Emulsifiable concentrate (EC)

Abstract

The invention relates to a composition which comprises pinoxaden, metribuzin and an auxiliary agent, wherein the adjuvant is a built-in oil type adjuvant.

Description

[0001] The present invention relates to a liquid herbicidal composition comprising pinoxaden, metribuzin and an in-built oil adjuvant; and to the use and preparation method of the liquid herbicidal composition.

[0002] Pinoxaden (8-(2,6-diethyl-4-methylphenyl)-9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo[1,2-d][1,4,5]oxadiazepin-7-yl 2,2-dimethylpropionate) is a herbicide suitable for controlling grass weeds in certain cereals. Due to the presence of the ester bond, pinoxaden is extremely sensitive to pH, water and salts and will therefore convert to the corresponding acid if the conditions are not appropriate. Metribuzin (4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one) is a herbicide for both pre- and post-emergence of crops and inhibits photosynthesis by disrupting photosystem II.

[0003] Many grass herbicides (graminicides) for cereals require adjuvants to exert their full biological activity. In many cases, the physicochemical properties of the active ingredients make it difficult to add adjuvants to the composition. Because the chemical or physical stability of the active ingredient is affected by the added adjuvant, or because the biological performance is insufficient. Due to the chemical and physical instability of the herbicides used, it is particularly challenging to manufacture biologically effective and stable compositions.

[0004] Typically, formulated pinoxaden products are always applied in combination with adjuvants (so-called tank mix adjuvants) that can be in-built or added to the spray tank. The application of pinoxaden and tank mix adjuvants is problematic because there are usually physical incompatibilities, which can lead to poor biological efficacy of the mixture and / or problems with application. These incompatibilities also lead to an increased degree of flocculation, which can cause clogging of the application equipment.

[0005] Adjuvants can also be incorporated into the herbicide composition (so-called in-built adjuvants). The advantage of using in-built adjuvants is to ensure the correct dosage of adjuvants is used in practice. If too little adjuvant is used, the full efficacy potential of the formulation cannot be achieved. However, if too high a dosage of adjuvant is given, there is a possibility of damaging the crop.

[0006] Due to the instability of pinoxaden and the difficulty in achieving physical compatibility between the in-built adjuvant and the rest of the formulation, the formulation of pinoxaden compositions containing in-built adjuvants is challenging. To date, the formulation has mainly relied on tris(2-ethylhexyl) phosphate (TEHP).

[0007] Due to the instability of pinoxaden and the difficulty in achieving physical compatibility between the in-built adjuvant and the rest of the formulation, the formulation of pinoxaden compositions containing in-built adjuvants is challenging. To date, the formulation has mainly relied on tris(2-ethylhexyl) phosphate (TEHP).

[0008] To solve these problems, the present invention therefore provides a composition comprising pyroxasulfone, metamitron and an adjuvant; wherein the adjuvant is an inbuilt oil adjuvant.

[0009] It has surprisingly been found that the composition according to the invention solves both the formulation problems discussed above and exhibits increased crop safety and technical performance. In particular, it has been found that the composition according to the invention shows better crop tolerance / safety towards crops (such as potatoes and wheat) while exhibiting higher efficacy such as a higher level of weed control.

[0010] Preferably, the inbuilt oil adjuvant is polypropylene glycol ether, even more preferably polypropylene glycol stearyl ether. Advantageously, polypropylene glycol stearyl ether has the following formula:

[0011] R-(O-CH2CH(CH3)) n -O-R1

[0012] wherein R is a C12 to C18 straight or branched chain alkyl or alkenyl group, n is from 1 to 30, and R1 is H or methyl. Preferably, n is from 5 to 18, and / or wherein R is a C 16 to C 18 straight or branched chain alkyl group.

[0013] Preferred polypropylene glycol stearyl ethers for the novel composition are stearyl ethers having between 10 and 20 polypropylene glycol units. Particularly preferred stearyl ethers include polypropylene-15-stearyl ether and polypropylene-11-stearyl ether. Polypropylene-15-stearyl ether and polypropylene-11-stearyl ether include E (ABITEC Corporation), Arlamol TM PS15 (Croda Chem. Europe Ltd), Arlamol TM PS15E (Croda Inc), TPP (Innospec), Jeecol PSA-11 (Jeen International), Jeecol PSA-15 (Jeen International), P-15 (LipoChemicals), Lumisolve CSA-70 (Lambent Tech), Lumisolve CSA-75 (Lambent Tech), Procol TM PSA-11 (Protameen), Procol TMPSA-15 (Protameen), Sympatens ASP-150 (Kolb), APS (Evonik), Witconol TM APS (Evonik), P (Innospec), and Prox-onic SA1-015 / P (Protex International).

