°C of about 1.45 g/l . Dimethenamid-P is typically formulated as an emulsifiable concentrate (EC) which is commercially available under the BASF SE brands Frontier® and Outlook®.
Combined application of different herbicides may be of interest for many reasons. For example, combined application of different herbicides usually broadens the spectrum of application towards the harmful plants to be controlled and may reduce the risk of crop damage or other undesirable side effects. In some cases, combined application allows for a better control of difficult to control weeds. In some cases, an increase in efficacy is achieved that exceeds what would have been expected from the individual application of the herbicides (synergism). Apart from this, combined application may be required for resistance management, since the application rates of the individual herbicides can be reduced by combined application.
WO 2009/115433 discloses the combined application of pyroxasulfone and dimethenamid P. WO 2009/115490 discloses the combined application of pyroxasulfone and saflufenacil. Both WO 2009/115433 and WO 2009/115499 suggest co-formulating the herbicide combinations.
Recently, it was found that the combination of pyroxasulfone, saflufenacil and dimethenamid-P in a certain weight ratio provides very good control of difficult to control weeds including, inter alia, barnyard grass, smooth pigweed, palmer amaranth, hophornbeam copperleaf, sicklepod, ivyleaf morningglory, pitted morningglory, and prickly sida and others. Therefore, there is a high interest in proving co-formulations of these three herbicide compounds. However, due to their different physicochemical properties, in particular, due to the fact that dimethenamid-P is a water-insoluble liquid while saflufenacil and pyroxasulfone are crystalline solids, it is difficult to incorporate these three compounds in a single formulation, in particular in an acceptable amount required for efficient application.
An attempt of the inventors to provide the three herbicide compounds in an emulsifiable concentrate failed because the compounds tend to crystallize upon dilution with water. Moreover, emulsifiable concentrates have the disadvantage that they require organic solvents which may cause unwanted side effects or may cause regulatory concerns. Another attempt of the inventors to provide a co-formulation of these three herbicide compounds as an oil dispersion failed because in some of the oils, crystal growth of the crystalline compounds pyroxasulfone and saflufenacil was observed upon storage while other oils provide insufficient solubility of dimethenamid- P.
It was surprisingly found that these problems could be overcome by providing a suspoemulsion formulation of pyroxasulfone, saflufenacil and dimethenamid-P as described herein.
A first aspect of the present invention relates to an aqueous herbicide formulation containing a) 2 to 10 wt.-%, in particular 3 to 8 wt.-% and especially 4 to 7 wt.-% based on the total weight of the formulation, of saflufenacil, b) 2 to 10 wt.-%, in particular 2.5 to 7.5 wt.-% and especially 3 to 6 wt.-% based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, in particular 24 to 35 wt.-% and especially 28 to 35 wt.-% based on the total weight of the formulation, of dimethenamid-P, d) 0.3 to 3 wt.-%, in particular 0.4 to 2.8 wt.-% and especially 0.5 to 2.5 wt.-%, based on the total weight of the formulation, of at least one dispersant D, selected from non-ionic polymeric dispersants and combinations thereof, e) 0.1 to 1 wt.-%, in particular 0.2 to 0.8 wt.-% and especially 0.3 to 0.7 wt.-%, based on the total weight of the formulation, of at least one anionic dispersant E which bears at least one anionic group selected from sulfonate, sulfate, phosphonate and phosphate groups, f) at least one thickener F, and g) water where the formulation is an aqueous suspoemulsion.
A second aspect of the present invention relates to a ternary combination of herbicide compounds consisting of pyroxasulfone, saflufenacil and dimethenamid P wherein the weight ratio of pyroxasulfone to saflufenacil is in the range of 3:1 to 1 :3, in particular in the range of 2: 1 to 1 :2 and especially in the range of 1.5: 1 to 1 : 1 .5, the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :8 to 1 :1 , in particular in the range of 1 :7 to 1 :2 and especially in the range of 1 :6.5 to 1 :3; where the weight ratio of pyroxasulfone to dimethenamid P is in the range of 1 :10 to 1 :1 , in particular in the range of 1 :9 to 1 :2 and especially in the range of 1 :8 to 1 :3.
A third aspect of the present invention relates to a process for producing the aqueous formulation of the invention:
(i) Providing an aqueous suspension of pyroxasulfone and saflufenacil containing at least one dispersant D as a component (i);
(ii) Providing an aqueous solution of the anionic dispersant as a component (ii);
(iii) Providing an aqueous emulsion of dimethenamid P in the component (ii); and
(iv) Mixing the component (i) with the emulsion provided in step (iii); where the component (i) and/or the emulsion provided in step (iii) contains at least one thickener.
The invention also relates to the use of a formulation as disclosed herein for controlling undesired plant growth. Yet, the invention also relates to the use of a combination as disclosed herein for controlling undesired plant growth.
Yet, a further aspect of the invention relates to method for controlling undesired plant growth which comprises applying a formulation as disclosed herein or a herbicide combination as disclosed herein to the undesired plants or to an area where the undesired plants will grow.
The aqueous herbicide formulations of the present invention and the combination of herbicide compounds has several benefits:
Due to the particular combination of the three herbicides pyroxasulfone, saflufenacil and dimethenamid P and their relative ratios, both the aqueous herbicide formulation and the herbicide combination of the present invention provide good and long-lasting control of undesired vegetation, in particular control of numerous difficult to control broadleaf weeds and does not result in crop injury, as long it is applied before the emergence of the crops. In particular, it is suitable for application in crops selected from corn, including field corn, popcorn and sweet corn, soybean, chickpea, edible pea, field pea, lentil, perennial grass for seed production, alfalfa, and others, but it can also be applied in fallow, for pre-plant burndown, for post harvest burndown and in non-crop land area.
The aqueous herbicide formulation of the present invention is storage stable, even if it is stored for a prolonged time at increased temperatures and/or with cycling temperatures. In particular, even after storage for 26 weeks, the formulation does not form sediment, and only little separation with small amount of layer formation occurs. The pH value increases only slightly upon prolonged storage, and no degradation of the active ingredients is observed.
The aqueous herbicide formulation of the present invention has a beneficial viscosity profile, i. e. it has a high zero-shear viscosity and a high storage module and a comparatively low viscosity at a shear rate of 100 S’1. Thus, on the one hand, the tendency of the sold actives saflufenacil and pyroxasulfone to segregate upon storage is low and, on the other hand, the formulation can be easily poured into water.
The aqueous herbicide formulation of the present invention can be easily diluted and does not tend to cream or form sediment. Moreover, no persistent foam is formed upon dilution.
The formulation is highly compatible with formulations of other herbicides in tank mix applications, in particular with formulations of water soluble herbicides, such as glufosinate, glyphosate, 2,4-D, dicamba or imidazolinones.
In the following, the present invention is explained in more detail.
As used herein, the term “ternary herbicide combination” refers to combinations or compositions of three different herbicide compounds, namely saflufenacil, pyroxasulfone and dimethenamid P which are co-applied and which do not comprise a further herbicide compound. Different salts of the same herbicide compound are considered as the same herbicide compound. In this context, the term “co-applied” refers to the simultaneous or sequential application of the three herbicide compounds to the same locus in a timely context. The “ternary herbicide combination” includes tank mix of the three herbicide compounds, single formulation of the three herbicide compounds, 2 or 3 separate formulations of the three herbicide compounds and also the combined application of the three herbicide compounds.
As used herein, the terms "controlling" and "combating" are synonyms, referring to inhibition of growth, control of growth, reduction of growth or complete destruction of the undesired plants. Preferably, the growth of the undesired plant(s) is essentially diminished (60-79%), more preferably the growth of the undesired plant(s) is largely or fully suppressed (80-100%), and in particular the growth of the undesired plant(s) is almost fully or fully suppressed (90-100%).
As used herein, the terms "undesirable vegetation", "undesirable species", "undesirable plants", "harmful plants", "undesirable weeds", “volunteer plants” or "harmful weeds" are used synonymously
Here and throughout the specification, the prefixes Cn-Cm used in connection with compounds or molecular moieties each indicate a range for the number of possible carbon atoms that a molecular moiety or a compound can have.
The term “alkyl” refers to a monovalent, linear or branched saturated hydrocarbon radical, which has e. g. 1 to 30 carbon atoms (C1-C30 alkyl) or 1 to 4 carbon atoms (Ci- 04 alkyl). Examples of alkyl include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl),
1 .1 -dimethylethyl (tert-butyl), pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
2.2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -di methyl propyl, 1 ,2-dimethylpropyl,
1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl,
1 .2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-di methyl butyl, 2,3-dimethylbutyl,
3.3-dimethylbutyl, 1 -ethylbutyl, 2-ethyl butyl, 1 , 1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, n- octyl, 2-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, 3,7-dimethyloctane-1-yl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl docosyl and in case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl docosyl their isomers. Examples of Ci-C4-alkyl are for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl. The term “alkyl” also includes saturated hydrocarbon radicals resulting from the oligomerization of C2-C4 olefins such as ethane, propene, 1 -butene and isobutene. These radicals will usually have 6 to 30 carbon atoms and are a mixture of different isomers.
A skilled person will readily appreciate that the term “suspoemulsion” refers to a liquid aqueous formulation, which contains a liquid disperse phase emulsified in an aqueous phase, which is a coherent phase, and a solid phase in the form of fine particles which are suspended in the liquid phase and/or the aqueous phase. The dispersed solid phase may be present suspended in the droplets of the emulsified liquid phase or adhere to the droplets but they may also be present as particles suspended in the aqueous phase.
