CN110996660A

CN110996660A - Oil-dispersible preparation

Info

Publication number: CN110996660A
Application number: CN201880052736.XA
Authority: CN
Inventors: V·古比瑞; S·温德里奇
Original assignee: Adama Agan Ltd
Current assignee: Adama Agan Ltd
Priority date: 2017-08-14
Filing date: 2018-08-13
Publication date: 2020-04-10
Also published as: WO2019034934A1

Abstract

The present invention provides a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet, an amount of at least one sulfonylurea herbicide, and an agrochemically acceptable non-aqueous liquid carrier, wherein flufenacet is dissolved in the non-aqueous liquid carrier, and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier. The present application also provides a method for controlling weeds comprising applying the stable formulation described herein; and methods for preparing the stable formulations described herein.

Description

Oil-dispersible preparation

This application claims priority from U.S. provisional application No. 62/545,351, filed on 8/14/2017, the contents of which are hereby incorporated by reference.

Throughout this application, various publications are referenced, including publications referenced in parentheses. The disclosures of all 10 of the cited publications are hereby incorporated by reference in their entireties into this application in order to more fully describe the state of the art to which this invention pertains.

The present subject matter relates to pesticidal compositions for agricultural pest control applications. In particular, the subject matter provides a stable herbicidal liquid formulation comprising flufenacet and at least one sulfonylurea herbicide.

Background

Sulfonylureas and oxyacetamides (including flufenacet) are generally known to have herbicidal activity.

Sulfonylurea herbicides are acetolactate synthase (ALS) inhibitors or acetohydroxyacid synthase (AHAS) inhibitors. They act by inhibiting the biosynthesis of branched-chain amino acids, such as valine and isoleucine, and thereby inhibit cell division and plant growth.

Oxyacetamides, including flufenacet, inhibit fatty acid metabolism and thereby also inhibit cell division and plant growth.

The administration of two active ingredients with two different modes of action has a number of advantages, such as reduced application rates, reduced number of applications and in some cases a synergistic effect (in which the efficacy is increased).

Combining different active ingredients has the added value of preventing the emergence of resistant species.

However, in the case where each active ingredient is in its own formulation, there is often a problem of incompatibility when the formulation is tank-mixed to combine the active ingredients for application in the field.

Due to the differences in the structure of the active ingredients, combining two active ingredients into one formulation can be challenging, especially when one or both active ingredients are highly unstable.

Flufenacet, an oxyacetamide herbicide, is a highly sensitive molecule that rapidly decomposes under a variety of conditions.

The N-isomer of flufenacet, which is less active and/or more toxic, is one of the breakdown products of flufenacet.

Sulfonylurea herbicides and oxyacetamide herbicides are each formulated into a solid preparation and a liquid preparation in the presence of a stabilizer such as a pH adjuster.

Sulfonylurea herbicides are sensitive to acidic conditions and hydrolyze rapidly in aqueous and/or acidic environments. Sulfonylurea herbicides can remain stable at pH values greater than 7.

Flufenacet, on the other hand, is unstable in neutral or alkaline conditions. In neutral or basic conditions, isomerization of the molecule occurs, resulting in the rapid formation and accumulation of the N-isomer.

In the prior art, flufenacet is formulated as a solid composition and is stabilized with an acid. EP922388B discloses solid dry compositions in which flufenacet is stabilized against the formation of the N-isomer by adding an amount of citric acid to lower the pH of the composition.

In foliar applications, liquid formulations are preferred because of the advantage of better miscibility which reduces flow problems.

The problem to be solved by the present invention is therefore to combine sulfonylureas and flufenacet into a single stable liquid formulation.

Disclosed herein are stable liquid formulations comprising a sulfonylurea herbicide and flufenacet.

Disclosure of Invention

The present invention provides a stable herbicidal non-aqueous liquid formulation comprising:

a) an amount of flufenacet;

b) an amount of at least one sulfonylurea herbicide; and

c) an agrochemically acceptable non-aqueous liquid carrier,

wherein flufenacet is dissolved in a non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier.

The present application also provides a method for controlling weeds, comprising: the stable herbicidal non-aqueous liquid formulation described herein is applied to weeds, a portion of a weed, an area adjacent to a weed, or soil and/or seeds of a weed to control the weed.

The present application also provides a method of controlling weeds, comprising:

a) obtaining a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet, an amount of at least one sulfonylurea herbicide, and an agrochemically acceptable non-aqueous liquid carrier, wherein flufenacet is dissolved in the non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier, and

b) the stable herbicidal formulation is applied to weeds, a portion of a weed, an area adjacent to a weed, or soil and/or seeds of a weed, thereby controlling the weed.

The present invention also provides a method for preparing a stable herbicidal non-aqueous liquid formulation as described herein, wherein the method comprises the steps of:

(i) dissolving flufenacet in a non-aqueous carrier to form a solution;

(ii) (ii) adding a sulfonamide herbicide to the solution of step (i) to form a suspension; and

(iii) the suspension is ground to obtain a stable formulation.

Detailed Description

Definition of

Before setting forth the subject matter in detail, it may be helpful to provide definitions of certain terms used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter belongs. For clarity, the following definitions are provided.

The terms "a" or "an," as used herein, include both the singular and the plural, unless expressly specified otherwise. Thus, the terms "a", "an" or "at least one" may be used interchangeably in this application.

As used herein, the term "about" when used in conjunction with a numerical value includes ± 10% of the indicated value. Further, all ranges herein directed to the same component or property are inclusive of the endpoints, independently combinable, and inclusive of all intermediate points and ranges. It is to be understood that where a range of parameters is provided, the invention also provides all integers and deciles thereof within that range. For example, "0.1-80%" includes 0.1%, 0.2%, 0.3%, etc., up to 80%.