[0014] Particularly preferred polypropylene glycol stearyl ethers are Arlamol TM PS15E, a stearyl ether having 11 polypropylene glycol units (Croda Chemicals Ltd. Goole, England).

[0015] Advantageously, the built-in oil-type adjuvant is present in an amount of 1% to 30% by weight, such as 5% to 25% by weight, 7% to 23% by weight, 11% to 19% by weight, or even 12% to 16% by weight.

[0016] Advantageously, the composition does not contain or is substantially free of tris(2-ethylhexyl) phosphate (TEHP). 'Substantially free' means less than 0.5% by weight.

[0017] Preferably, the composition contains pyroxasulfone in an amount of 0.05% to 50% by weight, 0.1% to 30% by weight, 0.5% to 20% by weight, 0.8% to 15% by weight, 1% to 9% by weight, or even 3% to 7% by weight.

[0018] Preferably, the composition contains metribuzin in an amount of 1% to 65% by weight, 2% to 55% by weight, 4% to 45% by weight, 5% to 35% by weight, 8% to 30% by weight, 9% to 25% by weight, 11% to 20% by weight, or even 15% to 19% by weight.

[0019] The composition may contain a safener, preferably cloquintocet-mexyl or mefenpyr-diethyl, and even more preferably cloquintocet-mexyl. Such a safener may be present in an amount of 0.5% to 5% by weight, such as 1% to 2% by weight.

[0020] Surfactants are included as emulsifiers, dispersants and wetting agents. Surfactants useful in the novel compositions are known in the art and include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; salts of aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol ethoxylate; alcohol-alkylene oxide adducts such as tridecanol ethoxylate; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl esters of sulfosuccinic acid such as sodium bis(2-ethylhexyl)sulfosuccinate; sorbitol esters such as ethoxylated sorbitol hexaoleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; fatty alcohol alkoxylates that may be alkyl-capped; block copolymers of ethylene oxide and propylene oxide; and salts of monoalkyl and dialkyl phosphates; alkylated polyvinylpyrrolidone, and also other substances, described, for example, in “McCutcheon's Emulsifiers & Detergents”, North American Edition, MC Publishing Company, 2018. Mixtures of one or more of these surfactants may also be used.

[0021] The surfactant may be present in a total amount of from 3% to 30% by weight, preferably from 4% to 25% by weight, such as from 5% to 20% by weight, or from 6% to 19% by weight.

[0022] Particularly preferred is the Ca-salt of dodecylbenzenesulfonic acid (which may be present in the range of 1% to 10% by weight, such as 1.5% to 5% by weight), the condensation product of castor oil and ethylene oxide (which may be present in the range of 1% to 15% by weight, such as from 3% to 9% by weight), and / or derivatives of block polymers of ethylene oxide and methylethylene oxide (which may be present in the range of 1% to 15% by weight, such as from 3% to 9% by weight).

[0023] The novel compositions may also contain additional formulation aids known in the art, such as crystallization inhibitors, viscosity-altering substances, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH-adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and also liquid and solid fertilizers.

[0024] Each additional formulation ingredient may be present in a weight / volume percentage (%) of from 0.01% to 5% by weight.

[0025] Preferably, the composition according to the invention is prepared in the form of an emulsion concentrate (EC).