In the suspoemulsion formulation according to the present invention, the liquid dimethenamid P forms the liquid disperse phase, which is emulsified in the aqueous phase, while pyroxasulfone and saflufenacil are present in the form of particles, which are dispersed in the aqueous phase and/or in the liquid emulsified dimethenamid P phase. In order to achieve a good stability, it is important that the concentrations of the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the aqueous formulation is as described above. In particular, it is beneficial if the concentrations of the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the aqueous formulation are as follows: a) the concentration of saflufenacil is in the range of 3 to 8 wt.-%, based on the total weight of the formulation, b) the concentration of pyroxasulfone is in the range of 2.5 to 7.5 wt.-%, based on the total weight of the formulation, and
c) the concentration of dimethenamid-P is in the range of 24 to 35 wt.-%, based on the total weight of the formulation.
Especially, the concentrations of the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the aqueous formulation are as follows: a) the concentration of saflufenacil is in the range of 4 to 7 wt.-% based on the total weight of the formulation, b) the concentration of pyroxasulfone is in the range of 3 to 6 wt.-% based on the total weight of the formulation, and c) the concentration of dimethenamid-P is in the range of 28 to 35 wt.-% based on the total weight of the formulation.
In particular, it is beneficial, if the formulation of the invention contains the active compounds saflufenacil, pyroxasulfone and dimethenamid P in the following relative amounts: the weight ratio of pyroxasulfone to saflufenacil is in the range of 3:1 to 1 :3, in particular in the range of 2:1 to 1 :1.5 and especially in the range of 1.5:1 to 1 :1 , the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :8 to 1 :1 , in particular in the range of 1 :7 to 1 :2 and especially in the range of 1 :6.5 to 1 :3; where the weight ratio of pyroxasulfone to dimethenamid P is in the range of 1 :10 to 1 :1 , in particular in the range of 1 :9 to 1 :2 and especially in the range of 1 :8 to 1 :3.
The active ingredients contained in the formulations according to the invention, i. e. saflufenacil, pyroxasulfone and dimethenamid P usually have the purities and qualities required for formulations of plant protection products. In particular, their chemical purity is at least 97% by weight. While different crystalline forms are known both of saflufenacil and pyroxasulfone it is possible to use any crystalline form of them.
In case of saflufenacil it is beneficial both for production and for stability of the formulation, if it is present as its crystalline anhydrate form. The crystalline anhydrate form of saflufenacil refers to the saflufenacil modification that has been disclosed in WO 2008/043835. Accordingly, the crystalline anhydrate form is an essentially solvent-free crystalline form of saflufenacil. In this connection the term "essentially solvent-free" means that the crystalline anhydrate form comprises no detectable amounts of solvents incorporated into the crystal lattice, i.e. the amount of solvent in the crystal lattice is less than 10 mol%, in particular not more than 5 mol%, based on saflufenacil.
The crystalline anhydrate form of saflufenacil can be identified by means of X-ray
powder diffractometry on the basis of its diffraction diagram. Thus, an X-ray powder diffractogram recorded at 25°C using Cu-Ka radiation (1.54178 A) shows at least 2, as a rule at least 4, frequently at least 6, in particular at least 8 and specifically all of the reflexes detailed in Table 1 hereinbelow as 20values, or as interplanar spacings d:
Studies on monocrystals of the anhydrate form at -170°C demonstrate that the underlying crystal structure is monoclinic. The unit cell has the space group P2(1)/c. The characteristic data of the crystal structure of the anhydrate form are compiled in Table 2.
Table 2: Crystallographic characteristics of the crystalline anhydrate form (measured at -170°C)
a,b,c = unit cell length a,p,y = unit cell angle
Z = number of molecules in the unit cell
Besides X-ray powder diffractometry and the crystallographic analysis, differential scanning calorimetry (DSC) can also be employed for identifying the anhydrate form. Thus, the anhydrate form shows a thermogram with a characteristic melting peak in the range between 170 and 200°C. The peak maximum is typically in the range of approximately 180°C to 190°C. The melting points indicated herein refer to data determined by means of differential scanning calorimetry (DSC, crucible material aluminum, heating rate 5 K/min).
The crystalline anhydrate form of saflufenacil may be prepared by controlled crystallization from a solution of saflufenacil in an organic solvent which is essentially free from water as described in WO 2008/043835.
The suspoemulsion of the present invention is stabilized against segregation and phase separation by a combination of d) at least one dispersant D which selected from non-ionic polymeric dispersants and carboxylated polymeric dispersants and combinations thereof and e) at least one anionic dispersant E which bears at least one anionic group selected from sulfonate, sulfate, phosphonate and phosphate groups.
The concentration of the total amount of dispersants D in the formulation is in the range of 0.2 to 5 wt.-%, in particular in the range of 0.4 to 2.8 wt.-% and especially in the range of 0.5 to 2.5 wt.-%, based on the total weight of the formulation.
T
The polymeric dispersant D is preferably a non-ionic dispersant. N on-ionic dispersants usually comprise at least one poly(oxy-C2-C3-alkylene) moiety, which imparts hydrophilicity to the polymeric dispersant. Here and in the following, the terms “poly(oxy-C2-C3-alkylene) moiety” and “poly(C2-C3-alkylene oxide) moiety” are used to synonymously and refer to a polyether group formed by oxy-1 ,2-ethylene (= O- CH2CH2) and/or oxy-1 ,2-propylene (= O-CH(CH3)CH2) repeating units, i. e. by polymerized units of ethyleneoxide and/or propyleneoxide. The term poly(oxy-C2-C3- alkylene) includes poly(oxyethylene) and poly(oxypropylene) and poly(oxyethylene-co- oxypropylene), where in the latter, the oxy-1 ,2-ethylene and oxy-1 ,2-propylene repeating units may be arranged randomly or blockwise.
The polymeric dispersants D typically have a molecular weight, which is higher than that of emulsifiers. Frequently, the polymeric dispersants D have a number average molecular weight Mn of at least 1500, in particular at least 2000 Dalton. In particular, the polymeric dispersants D have a number average molecular weight Mn in the range of 1500 to 100000 Dalton, especially in the range of 2000 to 50000 Dalton. The number average molecular weight Mn polymeric dispersants D can be determined by well known techniques, e. g. by gel permeation chromatography (GPC), which is also termed size exclusion chromatography.
In particular, the polymeric dispersant D is selected from block copolymers having a poly(C2-C3-alkylene oxide) moiety and graft polymers having a poly(C2-C3-alkylene oxide) moiety and combinations of such dispersants. In particular the polymeric dispersant comprises at least one block copolymer having a poly(C2-C3-alkylene oxide) moiety and at least one graft polymer having a poly(C2-C3-alkylene oxide) moiety.
Here and in the following, the term block copolymer refers to copolymers, where one type of monomer forms a at least one polymer block A, which is covalently bound to at least one second polymer block B. The block copolymers may have also one or more further polymer blocks C, D etc., which are attached to A or B. Typical arrangements of these blocks are A-B, A-B-A, B-A-B, A-B-A-B, A-B-C or A-B-A-C etc. Preference is given to diblock copolymers A-B and triblock copolymers A-B-A and B-A-B. In these block copolymers, the end groups of the block copolymers may be capped by non- polymeric radicals, such as Ci-C2o-alkyl.
Here and in the following, the terms “graft polymer” and “comb polymer” are used synonymously and refer to polymers having a polymer backbone formed by one or more first monomers and side chains formed by one or more second monomers and attached to the polymer backbone.
A first subgroup D-i) in the group of dispersants D are block copolymers which are selected from Ci-C2o-alkyl-poly(C2-C3-alkylene oxides), i. e. mono-Ci-C20-alkyl ethers of poly(C2-C3-alkylene oxides). These dispersants are referred to as dispersants D-i). These block copolymers are in particular selected from C1-C20 alkyl poly(ethylene oxide-co-propylene oxide), in particular C2-C10 alkyl poly(ethylene oxide-co-propylene oxide), where the oxyethylene and oxypropylene repeating units are arranged blockwise, in particular in two blocks. A particular example of a D-i) block copolymer is a poly(ethylene oxide-co-propylene oxide) monobutyl ether. Block copolymers of the group of dispersants D-i) are commercially available as Atlas® G-5000 and Atlas® G- 5002L, both of Croda.
A further subgroup D-ii) in the group of dispersants D are block copolymers having at least one block formed by a poly(C -C2o hydroxyalkanoic acid), in particular by polyhydroxystearic acid, and at least one block formed by poly(C2-C3-alkylene oxide), in particular by polyethylene oxide. These dispersants are referred to as dispersants D-ii). Amongst this group D-ii) dispersants, A-B-A block copolymers are preferred where A refers to the blocks formed by a poly(C -C2o hydroxyalkanoic acid), in particular by polyhydroxystearic acid, and B refers to a central block formed by poly(C2-C3-alkylene oxide), in particular by polyethylene oxide. In particular block polymers are preferred which have at least one block formed by polyhydroxystearic acid and at least one block formed by polyethylene oxide with particular preference given to the A-B-A block copolymers. Block copolymers of group of dispersants D-ii) are commercially available as Atlox® 4912 of Croda.