As used herein, the term "pesticide" broadly refers to an agent that can be used to control and/or kill pests. The term is understood to include, but is not limited to, fungicides, insecticides, nematicides, herbicides, miticides, parasiticides or other control agents. For chemical classifications and applications, as well as The specific compounds of each class, see "The Pesticide Manual, 13 th edition" (British Crop Protection Council, Hampshire, UK, 2003) and "The e-Pesticide Manual, 3 rd edition" (British Crop Protection Council, Hampshire, UK, 2003-04), The contents of each of which are incorporated herein by reference in their entirety.

As used herein, the term "weed" includes any undesirable vegetation.

As used herein, the term "plant" or "crop" includes reference to a whole plant, plant organ (e.g., leaf, stem, twigs, root, trunk, branch, shoot, fruit, etc.), plant cell, or plant seed. The term also includes plant crops such as fruits. In yet another embodiment, the term "plant" may include propagation material thereof, which may include all reproductive parts of plants (such as seeds) and vegetative plant material (such as cuttings and tubers), useful for the propagation of plants. This includes seeds, tubers, spores, bulbs, rhizomes, shoots (sprouts basal shoots), stolons and shoots and other parts of the plant, including seedlings and young plants to be transplanted after germination or after emergence from the soil.

As used herein, the term "locus" includes not only areas where pests (including weeds) may already be growing, but also areas where pests (including weeds) have not yet emerged, as well as areas of cultivation.

As used herein, the term "mixture" or "combination" refers to (but is not limited to) any physical form of combination, such as a mixture, solution, alloy, and the like.

As used herein, the term "effective amount" refers to an amount of a compound that is sufficient to achieve a good level of control when ingested, contacted, or detected.

As used herein, the phrase "agrochemically acceptable carrier" means a carrier known in the art and accepted for use in forming formulations for agricultural or horticultural use.

As used herein, the term "adjuvant" is broadly defined as any substance that is not an active ingredient by itself but that enhances or intends to enhance the effectiveness of the active ingredient with which it is used. Adjuvants are understood to include spreading agents, penetrants, compatibilizing agents and anti-drift agents (drift retardants).

As used herein, the term "additive" is defined as any substance that is not an active ingredient but is added to the formulation, such as stickers, surfactants, synergists, buffers, acidulants, defoamers, and thickeners.

As used herein, an "ultra-low naphthalene solvent" is a solvent having a naphthalene concentration of less than 0.1 wt.%.

As used herein, a "low naphthalene solvent" is a solvent having a naphthalene concentration of less than 1 weight percent.

As used herein, the term "stable" when used in conjunction with a formulation means that no significant decomposition of the active ingredient in the formulation is observed after storage for at least 7 days at a temperature of at least 20 ℃. For example, after storage at a temperature of at least 20 ℃ for at least 7 days, no significant amount of the flufenacet N-isomer is formed.

U.S. patent No. 6,479,432 discloses a liquid suspension formulation comprising one or more herbicidally active compounds selected from the group of sulfonylureas in suspended form and one or more active compounds partially or completely dissolved in the formulation. However, due to the unique chemistry of flufenacet, the preparation of formulations using sulfonylureas and flufenacet as taught in U.S. patent No. 6,479,432 will not result in stable formulations as defined above.

As used herein, the term "tank mix" means mixing two or more chemical pesticides or formulations in a spray can at the time of spray application.

As used herein, the term "safener" refers to an agent that increases the tolerance of a plant to herbicides without significantly affecting the effectiveness of the active ingredient.

As used herein, the term "thickener" refers to an agent that increases the viscosity of a liquid formulation without substantially changing other properties of the formulation.

As used herein, the term "non-aqueous" when used to describe an agrochemically acceptable carrier or formulation means that the agrochemically acceptable carrier or formulation is substantially free of water.

Water vapor is one of the most abundant atmospheric gases. Some compounds and formulations readily absorb moisture when they are exposed to moisture in the atmosphere. The amount and rate of absorption depends on a variety of factors such as the hygroscopicity of the compound or formulation, atmospheric conditions (e.g., humidity), and exposure time. Some compounds and formulations also tend to absorb moisture from other ingredients/components in the formulation. Thus, the agrochemically acceptable carriers and formulations of the present invention may contain small amounts of water, but they should be considered "non-aqueous" as long as water is not positively added to the agrochemically acceptable carrier or formulation.

The amount of water absorbed into the compound or formulation can be determined using a number of techniques, including Karl Fischer titration.

Non-aqueous liquid formulation

Agrochemical Oil Dispersions (ODs) are stable suspensions of agrochemical active ingredients, such as pesticides and crop protection chemicals, in non-aqueous fluids, which may contain other dissolved active ingredients. Oil dispersions are particularly useful for formulating organic, insoluble and solid active ingredients.

Oil dispersion formulations are concentrated non-aqueous liquid formulations which are diluted with water prior to use to prepare aqueous compositions for use in crop protection. To be dispersible in water, such formulations contain emulsifiers, dispersants and other formulation components such as thickeners, defoamers and solid carriers. Oil dispersions are usually chosen if the active ingredient is sensitive to water or if an oil is required as an adjuvant to improve the biological properties of the pesticide. Oil dispersions are generally free of water. This is to prevent degradation of the active ingredient and/or phase separation of the formulation.

Oil dispersion formulations offer certain advantages to farmers. Active ingredients which are normally unstable in water can now be formulated in solid suspension form. Oil-based adjuvants may also be combined with these types of formulations to enhance efficacy. In addition, suspending the active ingredient in a non-aqueous liquid carrier can result in a formulation with a higher concentration of active ingredient than would otherwise be possible. This is because the amount of active ingredient that can be added to the formulation has a solubility limit.

Furthermore, the non-aqueous liquid formulation may include an adjuvant and/or a safener therein as opposed to adding the adjuvant and/or safener to the spray can. This further benefits the farmer in logistics, packaging and storage as a single product can be used rather than two or more.