[0026] However, it is also contemplated that the compositions according to the invention can also be prepared in the form of an oil dispersion (OD), a suspoemulsion (SE) or a suspension concentrate (SC). Such formulations are diluted before use. The diluted formulations can be prepared, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0027] The oil carrier can be used as a medium for dispersing the active ingredient. The oil carriers suitable for the compositions of the invention can be selected from rapeseed oil, methylated rapeseed oil, synthetic paraffins (such as (C12-C16), (C14-C18), (C15-C21) and (C18-C26)), dipropylene glycol dibenzoate, hydrocarbons (such as C11-C14, normal alkanes, isoparaffins, cyclic hydrocarbons, and <2% aromatics), aromatic hydrocarbons (such as C10-C13, and <1% naphthalene), aromatic hydrocarbons (such as C9, and <0.1% benzene), mixtures of petroleum extracts comprising solvent dewaxed light paraffin and solvent dewaxed heavy paraffin distillates, solvent naphtha, citrate-based solvents, tri(2-ethylhexyl) O-acetylcitrate, cyclohexanedicarboxylic acid, dinonyl ester, tri-n-hexyl trimellitate, 1,2,4-benzenetricarboxylic acid, trihexyl ester, isopropyl myristate, sebacic acid, bis(1-methylethyl) ester, isobornyl acetate (IBA, >94%), C8-C10 fatty acid methyl esters, triacetylglycerol and isoparaffins, or mixtures thereof.

[0028] The preferred solvent / carrier is methyl benzoate.

[0029] In a second aspect of the invention, there is provided a method for inhibiting or controlling the growth of unwanted plants (such as weeds), wherein a herbicidally effective amount of the composition as described herein is applied to the plants or their habitat.

[0030] Crops of useful plants for which the compositions according to the invention can be used include in particular cereals, especially potatoes, wheat, durum wheat, triticale, rye and barley.

[0031] The term "crop" should be understood to also include crops which have been made tolerant to herbicides or herbicide classes (such as ALS, GS, EPSPS, PPO and HPPD inhibitors) by conventional breeding or genetic engineering methods. Examples of crops which have been given tolerance to, for example, imidazolinones (such as imazamox) by conventional breeding methods are summer rape (canola). Examples of crops which have been given tolerance to herbicides by genetic engineering methods include, for example, maize varieties having glyphosate and glufosinate resistance, which maize varieties are sold under the trade names and are commercially available. The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds, such as Stellaria, Apila, Avena, Setaria, Sinapis, Lolium, Echinochloa, Bromus, Alopecurus, Phalaris, Amaranthus, Chenopodium, Convolvulus, Chrysanthemum, Papaver, Cirsium, Polygonum, Matricaria, Galium, Viola, and Veronica.

[0032] Crop plants should also be understood to mean those crop plants that have been given resistance to harmful insects by genetic engineering methods, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the boll weevil), and also Bt potato (resistant to the Colorado beetle). An example of Bt corn is the Bt-176 corn hybrid (Syngenta Seeds). The Bt toxin is a protein that is naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins and transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073, and EP-A-427 529. Examples of transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are (maize), Yield (maize), NuCOTIN33BC (cotton), (cotton), (potato), and Plant crops and their seed materials can be herbicide-tolerant and at the same time insect-feeding-tolerant ("stacked" transgenic events). For example, the seeds can have the ability to express the insecticidal active Cry3 protein and at the same time be glyphosate-tolerant. The term "crop" should also be understood to include crops obtained by conventional breeding or genetic engineering methods due to the so-called output characteristics (such as improved flavor, storage stability, nutrient content).

[0033] The cultivation area should be understood to include the land on which crop plants have already grown, together with the land intended for cultivating those crop plants.

[0034] It is advantageous for the composition according to the invention to be used as a ready-to-use mixture.

[0035] In a third aspect of the invention, there is provided a method for preparing a composition as described herein.

[0036] Unless otherwise stated, all percentages are given as percentages by total weight, and all examples and preferred features can be combined in any combination.

[0037] The present invention is described by the following non-limiting examples.

[0038] Example

[0039] Compositions A and comparative composition B were prepared according to the present invention, wherein the components (in % by weight) are listed in Table 1.

[0040] For further comparison, with commercially available products containing pinoxaden (Composition D, Axial 50 ) and metribuzin (Composition E, Adrino 70 ). A tank mix (Composition C) containing the same amounts of Axial 50 and Adrino 70 as in Composition B (Compositions D and E) was also prepared. The relevant components of these compositions (where known) are also listed in Table 1.

[0041] Table 1

[0042]

[0043] Table 2

[0044]

[0045] Physical and chemical properties

[0046] A series of properties of Composition A were tested, as listed below.

[0047] pH

[0048] The method is based on CIPAC MT 75.3, in which a 1% dilution of the formulation in deionized water was measured.

[0049] Persistent foaming

[0050] The method is based on CIPAC MT 47.3. It specifies the ambient temperature, standard hard water 'D', and only the foam after 1 minute is recorded.