A further subgroup D-iii) in the group of dispersants D are graft copolymers having a polymer backbone, which is formed by polymerized ethylenically unsaturated monomers and side chains grafted to the polymer backbone, where the side chains are polyethylene oxide radicals and/or Ci-C4-alkyl-polyethylene oxide radicals. These dispersants are referred to as dispersants D-iii). In particular, the polyethylene oxide radicals and the Ci-C4-alkyl-polyethylene oxide radicals have a number average molecular weight in the range of 200 to 2000 Dalton. In particular, the polyethylene oxide part of the polyethylene oxide radicals and the Ci-C4-alkyl-polyethylene oxide radicals contribute 20 to 90%, especially 30 to 80% of the total weight of the graft copolymers. The ethylenically unsaturated monomers which form the backbone are
typically non-ionic monoethylenically unsaturated monomers. Preferably, the monomers forming the backbone are selected from Ci-C4-alkyl esters of a C3-C5 monoethylenically unsaturated carboxylic acid, such as Ci-C4-alkyl esters of acrylic acid or methacrylic acid (hereinafter also referred to as Ci-C4-alkyl (meth)acrylates, and combinations thereof with (meth)acrylic acid. Here the term (meth)acrylic acid refers to both acrylic acid and methacrylic acid. In particular, the polymer backbone is formed by methylmethacrylate or combinations thereof with methacrylic acid. If the backbone contains polymerized units of a monoethylenically unsaturated carboxylic acid, such as (meth)acrylic acid, their carboxyl group is typically esterified with polyethylene oxide radicals and/or Ci-C4-alkyl-polyethylene oxide radicals.
Usually, the graft copolymers of the group of dispersants D-iii) are obtainable by copolymerization of one or more non-ionic monoethylenically unsaturated monomers, such as Ci-C4-alkyl (meth)acrylates, in particular methyl methacrylate, with an ester of polyethylene oxide or polyethylene oxide mono-Ci-C4-alkyl ether with (meth)acrylic acid, or by polymer analogue esterification or transesterification of a polymer formed by Ci-C4-alkyl (meth)acrylate, or by a combination of at least one Ci-C4-alkyl (meth)acrylate with (meth)acrylic acid, with polyethylene oxide or polyethylene oxide mono-Ci-C4-alkyl ether. Copolymers of group of dispersants D-iii) are well known and commercially available as Tersperse® 2500 of Indorama (CAS-No. 1000934-04-1) or as Atlox® 4913 of Croda (CAS-No. 119724-54-8).
In particular, the dispersant D in the formulation is a combination of at least one dispersant D-i) and at least one further dispersant D, which is selected from dispersant D-ii), dispersant D-iii) and combinations of dispersants D-ii) and D-iii). In such combinations, the weight ratio of dispersant D-i) to the total amount of dispersants D-ii) to D-iii) is in the range of 5:1 to 1 :5, in particular in the range of 2:1 to 1 :2. In particular, the concentration of the dispersant D-i) is in the range of 0.15 to 2.5% wt.-%, especially in the range of 0.2 to 2.0 wt.-%, based on the total weight of the formulation. In particular the total concentration of the dispersants D-ii) and D-iii) is in the range of 0.15 to 2.5% wt.-%, especially in the range of 0.2 to 2.0 wt.-%, based on the total weight of the formulation.
Usually, the polymeric dispersants D have a hydrophilic-lipophilic balance, i. e. a HLB value in the range of 3 to 18, in particular in the range of 5 to 17. Here and in the following, HLB values refer to the HLB values according to Griffin (W. C. Griffin, J. Soc. Cosmet. Chem. 1 (1950), p. 311 , and J. Soc. Cosmet. Chem. 5 (1954), p. 249).
Preferably, the formulation of the present invention comprises at least one dispersant D having a HLB value of in the range of 3 to 8, in particular in the range of 3 to 7 and at least one dispersant D which has a HLB value of at least 9, in particular a HLB in the range of 9 to 18, especially in the range of 10 to 17. Dispersants having a HLB of at least 9, in particular in the range of 9 to 18, especially in the range of 10 to 17 are in particular the dispersants D-i) and D-iii). Dispersants having a HLB in the range of 3 to 8, especially in the range of 4 to 7 are in particular the dispersants D-ii). In such combinations, the weight ratio of the total amount of dispersant D having a HLB in the range of 3 to 8 to the total amount of dispersant D having a HLB of at least 9 is in the range of 1 :1 to 1 :10, in particular in the range of 1 :2 to 1 :4. In particular, the concentration of the total amount dispersant D having a HLB of at least 9 is in the range of 0.25 to 2.9% wt.-%, especially in the range of 0.3 to 2.5 wt.-%, based on the total weight of the formulation. In particular, the concentration of the total amount dispersant D having a HLB in the range of 3 to 8 is in the range of 0.05 to 1% wt.-%, especially in the range of 0.1 to 0.8 wt.-%, based on the total weight of the formulation.
The formulation of the present invention further contains at least one anionic dispersant E which has an anionic group selected from the group consisting of sulfonate, sulfate, phosphonate and phosphate. Suitable anionic dispersants E include, but are not limited to, the following groups E.1 to E.4 of dispersants, including combinations thereof.
E.1 aryl- and Ci-Ci6-alkylarylsulfonates such as naphthylsulfonate, mono-, di- and tri- Ci-Ci6-alkylnaphthylsulfonates such as dibutylnaphtylsulfonate; dodecyldiphenylether sulfonate, mono-, di- and tri-Ci-Ci6-alkylphenylsulfonates such as cumylsulfonate, octylbenzene sulfoanate, nonylbenzenesulfonate, dodecylbenzene sulfonate and tridecylbenzene sulfonate;
E.2 aryl ether sulfates, in particular aryl poly(C2-C3-alkylene oxide) ether sulfates, e.g. the sulfates of (poly)ethoxylated di- or tristyrylphenols and the sulfates of (poly)ethoxylated-co-propoxylated di- or tristyrylphenols;
E.3 aryl ether phosphates, in particular aryl poly(C2-C3-alkylene oxide) ether phosphates, e.g. the phosphate esters of (poly)ethoxylated di- or tristyrylphenols and the phosphate esters of (poly)ethoxylated-co-propoxylated di- or tristyrylphenols;
E.4 condensates of arylsulfonic acid, such as naphthalenesulfonic acid or phenolsulfonic acid, with formaldehyde and condensates of arylsulfonic acid, such as naphthalenesulfonic acid or phenolsulfonic acid, with formaldehyde and urea.
The anionic dispersants are usually present in the formulation of the invention as their salts, in particular the ammonium salts, the alkaline metal salts, such as the sodium or potassium salt, and the earth alkaline metal salts, in particular the calcium salts. Preferred anionic dispersants E are those of the groups E.2 and E.3, in particular the aryl poly(C2-C3-alkylene oxide) ether sulfates the and aryl poly(C2-C3-alkylene oxide) ether phosphates, especially the aryl poly(C2-C3-alkylene oxide) ether sulfates of the group E.2.
In the group of surfactants E.1 preference is given to mono- or di-C4-Cs-alkyl- naphthalene sulfonic acid and mono- or di-C4-Ci6-alkylbenzesulfonic acid and the ammonium salts, the alkaline metal salts, such as the sodium or potassium salt, and the earth alkaline metal salts, in particular the calcium salts thereof. Particularly suitable examples are Morwet® EFW (Akzo Nobel), and the like.
In the group of surfactants E.2 preference is given to the ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 70, in particular 10 to 60 or 15 to 50 ethylenoxide repeating units. Particularly suitable examples of sulfates of (poly)ethoxylated di- or tristyrylphenols are Soprophor® 4D384 of Solvay and the like.
In the group of surfactants E.3 preference is given to the ammonium salts and alkaline metal salts of phosphates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 50, in particular 10 to 50 or 15 to 50 ethylenoxide repeating units.
According to a preferred group (1) of embodiments, the formulation of the present invention is an aqueous suspoemulsion which contains: a) 2 to 10 wt.-%, in particular 3 to 8 wt.-% and especially 4 to 7 wt.-% based on the total weight of the formulation, of saflufenacil, b) 2 to 10 wt.-%, in particular 2.5 to 7.5 wt.-% and especially 3 to 6 wt.-% based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, in particular 24 to 35 wt.-% and especially 28 to 35 wt.-% based on the total weight of the formulation, of dimethenamid-P, d) 0.3 to 3 wt.-%, in particular 0.4 to 2.8 wt.-% and especially 0.5 to 2.5 wt.-%, based on the total weight of the formulation, of at least one dispersant D, which is selected from non-ionic block copolymers having a poly(C2-C3-alkylene oxide) moiety and non-ionic graft polymers having a poly(C2-C3-alkylene oxide) moiety, e) 0.1 to 1 wt.-%, in particular 0.2 to 0.8 wt.-% and especially 0.3 to 0.7 wt.-%, based on the total weight of the formulation, of at least one anionic dispersant E
which is selected from the anionic surfactants E.1 , E.2, E. 3 and E.4 as defined herein, and where the anionic dispersant E is in particular selected from aryl poly(C2-C3-alkylene oxide) ether sulfates and aryl poly(C2-C3-alkylene oxide) ether phosphates, and especially from tristyrylphenol poly(C2-C3-alkylene oxide) ether sulfates, with particular preference given to the ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 70, in particular 10 to 60 or 15 to 50 ethylenoxide repeating units; f) at least one thickener F, and g) water.
In the preferred group (1) of embodiments, the polymeric dispersant D is preferably a combination of at least one dispersant D-i) and at least one further dispersant D, which is selected from dispersants D-ii) and combinations of at least one dispersant D-ii) and at least one dispersant D-iii).
In the preferred group (1) of embodiments, it is particular preferred if the dispersant D comprises at least one dispersant D having a HLB value in the range of 3 to 8, in particular in the range of 3 to 7, which is preferably selected from dispersants D-ii), and at least one dispersant D which has a HLB value of at least 9, in particular a HLB in the range of 9 to 18, especially in the range of 10 to 17, which is selected from dispersants D-i) and combinations of at least one dispersant D-i) and at least one dispersant D-iii). In these combinations, the weight ratio of the total amount of dispersant D having a HLB in the range of 3 to 8 to the total amount of dispersant D having a HLB of at least 9 is in the range of 1 :1 to 1 : 10, in particular in the range of 1 :2 to 1 :4. In particular, the concentration of the total amount dispersant D having a HLB of at least 9 is in the range of 0.25 to 2.9% wt.-%, especially in the range of 0.3 to 2.5 wt.- %, based on the total weight of the formulation. In particular, the concentration of the total amount dispersant D having a HLB in the range of 3 to 8 is in the range of 0.05 to 1 % wt.-%, especially in the range of 0.1 to 0.8 wt.-%, based on the total weight of the formulation.