The non-aqueous liquid formulations of the present invention comprising flufenacet and at least one sulfonylurea herbicide were found to be stable and to not form breakdown products of flufenacet when the formulations were stored under different conditions and for different periods of time. Furthermore, the main advantage of this formulation is that it enables the suspension of at least one sulfonylurea herbicide in a non-aqueous liquid carrier and the dissolution of flufenacet without loss of stability of the formulation. This enables the combination of active ingredients with different physicochemical properties, which are usually formulated into separate formulations, such as Emulsifiable Concentrate (EC) formulations, Suspension Concentrate (SC) and water dispersible granule (WG) formulations, into a single formulation.

a) an amount of flufenacet;

b) an amount of at least one sulfonylurea herbicide; and

c) an agrochemically acceptable non-aqueous liquid carrier,

In some embodiments, the sulfonylurea herbicide is azimsulfuron (azimutulfuron), flazasulfuron (flazasulfuron), thifensulfuron-methyl (thifensulfuron), flucetosulfuron (flucetosulfuron), mesosulfuron (mesosulfuron), or nicosulfuron (nicosulfuron). In some embodiments, the sulfonylurea herbicide is mesosulfuron.

The non-aqueous liquid carrier refers to, but is not limited to, esters, amides, aromatic hydrocarbons, paraffins, petroleum, vegetable oils, alkyl esters of vegetable oils, alkyl phosphate esters, diesel, mineral oils, fatty acid amides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids, modified vegetable oils, and any combination thereof.

In some embodiments, the non-aqueous liquid carrier is selected from the group consisting of: esters, amides, aromatic hydrocarbons, paraffins, petroleum oils, vegetable oils, alkyl esters of vegetable oils, alkyl phosphate esters, diesel oil, mineral oil, fatty acid amides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids, modified vegetable oils, and any combination thereof.

In some embodiments, the non-aqueous liquid carrier is selected from the group consisting of aromatic hydrocarbons, paraffins, petroleum, diesel, mineral oil, fatty acids, tall oil fatty acids, and any combination thereof.

In some embodiments, the non-aqueous liquid carrier is an aromatic hydrocarbon. In some embodiments, the non-aqueous liquid carrier is a combination of an aromatic hydrocarbon and one or more additional non-aqueous liquid carriers.

In some embodiments, the aromatic hydrocarbon is selected from the group consisting of toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, cumene, tert-butyl benzene, naphthalene, and mono-or poly-alkyl substituted naphthalene.

In some embodiments, the aromatic hydrocarbon is a C10 aromatic hydrocarbon. In some embodiments, the aromatic hydrocarbon is a C12 aromatic hydrocarbon. In some embodiments, the aromatic hydrocarbon is an ultra low naphthalene solvent (ULN). In some embodiments, the aromatic hydrocarbon is a low naphthalene solvent (LN).

In some embodiments, the arene is Solvesso from ExxonMobil Chemical^TMStage, in particular Solvesso^TM100(CAS number 64742-95-6), Solvesso^TM150(CAS number 64742-94-5) and Solvesso^TM200(CAS number 64742-94-5). In some embodiments, the aromatic hydrocarbon is Caromax^TM28LN (sold by Petrochem Carless).

In some embodiments, the non-aqueous liquid carrier is a paraffin. In some embodiments, the alkane is selected from the group consisting of octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and branched chain isomers thereof.

In some embodiments, the alkyl ester of a fatty acid is a methyl ester of a fatty acid. In some embodiments, the methyl ester of a fatty acid is methyl octanoate/decanoate. In some embodiments, the methyl octanoate/decanoate is Stepan^TMC-25 (sold by Stepan Company). In some embodiments, the non-aqueous liquid carrier is a vegetable oil. In some embodiments, the vegetable oil is selected from the group consisting of olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, and tall oil.

In some embodiments, the non-aqueous liquid carrier is an alkyl ester of a vegetable oil. In some embodiments, the alkyl ester of the vegetable oil is selected from the group consisting of rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl ester, rapeseed oil butyl ester, and tall oil fatty acid ester.

In some embodiments, the non-aqueous liquid carrier is a fatty acid amide. In some embodiments, the fatty acid amide is selected from the group consisting of and C₆-C₁₈C of carboxylic acids₁-C₃Amines, alkylamines and alkanolamines.

In some embodiments, the non-aqueous liquid carrier is an alkyl ester of a fatty acid. In some embodiments, the alkyl esters of fatty acids are selected from C₈To C₂₂C of fatty acid₁-C₄Monohydric alcohol esters, such as methyl oleate and ethyl oleate.

In some embodiments, the non-aqueous liquid carrier is substantially free of water. In some embodiments, the non-aqueous liquid carrier comprises water in an amount less than or equal to 1.5 wt.%, or 1 wt.%, or 0.7 wt.%, or 0.5 wt.%, or 0.2 wt.%, or 0.1 wt.%. In some embodiments, the non-aqueous liquid carrier comprises 0.16 wt.% water. In some embodiments, the non-aqueous liquid carrier is free of water.

In some embodiments, the non-aqueous liquid formulation is substantially free of water. In some embodiments, the non-aqueous liquid formulation comprises water in an amount less than or equal to 1.5% or 1% or 0.7% or 0.5% or 0.2% or 0.1% by weight. In some embodiments, the non-aqueous liquid formulation comprises 0.16% by weight water. In some embodiments, the non-aqueous liquid carrier is free of water.

In some embodiments, the amount of water in the non-aqueous liquid carrier is measured by Karl Fischer titration. In some embodiments, the amount of water in the non-aqueous liquid formulation is measured by Karl Fischer titration.

In some embodiments, the non-aqueous liquid carrier is devoid of basic properties.

In some embodiments, the non-aqueous liquid carrier is not a vegetable oil. In some embodiments, the non-aqueous liquid carrier is not rapeseed oil. In some embodiments, the non-aqueous liquid carrier is not rapeseed oil methyl ester.

In some embodiments, the non-aqueous liquid carrier is not a dimethylamide of a fatty acid. In some embodiments, the non-aqueous carrier is not a methyl ester of a fatty acid. In some embodiments, the non-aqueous carrier is not a morpholine amide of a fatty acid.