[0051] Emulsion stability

[0052] It is based on CIPAC MT 36.3, in which the stability of the emulsion after 0.5 h and 2 h was tested for standard hard waters A and D.

[0053] 100 ml of an aqueous emulsion (0.4% v / v oil phase when diluted). The stability of the emulsion was then in terms of the amount of free 'oil' or 'cream' separated when the emulsion was left undisturbed for 0.5 h and 2 h.

[0054] Chemical stability at high temperature

[0055] The formulations were tested for their stability to chemical degradation at the temperatures and times listed below. The recoveries (in percentage) of the active ingredients, metribuzin, pinoxaden, and cloquintocet-mexyl, were measured as an indicator of stability.

[0056] The results are shown in Table 3.

[0057] Table 3

[0058]

[0059] Thus, it can be seen that Composition A exhibits a very high level of chemical stability and suitable physical properties.

[0060] Biological properties

[0061] At high application rates, Composition A showed better crop tolerance (i.e., reduced phytotoxicity) on potatoes and wheat compared to the equivalent TEHP-containing Composition B.

[0062] (DAA = Days after application.)

[0063] The results are shown in Tables 4 and 5.

[0064] Table 4

[0065]

[0066]

[0067] Table 5

[0068]

[0069] At the same dosage rate (50 + 175 g AI / ha), Composition A also showed better crop safety on wheat compared to the tank mix Composition C. The results are shown in Table 6.

[0070] Table 6

[0071]

[0072] Compared to the tank mix of PXD + MTB (Composition C) at the same dosage rate (50 + 175 g AI / ha) or PXD alone (Composition D) at 50 g AI / ha, Composition A promoted better control of grass (Phalaris minor) on potatoes. The results are shown in Table 7.

[0073] Table 7

[0074]

[0075] Composition A also enables the use of lower doses of MTB for weed control in potatoes, where the same effect is achieved compared to the standard dose rate of MTB alone (Composition E, 525 g AI / ha).

[0076] The test weed target Echinochloa colona was sprayed with Compositions A and E. Results were obtained by visual assessment at 28 days, 42 days, and 65 days after application, and the average values of the results are listed in Table 8 below.

[0077] Table 8

[0078]

[0079] It can be seen that the compositions according to the invention show improvements in both crop safety and weed control when compared to existing compositions.

[0080] The present invention is defined by the claims.

Claims

1. A composition comprising pyroxasulfone, metribuzin and an adjuvant; wherein the adjuvant is an in-built oil adjuvant.

2. The composition according to claim 1, wherein, The in-built oil adjuvant is polypropylene glycol ether.

3. The composition according to claim 2, wherein, The polypropylene glycol ether is polypropylene glycol stearyl ether.

4. The composition according to any one of claims 2 or 3, wherein The polypropylene glycol stearyl ether has the following formula: R-(O-CH2CH(CH3)) n -O-R1 wherein R is a C12 to C18 straight or branched chain alkyl or alkenyl group, n is from 1 to 30, and R1 is H or methyl.

5. The composition according to claim 4, wherein, n is from 5 to 18, and / or wherein R is C 16 to C 18 a straight-chain or branched-chain alkyl group.

6. The composition according to any one of the preceding claims, wherein, The in-built oil adjuvant is present in an amount of 1% to 30% by weight.

7. The composition according to any one of the preceding claims, wherein, The pyroxasulfone is present in an amount of 0.5% to 20% by weight.

8. The composition according to any one of the preceding claims, wherein, The metribuzin is present in an amount of 5% to 35% by weight.

9. The composition according to any one of the preceding claims, further comprising a safener, preferably cloquintocet-mexyl or pyraclonil.

10. The composition according to any one of the preceding claims, wherein, The composition is substantially free of tris(2-ethylhexyl) phosphate (TEHP).

11. The composition according to any one of the preceding claims, the composition being in the form of an emulsion concentrate (EC).

12. A method for suppressing or controlling unwanted plant growth, wherein, Apply a herbicidally effective amount of the composition according to any one of the preceding claims to the plant or its habitat.

13. A method for preparing the composition according to any one of claims 1 to 11.

14. Use of the composition according to any one of claims 1 to 11 for controlling unwanted plant growth, wherein, Apply a herbicidally effective amount of the composition according to any one of the preceding claims to the plant or its habitat.

15. The use according to claim 14, wherein, The plant is grass.

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