According to a particularly preferred group (2) of embodiments, the formulation of the present invention is an aqueous suspoemulsion which contains: a) 2 to 10 wt.-%, in particular 3 to 8 wt.-% and especially 4 to 7 wt.-% based on the total weight of the formulation, of saflufenacil, b) 2 to 10 wt.-%, in particular 2.5 to 7.5 wt.-% and especially 3 to 6 wt.-% based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, in particular 24 to 35 wt.-% and especially 28 to 35 wt.-% based on the total weight of the formulation, of dimethenamid-P,
d) 0.3 to 3 wt.-%, in particular 0.4 to 2.8 wt.-% and especially 0.5 to 2.5 wt.-%, based on the total weight of the formulation, of at least one dispersant D, which comprises at least one dispersant D having a HLB value of in the range of 3 to 8, in particular in the range of 3 to 7, which is in particular selected from dispersants D-ii) and at least one dispersant D which has a HLB value of at least 9, in particular a HLB in the range of 9 to 18, especially in the range of 10 to 17, which is in particular selected from dispersants D-i) and combinations of at least one dispersant D-i) and at least one dispersant D-iii); e) 0.1 to 1 wt.-%, in particular 0.2 to 0.8 wt.-% and especially 0.3 to 0.7 wt.-%, based on the total weight of the formulation, of at least one anionic dispersant E which is selected from the anionic surfactants E.1 , E.2, E. 3 and E.4 as defined herein, and where the anionic dispersant E is in particular selected from aryl poly(C2-C3-alkylene oxide) ether sulfates and aryl poly(C2-C3-alkylene oxide) ether phosphates, and especially from tristyrylphenol poly(C2-C3-alkylene oxide) ether sulfates, with particular preference given to the ammonium salts, alkaline metal salts and earth alkaline metal salts of sulfates of (poly)ethoxylated di- or tristyrylphenols, in particular of those having from 5 to 70, in particular 10 to 60 or 15 to 50 ethylenoxide repeating units; f) at least one thickener F, and g) water.
In the formulations of the particularly preferred group (2) of embodiments, the weight ratio of the total amount of dispersant D having a HLB in the range of 3 to 8 to the total amount of dispersant D having a HLB of at least 9 is preferably in the range of 1 :1 to 1 :10, in particular in the range of 1 :2 to 1 :4. In the formulations of the particularly preferred group (2) of embodiments, the concentration of the total amount dispersant D having a HLB of at least 9 is preferably in the range of 0.25 to 2.9% wt.-%, especially in the range of 0.3 to 2.5 wt.-%, based on the total weight of the formulation and the concentration of the total amount dispersant D having a HLB in the range of 3 to 8 is preferably in the range of 0.05 to 1 % wt.-%, especially in the range of 0.1 to 0.8 wt.-%, based on the total weight of the formulation.
The formulations of the invention contain at least one thickener as a component F. The following observations regarding the thickener likewise apply to the formulations according to the preferred groups (1) of embodiments and the particularly preferred group (2) of embodiments.
Suitable thickeners are compounds which affect the flow behavior of the suspoemulsion and may assist in stabilizing the suspoemulsion against phase separation and/or segregation of solids. Mention may be made, for example, of F.1 polysaccharide thickeners, such as methylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxypropylcellulose (e. g. Klucel® grades), Xanthan Gum (commercially available e.g. as Kelzan® grades from Kelco or Rhodopol® grades from Rhodia) and guar gum,
F.2 synthetic polymers such as acrylic acid polymers (Carbopol® grades), polyvinyl alcohol (e.g. Mowiol® and Poval® grades from Kuraray) or polyvinyl pyrrolones, F.3 inorganic thickeners, such as silicic acid or phyllosilicates such as montmorillonite, hectorite, smectites and bentonites, which may be hydrophobized, (commercially available as Attaclay® grades and Attaflow® grades from BASF SE; or as Veegum® grades and Van Gel® grades from R.T. Vanderbilt).
The concentration of thickener in the final formulations of the invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments will generally not exceed 2 wt.-%, based on the total weight of the final suspoemulsion, and is preferably in the range of 0.01 to 2 wt.-%, in particular in the range of 0.02 to 1 .5 % by weight and especially from 0.1 to 1 wt.-%, based on the total weight of the final suspoemulsion.
Preferably, the kind and amount of thickener is chosen such that the formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments have a zero shear viscosity, determined at 20°C of at least 30 Pa-s, in particular at least 100 Pa-s, e. g. in the range of 30 to 1000 Pa-s, in particular in the range of 100 to 600 Pa- s. Zero-shear viscosity can be determined by measuring the dynamic viscosity of a liquid with a rotational viscometer at very low shear rates.
The aqueous formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments are typically shear thinning, i. e. their dynamic viscosity decreases with increasing shear rates. Typically, the dynamic viscosity of the formulation of the present invention determined at 20°C at a shear rate of 100 s-1 does not exceed 1000 mPa-s in particular 500 mPa-s and is typically in the range of 20 to 500 mPa-s.
In the context of the present invention, the aqueous formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments contain preferably at least one polysaccharide thickener F.1. Preference is given to formulations, where the polysaccharide thickener comprises or consists of a Xanthan gum.
Particular preference is given to formulations of the present invention and likewise to the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments, wherein thickener comprises at least one polysaccharide thickener of group F.1 , in particular xanthan gum and at least one inorganic thickener F.3, which preferably comprises or in particular is a phyllosilicate. Particular preference is given to phyllosilicates of the group of smectite minerals.
In addition to the mandatory components A - F and water, the formulations of the present invention and likewise the formulations according to the preferred groups (1 ) of embodiments and the particularly preferred group (2) of embodiments may contain a water-immiscible organic solvent. Here, the term “water-immiscible solvent” refers to organic solvents which have a solubility in deionized water at 20°C and 1 bar of not more than 1 g/L. Suitable water-immiscible organic solvents include but are not limited to plant oils, aromatic hydrocarbons, fatty acid alkyl esters, in particular Ci-Cs-alkyl esters of Cs-C26-fatty acids, such as methyl or ethyl esters, fatty acid amides, in particular di-Ci-C4-alkyl amides of Cs-C26-fatty acids and mixtures thereof.
Here the term “plant oil” refers to any vegetable oil, including e. g. sunflower oil, corn oil, rapeseed oil, including also canola oil, coconut oil, cottonseed oil, olive oil, peanut oil, palm oil, palm kernel oil, safflower oil, soybean oil, sesame oil, and mixtures thereof.
Cs-C26-fatty acid refers to a fatty acid having from 8 to 26 carbon atoms. Examples for Cs-C26-fatty acids are the saturated fatty acids caprylic acid, caprinic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid; the mono-unsaturated fatty acids undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenic acid, cetoleic acid, erucic acid and nervonic acid; and the poly-unsaturated fatty acids linoleic acid, a- linolenic acid, y-linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid.
Preferably, the formulations of the invention and likewise the formulations according to the preferred groups (1) of embodiments and the particularly preferred group (2) of embodiments contain not more than 1 wt.-%, based on the total weight of the formulation, of water-immiscible solvents having a boiling point of less than 150°C at 1 bar. Preferably, the formulation of the invention contains not more than 1 wt.-%, based on the total weight of the formulation, of aromatic hydrocarbons. The total amount of water-immiscible solvent may vary and, if present, is typically in the range of 0.1 to 5 wt.-%, based on the total weight of the formulation.
The formulations of the present invention and likewise the formulations according to the preferred groups (1) of embodiments and the particularly preferred group (2) of embodiments may contain one or more additives which may usually contained in aqueous formulations of organic pesticide compounds. These additives include, but are not limited to, anti-freeze agents, anti-foam agents, dyes, pigments and preservatives to prevent microbial spoiling.
In particular the formulation includes at least one anti-freeze. Suitable anti-freeze agents are typically water-soluble solvents, including alcohols, such as ethanol, ethylene glycol, propylene glycol and glycerol. The amount of such anti-freeze may depend on the type of anti-freeze and, if present, is typically in the range of 0.5 to 10 wt.-%, based on the total weight of the formulation.
Antifoam agents suitable for the formulations according to the invention are, for example, silicone emulsions (such as, for example, Silicone SRE-PFL from Wacker or Rhodorsil® from Bluestar Silicones), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. The amount of such antifoam may depend on the type of antifoam and, if present, is typically in the range of 0.01 to 0.5 wt.-%, based on the total weight of the formulation.
Suitable preservatives to prevent microbial spoiling of the compositions of the invention include formaldehyde, alkyl esters of p-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1 ,3-diol, o-phenylphenol, thiazolinones, such as 1 ,2-benzisothiazol-3(2H)-one, 5-chloro-2-methyl-4-isothiazolinone (CIT), methylisothiazolinon (MIT) pentachlorophenol, 2,4-dichlorobenzyl alcohol and mixtures thereof. Commercially available preservatives that are based on isothiazolinones are for example marketed under the trademarks Proxel® (Arch Chemical), Acticide® grades, such as MV, MBS and B20 (Thor Chemie) and Kathon® MK (Rohm & Haas). 2-bromo-2-nitropropane-1 ,3-diol is commercially available as Acticide® L30.
The formulation of the present invention comprises water. The amount of water may vary and is generally in the range of 35 to 75 wt.-%, in particular in the range of 38 to 69 wt.-%, especially in the range of 40 to 63 wt.-%, based on the total weight of the formulation.