In some embodiments, the non-aqueous liquid carrier is not N-octyl-2-pyrrolidone.

In some embodiments, the amount of flufenacet is from 0.1 to 80% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is from 0.1 to 70% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 1 to 60% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is from 5 to 50% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 1 to 15% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 10 to 20% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 13% by weight, based on the total weight of the stable formulation.

In some embodiments, the concentration of flufenacet in the stable formulation is between 50 and 500 g/L. In some embodiments, the concentration of flufenacet in the stable formulation is between 50 and 300 g/L. In some embodiments, the concentration of flufenacet in the stable formulation is between 100 and 200 g/L. In some embodiments, the concentration of flufenacet in the stable formulation is between 100 and 150 g/L. In some embodiments, the concentration of flufenacet in the stable formulation is about 128 g/L.

In some embodiments, the amount of sulfonylurea herbicide is 0.1 to 80 weight percent, based on the total weight of the stable formulation. In some embodiments, the amount of sulfonylurea herbicide is from 0.1 to 70 weight percent, based on the total weight of the stable formulation. In some embodiments, the amount of sulfonylurea herbicide is from 0.1 to 60 weight percent, based on the total weight of the stable formulation. In some embodiments, the amount of sulfonylurea herbicide is 0.1 to 40 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of sulfonylurea herbicide is 0.1 to 25 weight percent, based on the total weight of the stable formulation. In some embodiments, the amount of sulfonylurea herbicide is 0.1 to 1 weight percent, based on the total weight of the stable formulation. In a specific embodiment, the amount of sulfonylurea herbicide is 0.5% by weight, based on the total weight of the stable formulation.

In some embodiments, the concentration of sulfonylurea in the stable formulation is between 1 and 50 g/L. In some embodiments, the concentration of sulfonylurea in the stable formulation is between 1 and 25 g/L. In some embodiments, the concentration of sulfonylurea in the stable formulation is between 1 and 10 g/L. In some embodiments, the concentration of sulfonylurea in the stable formulation is about 5 g/L.

In some embodiments, the amount of flufenacet and at least one sulfonylurea herbicide ranges from 0.1 to 90% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet and at least one sulfonylurea herbicide ranges from 0.5 to 30% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet and at least one sulfonylurea herbicide ranges from 1 to 15% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet and at least one sulfonylurea herbicide ranges from 1 to 10% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet and at least one sulfonylurea herbicide ranges from 3 to 8% by weight, based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet and at least one sulfonylurea herbicide is about 15% by weight, based on the total weight of the stable formulation.

In some embodiments, the concentration of flufenacet and sulfonylurea in the stable formulation is between 50 and 500 g/L. In some embodiments, the concentration of flufenacet and sulfonylurea in the stable formulation is between 50 and 300 g/L. In some embodiments, the concentration of flufenacet and sulfonylurea in the stable formulation is between 100 and 200 g/L. In some embodiments, the concentration of flufenacet and sulfonylurea in the stable formulation is between 100 and 150 g/L. In some embodiments, the concentration of flufenacet and sulfonylurea in the stable formulation is about 132 g/L.

In some embodiments, the amount of non-aqueous liquid carrier is 10 to 90 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of non-aqueous liquid carrier is 40 to 90 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of non-aqueous liquid carrier is 50 to 80 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of non-aqueous liquid carrier is 60 to 80 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of non-aqueous liquid carrier is 70 to 80 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of non-aqueous liquid carrier is 75 to 80 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of non-aqueous liquid carrier is 77% by weight based on the total weight of the stable formulation.

In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 300-900 g/L. In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 400-700 g/L. In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 500-600 g/L. In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 575-600 g/L.

In some embodiments, the formulation comprises at least one surfactant.

Surfactants may include, but are not limited to: alkyl-terminated ethoxylated glycols, alkyl-terminated alkyl block alkoxylated glycols, dialkyl sulfosuccinates, phosphate esters, alkyl sulfonates, alkylaryl sulfonates, tristyrylphenol alkoxylates, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohol alkoxylates, alkoxylated alcohols (such as n-butyl polyglycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), or combinations thereof.

In a preferred embodiment, the surfactant is an alkyl-terminated alkoxylate. In some embodiments, the adjuvant is a methyl-terminated ethoxylate. In some embodiments, the adjuvant is a methyl-terminated tridecyl ethoxylate. In some embodiments, the adjuvant is a methyl-terminated tridecyl ethoxylate having 6 ethylene oxide units.

In some embodiments, the surfactant is

XM-60。

XM-60(CAS number 345642-79-7, sold by Clariant) is based on

Methyl-capped ethoxylates of X060(CAS number 9043-30-5, sold by Clariant).

In a preferred embodiment, the surfactant is selected from the group consisting of synthetic capped alcohol alkoxylates and alkyl aryl sulfonates.

In some embodiments, the surfactant is calcium dodecylbenzenesulfonate. In some embodiments, the surfactant is

EVM 70/2E (sold by Huntsman International LLC).

In some embodiments, the surfactant is not isotridecyl alcohol polyglycol ether (6 EO). In some embodiments, the surfactant is not isotridecyl alcohol polyglycol ether (8 EO). In some embodiments, the surfactant is not

X060. In some embodiments, the surfactant is not

X080 (CAS9043-30-5, sold by Clariant). In some embodiments, the surfactant is not an anionic sulfosuccinate. In some embodiments, the surfactant is not dioctyl sulfosuccinate. In some embodiments, the surfactant is not sodium 1, 4-bis (2-ethylhexyl) sulfosuccinate. In some embodiments, the surfactant is not TRITON^TMGR-7ME (CAS number 577-11-7, sold by The Dow Chemical Company) or TRITON^TMGR-7M (CAS number 577-11-7, sold by The Dow Chemical Company). In some embodiments, the surfactant is not a mixture of fatty acid polyglycol esters. In some embodiments, the surfactant is not

VO/2003(CAS number 220037-02-5, sold by Rhodia Operations, a member of the SOLVAY group).

In some embodiments, the surfactant is present in the stable formulation in an amount between 0.1 to 40 weight percent, based on the total weight of the stable formulation. In some embodiments, the surfactant is present in the stable formulation in an amount between 0.1 to 35 weight percent, based on the total weight of the stable formulation. In some embodiments, the surfactant is present in the stable formulation in an amount between 0.1 to 30 weight percent, based on the total weight of the stable formulation. In some embodiments, the surfactant is present in the stable formulation in an amount between 1-20% by weight, based on the total weight of the stable formulation. In some embodiments, the surfactant is present in the stable formulation in an amount between 5-10% by weight, based on the total weight of the stable formulation. In some embodiments, the surfactant is present in the stable formulation in an amount of about 17% by weight, based on the total weight of the formulation.

In some embodiments, the formulation further comprises at least one adjuvant.

In some embodiments, the adjuvant is selected from the group consisting of alkyl ethoxylated glycols, alkyl block alkoxylated glycols, alkyl capped ethoxylated glycols, alkyl capped alkyl block alkoxylated glycols, dialkyl sulfosuccinates, ethoxylated alcohols, phosphate esters, ethoxylated tristyrylphenol phosphate esters, sorbitan esters, Tween esters, and combinations thereof.

In this regard, when an alkyl capped ethoxylated glycol nonionic surfactant, an alkyl capped alkyl block alkoxylated glycol, is used as an emulsifier, it may also act as an adjuvant.

In some embodiments, the adjuvants are added to the formulation simultaneously or separately as a tank mix.

In some embodiments, the adjuvant is present in an amount of at least 0.1% by weight, based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 5% by weight, based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 10 weight percent, based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 15% by weight, based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 20% by weight, based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 30% by weight, based on the total weight of the stable formulation.

In some embodiments, the formulation further includes additional physical stabilizers such as buffers, acidifying agents, antifoaming agents, thickeners, and anti-drift agents.

Thickeners useful herein are silica, organically modified bentonite of silica, inorganic clays, and any combination thereof.

The silica may be fumed silica and precipitated silica, and any combination thereof.

The fumed silica and precipitated silica can be hydrophobic silica and hydrophilic silica and any combination thereof.

Examples of fumed silicas that can be included in the formulations of the present invention are, but are not limited to:

A200、

R 202、

r972 and

r805 (both sold by Evonik).

Examples of precipitated silicas that may be included in the formulations of the present invention are, but are not limited to:

22S (sold by Evonik),

D17 (sold by Evonik) and

38 (sold by rhodia operations, members of Solvay group).

An example of an organically modified bentonite that can be used in the formulations of the present invention is

SD-1 (sold by Elementis Specialties). An example of an inorganic clay that may be used in the formulations of the present invention is

40 (sold by BASF).

Other examples of adjuvants that may be used in the formulations of the present invention include stickers, spreaders, synergists, penetrants, compatibilizers, buffers, acidifying agents, antifoaming agents, and anti-drift agents.

In some embodiments, the stable formulation further comprises a safener.

In some embodiments, the safener is selected from mefenpyr diethyl, cloquintocet mexyl, fenchlorazole, benoxacor, dichlormid, isoxadifen ethyl, and any combination thereof. In a preferred embodiment, the safener is mefenpyr-diethyl.

In some embodiments, the safener is added to the formulation simultaneously or separately as a tank mix.

In some embodiments, the amount of safener in the stable formulation is 0.1 to 80 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of safener in the stable formulation is 1 to 50 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of safener in the stable formulation is 1 to 25 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of safener in the stable formulation is 1 to 15 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of safener in the stable formulation is 1 to 10 weight percent based on the total weight of the stable formulation. In some embodiments, the amount of safener in the stable formulation is 1 to 5 weight percent based on the total weight of the stable formulation.

Other ingredients such as adhesives, neutralizing agents, binders, chelating agents (sequestrates), biocides, stabilizers, buffers, preservatives, antioxidants or anti-freeze agents may also be added to the compositions of the present invention to increase the stability, density and viscosity of the composition.

In some embodiments, the stable formulation is an oil formulation. In some embodiments, the stable formulation is an oil-dispersible formulation.

In one embodiment, a stable formulation comprises:

a) 1.0-15% by weight of flufenacet;

b) 0.1-25% by weight of at least one sulfonylurea herbicide;

c) 10-90% by weight of a non-aqueous liquid carrier; and

d) optionally 0.1-30 wt% of safeners and/or adjuvants.

In some embodiments, the formulation is stable after 7 days of storage. In some embodiments, the formulation is stable after 10 days of storage. In some embodiments, the formulation is stable after 14 days of storage.

In some embodiments, the formulation is stored at a temperature of 20 to 55 ℃. In some embodiments, the formulation is stored at a temperature of 40 to 55 ℃. In some embodiments, the formulation is stored at a temperature of 50 to 55 ℃. In some embodiments, the formulation is stored at a temperature of 54 ℃.

In some embodiments, the formulation is stable after 14 days of storage at a temperature of 54 ℃.

In some embodiments, the formulation comprises less than 5% flufenacet N-isomer. In some embodiments, the formulation comprises less than 2% flufenacet N-isomer. In some embodiments, the formulation comprises less than 1% flufenacet N-isomer. In some embodiments, the formulation comprises less than 0.5% flufenacet N-isomer. In some embodiments, the formulation comprises less than 0.1% flufenacet N-isomer. In some embodiments, the formulation comprises an undetectable amount of flufenacet N-isomer. In some embodiments, the formulation is free of flufenacet N-isomer.

In addition, the agricultural compositions herein may be used in combination with one or more other pesticides to control a wider variety of undesirable pests. When used in combination with other pesticides, the compositions described herein may be formulated with the other pesticide, tank-mixed with the other pesticide, or applied sequentially with the other pesticide. In addition, the compositions described herein may optionally be combined or mixed with other pesticidal compositions. The mixtures with other pesticidal compositions are useful for controlling pests in crop and non-crop environments.