As explained, the suspoemulsions of the present invention have a continuous aqueous phase, a liquid phase containing dimethenamid P and a solid phase formed by saflufenacil and pyroxasulfone. The liquid phase is present emulsified as small droplets, while the solid phase is present as finely dispersed particles. The size of the droplets and the solid particles is characterized by a size distribution, which can be determined by laser light scattering of dilute samples of the suspoemulsion. The mean diameter of the droplets/particles, i.e. the D[v, 0.5] value of the size distribution is typically in the range of 0.5 to 10 pm, in particular in the range of 1 to 5 pm. Typically the D[v, 0.9] value of the size distribution does not exceed 50 pm and is typically at most 40 pm and may be as low as 2 or 3 pm.
Here and hereinafter, all figures for particle sizes, particle diameters and particle size distributions, including the D[v, 0.1], D[v, 0.5], D[v, 0.9], values, are based on the size distributions ascertained by static laser light scattering to ISO 13320:2020 on dilute samples of the suspoemulsion. The abbreviation SLS is also used hereinafter for the expression "static laser light scattering to ISO 13320:2020". In this connection, the D[v, 0.1] value means that 10% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v, 01], Accordingly, the D[v, 0.5] value means that 50% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v, 0.5], and the D[v, 0.9] value means that 90% by volume of the particles of the measured sample have a particle diameter below the value reported as D[v, 0.9],
The aqueous formulations are preferably produced by a process comprising the aforementioned steps (i) to (iv). It is clear to a skilled person that steps (i) and (ii) may be carried out in an arbitrary order.
In step (i) of the process of the invention an aqueous suspension of pyroxasulfone and saflufenacil is provided. Typically, the suspension contains at least one of the dispersants D, in particular at least one dispersant D-i) and/or D-iii) in order to stabilize the suspension during production and storage. The suspension may also contain a portion of the thickener, in particular a portion or the total amount of the inorganic thickener, in particular the phyllosilicate. The suspension may also contain antifoam to avoid foaming during production.
In general, the sequence in which the individual components of the suspension are combined is not critical. However, it may be advantageous to carry out step (i) out by firstly mixing the water and a portion of the dispersant D and optionally a portion of the thickener until a homogenous mixture is obtained, and then adding the saflufenacil and pyroxasulfone with shear to said homogenous mixture. This yields a mixture including the components, wherein saflufencacil and pyroxasulfone are present in the form of solid particles which are dispersed in the homogeneous aqueous phase formed by the water and the dispersant D. The mixture is then usually subjected to suitable means for reducing the particle size of the saflufenacil and pyroxasulfone particles present in the mixture typically to a mean particle size D[v, 0.5] below 10 pm, preferably to below 7 pm and in particular to below 5 pm. This step may be carried out by any physical attrition method, such as grinding, crushing or milling, in particular by wet grinding or wet milling, including e.g. bead milling, hammer milling, jet milling, air classifying milling, pin milling, cryogenic grinding processes and the like. Mixing and reducing particle size are usually performed subsequently. However it is also possible to perform these steps together. Step (i) is usually carried out at temperatures in the range of 10 to 60°C.
In step (ii) of the process of the invention, an aqueous solution of the anionic dispersant is provided as a component (ii). The aqueous solution may contain one or more dispersants D, in particular a dispersant of group D-i). Preferably, the aqueous solution contains at least a portion of the thickener, in particular a polysaccharide based thickener. The aqueous solution may also contain a portion or the total amount of inorganic thickener, in particular the phyllosilicate. The aqueous solution may also contain one or more bactericides and/or antifreeze. However, it is also possible to blend the final suspoemulsion with one or more bactericides and/or antifreeze. The aqueous solution may also contain antifoam to avoid foaming during production of the emulsion in step (iii). The aqueous solution can be prepared simply by mixing the components of the aqueous solution in an arbitrary order. However, it may be beneficial to predissolve the carbohydrate thickener, if present, in water and or a mixture of water and anti-freeze. Step (ii) is usually carried out at temperatures in the range of 10 to 70°C and preferably in the range of 15 to 60°C.
In step (iii) of the process of the invention, the dimethenamid-P is emulsified in the aqueous solution provided in step (ii). If the final suspoemulsion contains a surfactant D-ii) it is preferred to dissolve the dispersant D-ii) in the dimethenamid prior to emulsification. The dimethenamid may also be blended with a water-immiscible solvent, in particular with at least one plant oil prior to emulsification in order to reduce
the viscosity and/or for increasing the compatibility with the dispersant D-ii), if present. The amount of organic solvent, if present, is typically in the range of 0.1 to 10%, based on the total weight of dimethenamid-P and solvent. The dimethenamid-P, which is optionally blended with the further ingredients is then emulsified in the aqueous phase obtained in step (ii). For this, the aqueous phase and the dimethenamid, which optionally has previously been blended with further ingredients, are mixed and optionally homogenized. Typically homogenization is carried out to a mean droplet size D[v, 0.5] below 7 pm, preferably to below 5 pm and in particular to below 2 pm. Step (iii) is usually carried out at temperatures in the range of 10 to 70°C and preferably in the range of 15 to 60°C.
In step (iv) of the process of the invention, the thus obtained emulsion is then mixed with the aqueous suspension of pyroxasulfone and saflufenacil provided in step (i) to obtain a suspoemulsion. Optionally, one or more of the further ingredients, such as a defoamer, an antifreeze, bacterizides and/or water, are added at this stage. Mixing can be done by any conventional means for mixing liquids. Typically, the mixing is carried out in in a stirred tank.
The aqueous formulation of the present invention, i. e. the suspoemulsion of saflufenacil, pyroxasulfone and dimethenamid P, as well as the herbicide combination of saflufenacil, pyroxasulfone and dimethenamid P of the present invention are suitable for controlling undesired plant growth, in particular undesired plant growth in crop. For this, the aqueous formulation is applied to the undesired plants or to an area where the undesired plants will grow.
The application of the formulation of the present invention, and also the application of the herbicide combination may result in a synergistic effect.
As used herein, the terms “synergistic effect” and “synergism” are used synonymously and mean that the application of the combination of herbicidal components demonstrates a greater herbicidal effect than expected from the effect of the application of the individual herbicidal components when applied singly.
Synergism can be determined by the Colby method (Colby, S.R., Weeds, 1967(15), p. 20-22), i.e. the expected (or predicted) response of the combination is calculated by taking the product of the observed response for each individual component of the combination when applied alone divided by 100 and subtracting this value from the sum of the observed response for each component when applied alone. Synergism of the combination is then determined by comparing the observed response of the
combination to the expected (or predicted) 10 response as calculated from the observed responses of each individual component alone. If the observed response of the combination is significantly greater than the expected (or predicted) response as determined by Fisher's protected 15 Least Significant Difference (LSD) test using significance level 0.05, than the combination is said to be synergistic. For combinations of three components Colby equation is as follows:
Exp = X + Y + Z - (XY + XZ + YZ)/100 + (X-Y Z/10000) where X = effect in percent using herbicide A, here saflufenacil, at an application rate a;
Y = effect in percent using herbicide B, here pyroxasulfone, at an application rate b;
Z = effect in percent using herbicide C, here dimethenamid P at an application rate c;
E = expected effect (in %) of A + B + C at application rates a + b + c. and
Synergism = (Obs. — Exp. ) > LSD, wherein a combination is composed of components X, Y and Z, and Obs. designates the observed response of this combination. The synergistic effect may also be given as the ratio of the observed response and the expected response in percent, i.e. synergistic effect [%] = Obs./Exp. x 100
Here and in the following, the observations apply to both the formulation of the invention and the combination of the present invention, if not stated otherwise.
The formulation of the invention and the combinations of the invention can be applied in numerous crops. The crops include in particular field corn, including field corn grown for producing grain, seed or silage, popcorn, sweet corn, soybean, chickpea, edible pea, field pea, lentils, including green and red type, perennial grasses, in particular when grown for seed production, alfalfa, in particular in established stands of dormant alfalfa, in cereals, legume and oilseed cover crops. The formulations are active against broad-leaved weeds and grass weeds without inflicting substantial damage to the crop plants. For this, the formulations and the combinations of the invention are preferably applied pre-emergently, i. e. before the undesired plants emerge. Pre-emergent application in crops may be carried out shortly before or shortly after the crop has been planted but preferably before the crop plants emerge.
The formulation of the invention and the combinations of the invention can be applied in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait. Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Examples of genetically modified crops in which the formulations and combinations can be used include in particular corn and soybean:
Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN 10211 , BXN 10215, BXN 10222, BXN 10224, MON 1445, MON 1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
The formulations and the combinations of the invention provide a very good control of vegetation during the fallow period, i. e. the period following harvest and before the following crop is planted.
The formulations and the combinations of the invention provide a very good control of
vegetation also in non-crop areas, especially at high application rates.