Methods of use of the formulations described herein

The formulations described herein are suitable for use in controlling weeds.

The present invention also provides a method for controlling weeds, comprising: the stable herbicidal non-aqueous liquid formulation described herein is applied to weeds, a portion of a weed, an area adjacent to a weed, or soil and/or seeds of a weed to control the weed.

The present invention also provides a method of controlling weeds, comprising:

b) applying the stable herbicidal non-aqueous liquid formulation to weeds, a portion of a weed, an area adjacent to a weed, or soil and/or seeds of a weed, thereby controlling the weed.

The method comprises the following steps: the stable herbicidal non-aqueous liquid formulation is added to a carrier (e.g., water) and the resulting solution containing the herbicidal organic formulation is used for spray application to control weeds in plants or plant propagation material thereof in a crop environment or a non-crop environment. By diluting the stable herbicidal non-aqueous liquid formulation in water (i.e., positively adding water to the formulation), a suspoemulsion can be formed.

An effective application rate of the herbicidal composition cannot generally be defined because it varies depending on various conditions such as the type of weeds, weather conditions, the nature of the soil, and the kind of crop.

In one embodiment, the stable herbicidal nonaqueous liquid formulation is typically applied at a rate of about 1 to about 5L/ha. In a preferred embodiment, the stable herbicidal nonaqueous liquid formulation is applied at a rate of about 2 to 3L/ha. In a specific embodiment, the stable herbicidal nonaqueous liquid formulation is applied at a rate of about 2L/ha. In another specific embodiment, the stable herbicidal nonaqueous liquid formulation is applied at a rate of about 3L/ha. In another specific embodiment, the stable herbicidal nonaqueous liquid formulation is applied at a rate of about 2.5L/ha.

In one embodiment, the stable herbicidal nonaqueous liquid formulation may be diluted in a carrier such as water in an amount of about 1 to 100L of the stable formulation per 1000L of water. In another embodiment, the stable herbicidal nonaqueous liquid formulation can be diluted in a carrier such as water in an amount of about 1 to 30L of the stable formulation per 1000L of water. In yet another embodiment, the stable herbicidal nonaqueous liquid formulation can be diluted in a carrier such as water in an amount of about 5 to 15L of stable formulation per 1000L of water.

In some embodiments, crop plants may include, but are not limited to: cereals, soybeans, corn, rice, papaya, melon, cocoa, and coffee.

Cereals may include, but are not limited to: wheat, barley, rye and oats.

In another embodiment, weeds may include, but are not limited to, grasses such as precocious grasses (Poa), toxifolium (lilium), and broadleaf weeds.

The stable herbicidal nonaqueous liquid formulations described herein can be mixed with water and/or fertilizer and applied to the desired locus by any means, such as an aircraft spray tank, backpack spray tank, livestock dipping vat (cattledipping vat), farm equipment for ground spraying (e.g., a boom sprayer, a hand sprayer), and the like. The desired location may be soil, plants, etc.

The stable herbicidal nonaqueous liquid formulations of the present invention may include additional crop protection agents such as insecticides, herbicides, fungicides, bactericides, nematicides, molluscicides, growth regulators, biological agents, fertilizers or mixtures thereof. When used in combination with additional crop protection agents, the compositions may be formulated with these adjuvants, tank-mixed with these adjuvants or applied sequentially with these adjuvants.

Method for preparing formulations described herein

The present invention provides a process for the preparation of a stable herbicidal non-aqueous liquid formulation comprising an effective amount of flufenacet and an effective amount of at least one sulfonylurea herbicide, wherein the process comprises the steps of:

(i) dissolving flufenacet in a non-aqueous carrier to form a solution;

(ii) (ii) adding a sulfonylurea herbicide to the solution of step (i) to form a suspension; and

(iii) the suspension is ground to obtain a stable formulation.

In some embodiments, a non-aqueous carrier is added during step (ii).

In some embodiments, the method further comprises the steps of: (iii) adding at least one surfactant and/or adjuvant to the solution of step (i) prior to performing step (ii). In some embodiments, the method further comprises the steps of: (iv) adding at least one surfactant and/or adjuvant to the solution of step (ii) prior to performing step (iii).

In some embodiments, the method further comprises the step of adding a safener to the solution of step (i) prior to performing step (ii). In some embodiments, the safener is mefenpyr-diethyl.

In some embodiments, the method further comprises the step of adding at least one surfactant to the solution of step (i) prior to performing step (ii). In some embodiments, the surfactant is calcium dodecylbenzenesulfonate and/or a methyl-terminated ethoxylate.

In some embodiments, the method further comprises the step of adding a thickening agent to the suspension of step (ii) prior to performing step (iii). In some embodiments, the thickening agent is fumed silica.

In some embodiments, the non-aqueous liquid carrier is heated to completely dissolve the flufenacet and/or the additive. Additives may include, but are not limited to, safeners and adjuvants.

In some embodiments, step (i) is performed at a temperature of 15 ℃ to 65 ℃. In some embodiments, step (i) is performed at a temperature of about 20 ℃, 30 ℃, 40 ℃, 50 ℃, or 60 ℃.

In some embodiments, the suspension is milled until 90% of the particles have a particle size of about 1-10 μ. In some embodiments, the suspension is milled until 90% of the particles have a particle size of less than 8 μ.

With respect to the foregoing embodiments, the embodiments disclosed herein are deemed to be applicable to the other disclosed embodiments. Furthermore, elements recited in formulation embodiments may be used in the method embodiments and use embodiments described herein, and vice versa.

The present invention will be better understood by reference to the experimental section that follows, but it will be readily understood by those skilled in the art that the specific experiments detailed are merely illustrative of the invention as more fully described hereinafter in the claims that follow.

Experimental part

Combining sulfonylurea herbicides and flufenacet into one formulation is particularly challenging because sulfonylurea herbicides and flufenacet are generally stable under different conditions. In addition, flufenacet is highly sensitive and rapidly decomposes under a variety of conditions.

In particular, sulfonylurea herbicides are stable at pH values greater than 7 and hydrolyze rapidly in aqueous and/or acidic environments. Flufenacet, on the other hand, is stable under acidic conditions. Under neutral or alkaline conditions, flufenacet decomposes, with one of the decomposition products being the less active and/or more toxic N-isomer.

Attempts to combine sulfonylurea herbicides (e.g. mesosulfuron) and flufenacet into one formulation have failed several times.

In aqueous based suspension concentrate or suspoemulsion formulations, the mesosulfuron is decomposed by the presence of water.

In water dispersible granule formulations, there is always decomposition of one active ingredient, depending on the pH of the formulation (after dilution in water). Specifically, flufenacet decomposes during accelerated storage at pH >7(pH 8), while mesosulfuron decomposes during accelerated storage at pH <7(pH 4).

In oil dispersion formulations in vegetable oils, in which both active ingredients are in a dispersed state, flufenacet granules crystallize.

In oil dispersion formulations, in which the mesosulfuron-methyl is dispersed in a solvent and the flufenacet is dissolved in a solvent, the stability of the formulation depends on the solvent and surfactant used. In fact, approximately 20 different experiments were attempted using different surfactants and solvents to obtain stable formulations as described in the examples below.

Example 1

Oil Dispersion (OD) formulation 5/125/15 of mesosulfuron-methyl, flufenacet and mefenpyr-diethyl

Flufenacet Tech (128g) (supplied by Jiangsu Luye (China)) and mefenpyr-diethyl (16g) were dissolved in 795.3g Caromax^TM28 LN. The mixture was then heated to 50 to enhance dissolution. When all the substances are dissolved, adding

EVM 70/2E (6.2g) and

XM-60(56.1g), and mix until homogeneous. When uniform, 5.3g of Mesosulfuron Tech and 31.1g of fumed silica were added and dispersed uniformly in the solution. The dispersion was milled in a bead mill to a particle size D (90%) of less than 8 μ.

The oil dispersion formulations of flufenacet 125, mesosulfuron 5, mefenpyr-diethyl 15 were subjected to an accelerated storage stability test, carried out at 54 ℃ for 14 days. All active ingredients were found to be stable. No decomposition products (such as the N-isomer) of flufenacet were found after accelerated storage.

The stable herbicidal nonaqueous liquid formulations exemplified above have significant advantages over mixtures and formulations known in the art. The formulation is physically stable and easy to use in the field.

To evaluate the effectiveness of the formulations of the present invention when used with crops, the formulations were applied to wheat and the results showed that the herbicidal nonaqueous liquid formulations performed at least as effectively as the mixtures and formulations known in the art.

While the invention has been shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various substitutions, modifications and changes may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims.

All publications, patents and patent applications mentioned in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated herein by reference.

Claims

1. A stable herbicidal non-aqueous liquid formulation comprising:

a) an amount of flufenacet;

b) an amount of at least one sulfonylurea herbicide; and

c) an agrochemically acceptable non-aqueous liquid carrier,

2. The stable formulation of claim 1, wherein the sulfonylurea herbicide is selected from the group consisting of azimsulfuron, flazasulfuron, thifensulfuron-methyl, flucetosulfuron, mesosulfuron-methyl, and nicosulfuron.

3. The stable formulation of claim 1 or 2, wherein the sulfonylurea herbicide is mesosulfuron-methyl.

4. The stable formulation of any one of claims 1-3, wherein the non-aqueous liquid carrier is selected from the group consisting of aromatic hydrocarbons, paraffins, petroleum, diesel, mineral oil, fatty acid amides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids, modified vegetable oils, and any combination thereof.

5. The stable formulation of claim 4, wherein the non-aqueous carrier is selected from the group consisting of aromatic hydrocarbons, paraffins, petroleum, diesel, mineral oil, fatty acids, tall oil fatty acids, and any combination thereof.

6. The stable formulation of any one of claims 1-5, wherein the non-aqueous liquid carrier is an aromatic hydrocarbon.

7. The stable formulation of claim 6, wherein the aromatic hydrocarbon is selected from the group consisting of toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, cumene, tert-butyl benzene, naphthalene, mono-or poly-alkyl substituted naphthalene, C10 aromatic hydrocarbon, and C12 aromatic hydrocarbon.

8. The stable formulation of any one of claims 1-7, wherein the non-aqueous liquid carrier is a low naphthalene solvent.

9. The stable formulation of any one of claims 1-8, wherein the non-aqueous liquid carrier is an ultra-low naphthalene solvent.

10. The stable formulation of any one of claims 1-9, wherein the flufenacet is in an amount of 0.1 to 80% by weight, based on the total weight of the stable formulation.

11. The stable formulation of any one of claims 1-10, wherein the amount of flufenacet is 10-20% by weight, based on the total weight of the stable formulation.

12. The stable formulation of any one of claims 1-11, wherein the amount of sulfonylurea herbicide is 0.1 to 80 weight percent, based on the total weight of the stable formulation.

13. The stable formulation of any one of claims 1-12, wherein the amount of sulfonylurea herbicide is 0.1 to 25 weight percent, based on the total weight of the stable formulation.

14. The stable formulation of any one of claims 1-13, wherein the amount of sulfonylurea herbicide is 0.1 to 1 weight percent, based on the total weight of the stable formulation.

15. The stable formulation of any one of claims 1 to 14, wherein the amount of the non-aqueous liquid carrier is 10 to 90 weight percent based on the total weight of the stable formulation.

16. The stable formulation of any one of claims 1 to 15, wherein the amount of the non-aqueous liquid carrier is 70 to 80 weight percent based on the total weight of the stable formulation.

17. The stable formulation of any one of claims 1-16, further comprising at least one adjuvant.

18. The stable formulation of claim 17, wherein the adjuvant is added to the formulation as a tank mix.

19. The stable formulation of claim 17 or 18, wherein the adjuvant is present in an amount of at least 0.1% by weight, based on the total weight of the stable formulation.