The formulations and the combinations of the invention provide a very good control of the following plants, including broadleaf weeds, such as Amaranth, Palmer {Amaranthus palmeri), Amaranth, Powell {Amaranthus powellii), Bedstraw, catchweed {Gaiium aparine), Beggarticks, hairy {Bidens piiosa), Beggarweed, Florida {Desmodium tortuosum), Bindweed, field {Convolvulus arvensis , Buckwheat, wild Polygonum convolvulus), Buffalobur {Solanum rostratum) C. Burcucumber {S icy os angulatus) S, Canola, volunteer (rapeseed), all types {Brassica spp.), Carpetweed {Mollugo verticillata), Chamomile, mayweed {Anthemis cotula), Chickweed, common {Stellaria media), Cocklebur, common {Xanthium strumarium), Copperleaf, Virginia {Acalypha virginica), Cotton, volunteer {Gossypium hirsutum), Cowcockle { Vaccaria pyramidata), Dandelion ( Taraxacum officinale), Devil’s-claw {Proboscidea Louisiana), Eclipta {Edipta prostrata , Eveningprimrose, cutleaf {Oenothera laciniata), Galinsoga, smallflower {Gah'nsoga parviflora), Falseflax, smallseed {Cameh'na macrocarpa), Filaree, redstem {Erodium cicutarium), Fleabane, hairy {Conyza bonariensis), Flixweed {Descurainia sophia , Groundcherry, cutleaf {Physalis angulate), Groundsel, common {Senecio vulgaris), Hawksbeard, narrowleaf {Crepis tectorum), Hemlock, poison {Conium maculatum), Henbit {Lamium amplexicaule), Horseweed (marestail) {Conyza canadensis , Jimsonweed {Datura stramonium , Knotweed, prostrate {Polygonum aviculare), Kochia {Kochia scoparia , Ladysthumb {Polygonum persicaria), Lambsquarters, common {Chenopodium album), Lambsquarters, narrowleaf {Chenopodium pratericola), Lettuce, prickly {Lactuca serriola), Mallow, common {Malva neglecta), Mallow, little (cheeseweed) {Malva parviflora), Mallow, Venice {Hibiscus trionum , Marestail (horseweed) {Conyza canadensis , Morningglory, entireleaf {Ipomoea hederacea van integriuscula), Morningglory, ivyleaf {Ipomoea hederacea), Morningglory, palmleaf {Ipomoea wrightii), Morningglory, pitted {Ipomoea lacunose), Morningglory, tall {Ipomoea purpurea , Mustard, black {Brassica nigra , Mustard, tumble {Sisymbrium altissimum), Mustard, wild {Sinapis arvensis , Nettle, burning {Urtica urens), Nightshade, black {Solanum nigrum , Nightshade, cutleaf {Solanum trifiorum), Nightshade, Eastern black {Solanum ptycanthum), Nightshade, hairy {Solanum sarrachoides), Parthenium {Parthenium hysterophorus), Pennycress, field { Thlaspi arvense), Pigweed, prostrate {Amaranthus bh'toides), Pigweed, redroot {Amaranthus retroflexus), Pigweed, smooth {Amaranthus hybridus), Pigweed, tumble {Amaranthus albus), Puncturevine ( Tribulus terrestris), Purslane, common {Portulaca oleracea), Pusley, Florida {Richardia scabra), Ragweed, common {Ambrosia artemisiifoh'a), Ragweed, giant {Ambrosia trifida), Rocket, London {Sisymbrium irio), Sesbania, hemp {Sesbania exaltata), Shepherds-purse {Capsella bursa-pas ton's),
Sida, prickly {Sida spinosa), Smartweed, Pennsylvania {Polygonum pensyivanicum), Sowthistle, annual {Sonchus arvensis), Spurge, nodding {Chamaesyce nutans), Spurge, spotted {Chamaesyce maculate), Starbur, bristly {Acanthospermum hispidum), Sunflower, common {Heiianthus annuus), Tansymustard, pinnate {Descurainia pinnata), Texasweed {Caperonia paiustris), Thistle, Canada {Cirsium arvense), Thistle, Russian {Saisoia kaii), Velvetleaf {Abutiion theophrasti), Waterhemp {Amaranthus tubercuiatus) and Willowweed {Epiiobium adenocauioriy,
Annual grass weeds, such as Barley, hare {Hordeum murinums . leporinumy, Barnyardgrass {Echinochioa crus-galli), Bluegrass, annual {Poa annua), Bluegrass, roughstalk {Poa triviah's), Brome, California {Bromus carinatus), Brome, downy {Bromus tectorum), Brome, Japanese {Bromus japonicus), Canarygrass {Phaiaris canadensis), Cheat {Bromus secah'nus), Crabgrass, large {Digitaria sanguinah's), Crabgrass, smooth {Digitaria ischaemum), Crowfootgrass {Dactyioctenium aegyptium), Cupgrass, Southwestern {Eriochioa gracilis), Cupgrass, woolly {Eriochioa viiiosa), Fescue, rattail {Vuipia myuros), Foxtail, giant Setaria faberi), Foxtail, green Setaria viridis), Foxtail, yellow Setaria pumiia), Goosegrass Eleusine indica), Johnsongrass (seedling) Sorghum haiepense), Millet, Texas Urochioa texana), Millet, wild proso {Panicum miiiaceum), Oat, wild {Avena fatua), Panicum, fall {Panicum dichotomifiorum), Panicum, Texas Panicum texanum), Rice, red {Oryza sativa), Ryegrass, Italian {Loiium muitifiorum), Ryegrass, rigid {Loiium rigidum), Sandbur {Cenchrus spp.), Shattercane Sorghum bicoloi), Signalgrass, broadleaf {Brachiaria piatyphyiia), Witchgrass Panicum capiHare), Flatsedge, rice {Cyperus iria) and Nutsedge, yellow Cyperus escuientus).
The application of the formulation of the invention may vary depending on the rate may depend on the kind of ground to which the suspoemulsion is applied is typically in the range of 1 to 100 kg/h, in particular in the range of 5 to 50 kg/ha.
The individual application rates of saflufenacil is typically in the range of 5 to 250 g/ha, in particular in the range of 15 to 120 g/ha.
The individual application rates of pyroxasulfone is typically in the range of 5 to 250 g/ha, in particular in the range of 15 to 120 g/ha.
The individual application rates of dimethenamid P is typically in the range of 50 to 1500 g/ha, in particular in the range of 120 to 750 g/ha.
The formulations and the combinations of the present invention may be applied preplant, preemergence, or as burndown application, in particular in the fall. Preplant application may be done to the surface or by incorporating the formulation or the individual herbicides of the combination into the ground.
Preplant surface application is typically carried out by applying a uniform broadcast to the soil surface. Preplant surface application is usually carried out within 30 days of planting and before crop emergence. For preplant incorporated (PPI) application the formulation or the individual herbicides of the combination are usually incorporated into the upper soil surface, e. g. into a depth of 2 to 6 cm, preferably within 14 days of planting. Incorporation may be carried out by shallow incorporation, including a field cultivator, harrow, rolling cultivator, or finishing disc.
The application of the formulation of the invention or formulations or co-formulations of the individual herbicides of the combination of the invention may be carried out using water or a fluid nitrogen fertilizer as a spray carrier. For this, the respective formulations are diluted with water or the liquid nitrogen fertilizer to obtain a liquid spray liquor. Frequently, the amount of water used is at least 20 L/ha, in particular at least 25 L/ha and may be as high as 1000 L/ha.
In case of the combinations of the invention, the components of the combination are typically formulated separately or as co-formulations of two components of the herbicide combination of the invention. For example, pyraxasulfone is commercially available in the form of suspension concentrates and as wettable granules, e. g. under the brands Zidua® SC and Zidua® WG. Likewise, saflufenacil is commercially available in the form of suspension concentrates and as wettable granules, e. g. under the brands Sharpen® or Treevix®, both of BASF Corp. Saflufenacil may be also be formulated as an oil dispersion as described in WO 2011/070051. Dimethenamid P is commercially available as an emulsion concentrate, e.g. under the BASF SE brands Frontier® and Outlook®. The components of the combination of the invention may also be formulated as co-formulations e. g. as co-formulations of saflufenacil and pyroxasulfone as suggested in WO 2009/115490 or as a co-formulation of pyroxasulfone and dimethenamid P as suggested in WO 2009/115433.
The combination of the invention may also be in the form of a two package formulation, wherein one package is a formulation of pyroxasulfone while the other package contains a co-formulation of saflufenacil and dimethenamid-P, wherein all formulations contain at least one carrier material, if desired, one or more surfactants
and, if desired, one or more further auxiliaries customary for crop protection compositions. The combination of the invention may also be in the form of a three package formulation, wherein one package is a formulation of pyroxasulfone while the other two packages contain separate formulations of saflufenacil and dimethenamid-P, wherein all formulations contain at least one carrier material, if desired, one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.
In the case of individual formulations of the herbicides comprised in the combination of the present invention, the individual formulations are usually mixed prior to application in the desired ratios and applied as a spray liquor containing the herbicide combination of the present invention. Preferably, the mixing is performed as a tank mix, i.e. the formulations are mixed immediately prior or upon dilution with water or aqueous fertilizer. It is also possible to apply the individual formulations of the present invention as separate spray liquors which may be applied simultaneously or successively.
The spray liquors can be applied in conventional manner by using techniques as skilled person is familiar with. Suitable techniques include spraying, atomizing, dusting, spreading or watering. The type of application depends on the intended purpose in a well-known manner; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.
It is also possible to apply the formulations or combinations of the present invention in the form of fertilizer granules which have been impregnated with the formulations of the present invention or with formulations of the individual components.
To achieve a broader activity spectrum it may be possible to co-apply the formulation of the present invention or the combination of the present invention with a further herbicide. It is also possible to combine the application
The formulation of the present invention and the combination of the present invention may be applied together with an adjuvant as action improver. A particular preferred adjuvant is described in WO 00/53014 and in WO2010/037734. Said adjuvant is a combination of a Ci-Cs-alkyl C5-C22-alkanoate, a Cio-C2o-carboxylic acid, a partial phosphoric or sulfuric acid ester of a monohydroxy-functional polyalkyl ether and an alkyl polyoxyalkylene polyether. Preferred Ci-Cs-alkyl C5-C22-alkanoates are methyl oleate, methyl palmitate and ethyl oleate and mixtures thereof. Specifically, the C1-C5- alkyl Cs-C22-alkanoate comprises at least 70% by weight of methyl oleate or of a mixture of methyl oleate and methyl palmitate. Such action improver systems are commercially available under the name DASH®, e.g. DASH® HC, from BASF
Corporation, USA. Further action improvers include but are not limited to those adjuvants conventionally used in combination with glyphosate, such as non-ionic surfactants (NIS), ammonium sulfate, alkyl sulfates of Ce-is alkanols such as sodium dodecyl sulfate, alkyl ether sulfates of Ce-is alkanols, methylated soybean oil (MSO) and crop oil concentrate (COC).