20. The stable formulation of any one of claims 17-19, wherein the adjuvant is a surfactant selected from the group consisting of: an alkyl terminated ethoxylated glycol, an alkyl terminated alkyl block alkoxylated glycol, a dialkyl sulfosuccinate, a phosphate ester, an alkyl sulfonate, an alkyl aryl sulfonate, a tristyrylphenol alkoxylate, a natural or synthetic fatty acid alkoxylate, a natural or synthetic fatty alcohol alkoxylate, an alkoxylated alcohol, a block copolymer, or any combination thereof.

21. The stable formulation of claim 20, wherein the surfactant is an alkyl-terminated alkoxylate or the adjuvant is a dialkyl-terminated polyalkoxy glycol.

22. The stable formulation of claim 21, wherein the alkyl-terminated alkoxylate is a methyl-terminated tridecyl ethoxylate having 6 ethylene oxide units.

23. The stable formulation of claim 20, wherein the surfactant is selected from the group consisting of synthetic alcohol alkoxylates and alkyl aryl sulfonates.

24. The stable formulation of claim 23, wherein the surfactant is calcium dodecylbenzenesulfonate.

25. The stable formulation of any one of claims 20 to 24, wherein the surfactant is present in the stable formulation in an amount between 0.1 to 40 weight percent, based on the total weight of the stable formulation.

26. The stable formulation of any one of claims 20-25, wherein the surfactant is present in the stable formulation in an amount between 5-10% by weight, based on the total weight of the formulation.

27. The stable formulation of any one of claims 17-26, wherein at least one adjuvant is a thickening agent.

28. The stable formulation of claim 27, wherein the thickener is selected from the group consisting of fumed silica, precipitated silica, organically modified bentonite, inorganic clay, and any combination thereof.

29. The stable formulation of claim 28, wherein the thickener is fumed silica.

30. The stable formulation of any one of claims 1-29, further comprising a safener.

31. The stable formulation of claim 30, wherein the safener is selected from the group consisting of mefenpyr-diethyl, clethodim, dichlormid, isoxadifen-ethyl and any combination thereof.

32. The stable formulation of claim 31, wherein the safener is mefenpyr-diethyl.

33. The stable formulation of any one of claims 30-32, wherein the safener is added to the formulation as a tank mix.

34. The stable formulation of any of claims 30 to 33, wherein the amount of the safener in the stable formulation is from 0.1 to 80 weight percent, based on the total weight of the stable formulation.

35. The stable formulation of any of claims 30-34, wherein the amount of the safener in the stable formulation is 1-5% by weight based on the total weight of the stable formulation.

36. The stable formulation of any one of claims 1-35, wherein the formulation comprises:

a) 0.1-25% by weight of at least one sulfonylurea herbicide;

b) 1.0-15% by weight of flufenacet;

c) 10-90% by weight of a non-aqueous liquid carrier; and

d) optionally 0.1-30 wt% of safeners and/or adjuvants.

37. The stable formulation of any one of claims 1-36, wherein the stable formulation is an oil-dispersible formulation.

38. The stable formulation of any one of claims 1-37, wherein the formulation is stable after 14 days of storage at a temperature of 54 ℃.

39. The stable formulation of any one of claims 1-38, wherein the formulation comprises less than 5% flufenacet N-isomer.

40. The stable formulation of any one of claims 1-39, wherein the non-aqueous liquid carrier comprises equal to or less than 1.5% water by weight.

41. The stable formulation of any one of claims 1-40, wherein the stable formulation comprises equal to or less than 1.5 wt% water.

42. A herbicidal suspoemulsion formulation comprising the stable formulation of any one of claims 1-41.

43. A method of controlling weeds, comprising: applying the formulation of any one of claims 1-42 to weeds, to a portion of a weed, to an area adjacent to a weed, or to soil and/or seeds of a weed, thereby controlling the weed.

44. A method of controlling weeds, comprising:

45. The method of claim 43 or 44, wherein the formulation is applied at a rate of about 1 to about 5L/ha.

46. The method of any one of claims 43-45, wherein the formulation is diluted in the carrier in an amount of about 1 to 100L of stable formulation per 1000L of carrier.

47. The method of any one of claims 43-46 for controlling weeds in a plant or plant propagation material thereof.

48. The method of claim 47, wherein the plant is a cereal, soybean, corn, rice, papaya, melon, cocoa, and coffee.

49. The method of any one of claims 43-48, wherein the weed is a Poa, and broadleaf weed.

50. A process for the preparation of a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet and an amount of at least one sulfonylurea herbicide, wherein the process comprises the steps of:

(i) dissolving flufenacet in a non-aqueous carrier to form a solution;

(iii) the suspension is ground to obtain a stable formulation.

51. The method of claim 50, wherein the method further comprises the step of adding at least one adjuvant to the solution of step (i) prior to performing step (ii).

52. The method of claim 50 or 51, wherein the method further comprises the step of adding at least one adjuvant to the solution of step (ii) prior to performing step (iii).

53. The method of claim 51 or 52, wherein the adjuvant is a surfactant.

54. The method of claim 53, wherein the surfactant is calcium dodecylbenzenesulfonate and/or a methyl terminated ethoxylate.

55. The method of any one of claims 50-54, wherein the method further comprises the step of adding a thickener to the suspension of step (ii) prior to performing step (iii).

56. The method of claim 53, wherein the thickener is fumed silica.

57. The method of any one of claims 50-56, wherein the method further comprises the step of adding a safener to the solution of step (i) prior to performing step (ii).

58. The method of claim 57, wherein the safener is mefenpyr-diethyl.

59. The process of any one of claims 50 to 58, wherein the non-aqueous liquid carrier is heated to completely dissolve the flufenacet and/or the additive.

60. The method of any one of claims 50-59, wherein step (i) is performed at a temperature of 15 ℃ to 65 ℃.