The following examples are intended to further illustrate the present invention without limiting its scope in any way.
I. Analytics:
Particle sizes were determined by laser diffraction with a Malvern Mastersizer 2000 system at 23°C using the Fraunhofer model.
Viscosity was determined by Brookfield method (using spindle no. 2 at 30 rpm) and with an Anton Paar Rheometer.
The herbicide content was analysed by common HPLC methods.
Optical evaluation was carried out by light microscopy.
II. Ingredients:
Surfactant 1 : monobutyl ether of poly(ethylene oxide)-poly(propylene oxide) block copolymer (HLB: 17) - Atlas™ G 5000 (Croda);
Surfactant 2: monoether of polyethylene oxide)-poly(propylene oxide) block copolymer - Atlas™ G 5002L (Croda);
Surfactant 3: block copolymer of polyethylene glycol and 12-hydroxystearic acid (HLB: 6) - Atlox™ 4912 (Croda);
Surfactant 4: polymethyl methacrylate-polyethylene glycol graft copolymer (HLB: 11-12) - Atlox™ 4913 (Croda);
Surfactant 5: polyethylene glycol mono(tristyryl phenyl) ether sulfate ammonium salt - Soprophor® 4D/384 (Solvay);
Thickener 1 : xanthan gum - Rhodopol® 23 (Solvay);
Thickener 2: magnesium aluminum silicate which is a phyllosilicate of the smectite group - Van Gel® ES (Vanderbilt Minerals);
Antifoam 1 : polydimethylsiloxane - SAG™ 1572 (Momentive);
Biocide 1 : 1 ,2-benzisothiazol-3(2H)-one - Acticide® B 20 (Thor GmbH);
Biocide 2: 2-bromo-2-nitro-1 ,3-propandiol - Acticide® L 30 (Thor GmbH);
Biocide 3: mixture of 5-chloro-2-methyl-4-isothiazolin-3-one (1.11 %) and 2- methyl-4-isothiazolin-3-one (0.37%) - Acticide® MV (Thor GmbH);
Biocide 4: mixture of 1 ,2-benzisothiazol-3(2H)-one (2.5%) and 2-methyl-4- isothiazolin-3-one (2.5%) - Acticide® MBS (Thor GmbH);
Canola oil rapeseed oil with a low erucic acid content;
III. Preparation of the compositions of the invention
111.1 a Example 1 : Preparation of aqueous suspoemulsion 1 (without an inorganic thickener)
First, the three components for preparing the suspoemulsion, namely an aqueous millbase, an aqueous phase and an oil phase, were prepared separately.
To prepare the mill base, the components of Table 1 below were added together in the indicated weight ratio, mixed using a Silverson® high shear mixer or a MagicLab mixer, and then milled in an Eiger Torrance beadmill to below 10 pm. The particle size was monitored by microscopy.
To prepare the oil phase the three components listed in Table 2 were combined in the indicated weight ratio and then mixed until a homogeneous mixture was obtained.
Table 2
For preparing the aqueous phase initially the surfactants 1 and 5 were melted at 50 °C. Afterwards the Biocide 4 and water were mixed using a Silverson® high shear mixer and the melted surfactants were added and mixed until dissolved. Finally, the Thickener 1 was added with mixing. The five components were each used in the weight percentages shown in Table 3.
The oil phase was then slowly poured into the aqueous phase with mixing and mixing was continued for 5 minutes. Afterwards a median particle diameter D50 of 0.77 pm was measured.
The resulting emulsion was then mixed with the millbase and further components listed in Table 4 in the indicated weight ratio using an overhead stirrer fitted with a sawthooth blade until a homogeneous suspoemulsion was obtained.
111.1 b Properties of the aqueous suspoemulsion 1 Chemical Stability:
The chemical stability of the suspoemulsion 1 was monitored by measuring the weight percentages of saflufenacil, pyroxasulfone and dimethenamid-P before and after different storage conditions by HPLC. The results are given in weight percentages [% (w/w)] in Table 6 below. The additionally given numbers in brackets are the percentages of the respective initial weight percentage.
Density: Measurement of the density of the neat suspoemulsion 1 at a temperature of 20°C gave 1 .105 g/ml.
Appearance:
Initially the suspoemulsion 1 was an opaque, off-white, mobile liquid with medium viscosity. Over a period of 12 weeks at a temperature of 20°C, the appearance remained unchanged.
Stability of the formulation:
The stability of the suspoemulsion 1 formulation was monitored by assessing to what extent a clear layer or sediment is formed under different storage conditions. Results are given as scores on a scale of 1 to 10, where 0 represents no formation of a clear layer or of sediment and 10 represents unacceptable phase separation. The results are listed in Table 7 below.
Particle size distribution:
The particle size distribution of the suspoemulsion 1 was monitored by determining the Dio, D50 and D90 by laser diffraction before and after different storage conditions. The results are listed in Table 8 below.
The pH values were measured in accordance to the standard procedure CIPAC MT 75.2. The measurements were carried out on the neat suspoemulsion 1 and as a 1% dilution in deionized water before and after different storage conditions. The results are listed in Table 9 below.
Foam persistence:
The foam persistences were measured in accordance to the standard procedure CIPAC MT 47.2. The measurements were carried out on 5 % (v/v) dilutions of the suspoemulsion 1 in CIPAC D water. The dilutions were made of samples taken from the suspoemulsion before and after it was exposed to various storage conditions. The foam layers remaining in each case after 10 seconds, 1 minute, 3 minutes and 12 minutes were determined in mm. The results are listed in Table 10 below.
Wet sieve residue:
The particle size distribution of the suspoemulsion 1 was examined according to the standard procedure CIPAC MT 185 using stacked sieves having mesh sizes of 75 and 150 pm before and after different storage conditions. The respective residues obtained are listed in weight percent relative to the total weight in Table 11.
Dilution test:
The stability of dilutions of the suspoemulsion 1 were examined in accordance to the standard procedure CIPAC MT 180. The measurements were carried out on 5 % (v/v) dilutions of the suspoemulsion that were prepared with CIPAC D water at a temperature of 30°C. The dilutions were made of samples taken from the suspoemulsion before and after it was exposed to various storage conditions. The
volumes of cream and sediment formed in the dilutions after 30 minutes and 24.5 hours are given in Table 12 below.
Viscosity (Brookfield):
The Brookfield viscosity of the suspoemulsion 1 was measured by using spindle no. 2 at 30 rpm at 20°C before and after different storage conditions. The results are listed in Table 13 below.
Viscosity at different shear rates:
The viscosity of the suspoemulsion 1 was determined with a rheometer at different shear rates at 20°C before and after different storage conditions. The measured viscosities in mPa-s at shear rates of- 10 s-1 and 100-s-1 are given in Table 14 below.
First, the three components for preparing the suspoemulsion, namely an aqueous millbase, an aqueous phase and an oil phase, were prepared separately.
To prepare the mill base, the components of Table 15 below were added together in the indicated weight ratio and then mixed using a Silverson® high shear mixer with a disintegrating head and finally milled with a beadmill (Eiger Torrance mini motormill).
To prepare the oil phase the three components listed in Table 16 were combined in the indicated weight ratio and then mixed until a homogeneous mixture was obtained.
To prepare the aqueous phase the three components listed in Table 17 were combined in the indicated weight ratio and then mixed with a Silverson® high shear mixer fitted with a dispersing head until the thickeners were homogeneously dispersed.
The oil phase and the aqueous phase were mixed with a Silverson® high shear mixer with a emulsion head in a ratio so that an emulsion consisting of 49.17 %(w/w) oil phase and 50.83%(w/w) aqueous phase was obtained.
The resulting emulsion was then blended with the millbase and further components listed in Table 18 in the indicated weight ratio until a homogeneous suspoemulsion was obtained. Table 18
The obtained aqueous suspoemulsion 2 had the composition shown in Table 19.
111.2b Properties of the aqueous suspoemulsion 2
Chemical Stability:
The chemical stability of the suspoemulsion 2 was monitored by measuring the weight percentages of saflufenacil, pyroxasulfone and dimethenamid-P before and after different storage conditions as described above for suspoemulsion 1 .
Density:
Measurement of the density of the neat suspoemulsion 2 at a temperature of 20°C gave 1.110 g/ml.
Appearance:
Initially the suspoemulsion 2 was an opaque, off-white, mobile liquid with medium viscosity. Over a period of 12 weeks at a temperature of 20°C, the appearance remained unchanged.
Stability of the formulation:
The stability of the suspoemulsion 2 formulation was monitored by assessing to what extent a clear layer or sediment formed under different storage conditions. The protocol described for suspoemulsion 1 was used. The results are in Table 21 below.
Table 21
Particle size distribution:
The particle size distribution of the suspoemulsion 2 was monitored by determining the Dio, D50 and D90 as described for suspoemulsion 1. The results are summarized in Table 22 below.
The pH values were measured in accordance to the standard procedure CIPAC MT
75.2 as described for suspoemulsion 1. The results are listed in Table 23 below.
Foam persistence:
The foam persistences were measured in accordance to the standard procedure CIPAC MT 47.2 as described for suspoemulsion 1. The results are listed in Table 24 below.
Wet sieve residue:
The particle size distribution of the suspoemulsion 2 was examined according to the standard procedure CIPAC MT 185 as described for suspoemulsion 1. The respective residues obtained are listed in weight percent relative to the total weight in Table 25.
Dilution test:
The stability of dilutions of the suspoemulsion 2 were examined in accordance to the standard procedure CIPAC MT 180 as described for suspoemulsion 1 . The volumes of cream and sediment formed in the dilutions after 30 minutes and 24.5 hours are given in Table 26 below.
Viscosity (Brookfield):
The Brookfield viscosity of the suspoemulsion 2 was measured at 20°C of the neat formulation by using spindle no. 2 at 30 rpm. before and after different storage conditions. The results are listed in Table 27 below.
Table 27
Viscosity at different shear rates:
The viscosity of the suspoemulsion 2 was determined with a rheometer at different shear rates before and after different storage conditions. The measured viscosities in mPa-s at shear rates of- 10 s-1 and 100-s-1 are given in Table 28 below.
I II ,2bc Preparation of aqueous suspoemulsion 3 (including an inorganic thickener)
Suspoemulsion 3 was prepared by the protocol of suspoemulsion 2, where the rapeseed oil was replaced by same amount of canola oil. Thus, the composition of suspoemulsion 3 is the same as of suspoemulsion 2, except for containing canola oil instead of rapeseed oil. The suspoemulsion 3 had the same properties as suspoemulsion 2 regarding viscosity, chemical stability, formulation stability and foam persistence.
Field Weed Efficacy Study Method
Experiments were conducted at multiple field locations over multiple seasons to measure efficacy of Suspoemulsion 1 on various weed species under various environmental conditions. For these studies, the herbicide treatments were applied using a randomized complete block design to plots approximately 2 x 9 m, using a backpack sprayer at 140-187 l/ha spray volume. Each treatment was replicated three times in a study. Herbicides were applied at a PRE (preemergence) timing 1 day of planting of crop and before the emergence of weeds. Herbicides were activated with irrigation/rainfall within a week after application. Weed control efficacy was evaluated by rating the plots for weed control (0-100% scale, where 0% = healthy weed and 100% = dead weed) based on visual assessments at weekly intervals. Higher control
rating indicates a better weed efficacy profile for a given treatment. For comparison purpose, an untreated weedy check was included in the studies.
According to the results in Table 29, suspoemulsion 1 provided strong long-season residual control of several broadleaf and grass weed species.
Claims
1 . Aqueous herbicide formulation containing a) 2 to 10 wt.-%, based on the total weight of the formulation, of saflufenacil b) 2 to 10 wt.-%, based on the total weight of the formulation, of pyroxasulfone, c) 20 to 35 wt.-%, based on the total weight of the formulation, of dimethenamid-P, d) 0.3 to 3 wt.-%, based on the total weight of the formulation, of at least one dispersant D, selected from non-ionic polymeric dispersants, e) 0.1 to 1 wt.-%, based on the total weight of the formulation, of at least one anionic dispersant E which bears at least one anionic group selected from sulfonate, sulfate, phosphonate and phosphate groups, f) at least one thickener F, and g) water where the formulation is an aqueous suspoemulsion.
2. The formulation of claim 1 , wherein the polymeric dispersant D is selected from block copolymers having a poly(C2-C3-alkylene oxide) moiety and graft polymers having a poly(C2-C3-alkylene oxide) moiety.
3. The formulation of claim 2, wherein the polymeric dispersant D is selected from
D-i) block copolymers of the group of Ci-C2o-alkyl-poly(C2-C3-alkylene oxides) as dispersant D-i),
D-ii) block copolymers having at least one block formed by polyhydroxy-Cio-C2o alkanoic acid and at least one block formed by a poly(C2-C3-alkylene oxide) as dispersant D-ii),
D-iii) graft copolymers having a polymer backbone, which is formed by ethylenically unsaturated monomers, e.g. Ci-C4-alkyl (meth)acrylates and (meth)acrylic acid, and side chains grafted to the polymer backbone, which are polyethylene oxide groups and/or Ci-C4-alkyl-polyethylene oxide groups as dispersant D-iii), and combinations thereof.
4. The formulation of claim 3 where the dispersant D is a combination of at least one dispersant D-i) and at least one further dispersant D, which is selected from dispersants D-ii), dispersants D-iii) and combinations of at least one dispersant D-ii) and at least one dispersant D-iii).
The formulation of any one of the preceding claims, wherein the dispersant D comprises at least one dispersant D having a HLB value of in the range of 3 to 8 and at least one dispersant D which has a HLB value of at least 9. The formulation of any one of the preceding claims, wherein the anionic dispersant E is selected from
E.1 aryl- and Ci-Ci6-alkylarylsulfonates such as naphthylsulfonate, mono-, di- and tri-Ci-Ci6-alkylnaphthylsulfonates such as dibutylnaphtylsulfonate, dodecyldiphenylether sulfonate, mono-, di- and tri-Ci-Ci6- alkylphenylsulfonates such as cumylsulfonate, octylbenzene sulfoanate, nonylbenzenesulfonate, dodecylbenzene sulfonate and tridecylbenzene sulfonate;
E.2 aryl ether sulfates, in particular aryl poly(C2-C3-alkylene oxide) ether sulfates, e.g. the sulfates of (poly)ethoxylated di- or tristyryl phenols and the sulfates of (poly)ethoxylated-co-propoxylated di- or tristyrylphenols;
E.3 aryl ether phosphates, in particular aryl poly(C2-C3-alkylene oxide) ether phosphates, e.g. the phosphate esters of (poly)ethoxylated di- or tristyrylphenols and the phosphate esters of (poly)ethoxylated-co- propoxylated di- or tristyrylphenols;
E.4 condensates of arylsulfonic acid, such as naphthalenesulfonic acid or phenolsulfonic acid, with formaldehyde and condensates of arylsulfonic acid, such as naphthalenesulfonic acid or phenolsulfonic acid, with formaldehyde and urea. and combinations thereof. The formulation of any one of the preceding claims, wherein the anionic dispersant E is selected from aryl poly(C2-C3-alkylene oxide) ether sulfates and aryl poly(C2-C3-alkylene oxide) ether phosphates. The formulation according to any one of the preceding claims, where the formulation in addition to the components a)-c) contains: d) 0.3 to 3 wt.-%, based on the total weight of the formulation, of at least one dispersant D which is selected from non-ionic block copolymers having a poly(C2-C3-alkylene oxide) moiety and non-ionic graft polymers having a poly(C2-C3-alkylene oxide) moiety; e) 0.1 to 1 wt.-%, based on the total weight of the formulation, of at least one anionic dispersant E which is selected from aryl poly(C2-C3-alkylene oxide) ether sulfates and aryl poly(C2-C3-alkylene oxide) ether phosphates,
f) at least one thickener F, and g) water.
9. The formulation of claim 8, wherein the polymeric dispersant D is a combination of a) at least one dispersant D-i) selected from block copolymers of the group of Ci-Cio-alkyl-poly(C2-C3-alkylene oxides) and b) at least one further dispersant D, which is selected from dispersants D-ii) and combinations of at least one dispersant D-ii) and at least one dispersant D-iii), where the dispersant D-ii) is selected from block copolymers having at least one block formed by polyhydroxy-Cio-C2o alkanoic acid and at least one block formed by a poly(C2-C3-alkylene oxide), and where the dispersant D-iii) is selected from graft copolymers having a polymer backbone, which is formed by ethylenically unsaturated monomers, e.g. Ci-C4-alkyl (meth)acrylates and (meth)acrylic acid, and side chains grafted to the polymer backbone, which are polyethylene oxide groups and/or Ci-C4-alkyl-polyethylene oxide groups.
10. The formulation of claim 9, wherein the dispersant D comprises at least one dispersant D having a HLB value of in the range of 3 to 8, which is selected from dispersants D-ii) and at least one dispersant D which has a HLB value of at least 9, which is selected from dispersants D-i) and combinations of at least one dispersant D-i) and at least one dispersant D-iii).
11 . The formulation of any one of the preceding claims, wherein the thickener F comprises at least one polysaccharide thickener.
12. The formulation of claim 11 , where the thickener F further comprises an inorganic thickener, which is in particular a phyllosilicate.
13. The formulation of claim 12, where the inorganic thickener comprises a phyllosilicate which is a smectite mineral.
14. The formulation of any one of claims 11 to 13, wherein the polysaccharide thickener comprises xanthan gum.
15. The formulation of any one of the preceding claims further comprising at least one anti-freeze.
The formulation of any one of the preceding claims, wherein the weight ratio of pyroxasulfone to saflufenacil is in the range of 3:1 to 1 :3, the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :8 to 1 :1 and where the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :10 to 1 :1. A process for producing an aqueous herbicide formulation according to any one of the preceding claims, which comprises:
(i) Providing an aqueous suspension of pyroxasulfone and saflufenacil containing at least one dispersant D as a component (i),
(ii) Providing an aqueous solution of the anionic dispersant E as a component (ii);
(iii) Providing an aqueous emulsion of dimethenamid P in the component (ii),
(iv) Mixing the component (i) with the emulsion provided in step (iii); where the component (i) and/or the emulsion provided in step (iii) contains at least one thickener F. A combination of herbicide compounds consisting of pyroxasulfone, saflufenacil and dimethenamid P wherein the weight ratio of pyroxasulfone to saflufenacil is in the range of 3:1 to 1 :3, the weight ratio of saflufenacil to dimethenamid P is in the range of 1 :8 to 1 :1 and where the weight ratio of pyroxasulfone to dimethenamid P is in the range of 1 :10 to 1 :1 . The use of a formulation as defined in any one of claims 1 to 16 or a herbicide combination as defined in claim 18 for controlling undesired plant growth. A method for controlling undesired plant growth which comprises applying a formulation as defined in any one of claims 1 to 16 or a herbicide combination as defined in claim 18 to the undesired plants or to an area where the undesired plants will grow.
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