Stable agrochemical suspension concentrate compositions

Abstract

This invention relates to an aqueous suspension concentrate composition comprising an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a grafted or comb-type copolymer containing a polyalkylene ether portion grafted onto the polymer backbone; b) an anionic dispersant having an SO3 group; and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene. The invention further relates to a suspension concentrate composition comprising an aniline herbicide and an antifreeze combination of urea and propane-1,2-diol. A method for preparing this composition and its use for controlling unwanted plants are disclosed.

Description

Technical Field

[0001] Invention Field

[0002] This invention relates to agrochemical compositions. Specifically, it relates to a stable aniline herbicide concentrated suspension. The invention further relates to a method for preparing the suspension and its use in crop protection. Prior Technology

[0003] Background of the Invention

[0004] Crop protection components can be formulated in different ways. Generally, highly concentrated formulations may need to be diluted by the end user before being applied to the field.

[0005] Suspension concentrates (SCs) are defined as suspensions of solid particulate active ingredients in a liquid medium intended for dilution prior to use. The liquid medium can be water, or a mixture of water and any organic / inorganic solvent, wherein the active ingredient is insoluble or only slightly soluble. SCs are superior to powder concentrates in that they do not produce dust after reconstitution. The advantage of aqueous suspension concentrates is that they eliminate the need for organic solvents, thus providing good safety and user convenience.

[0006] However, the preparation of diazepam suspension concentrate formulations is a challenging task. A major obstacle in formulating water-slightly soluble active ingredients (such as propanil) into aqueous SCs is Ostwald ripening, in which larger crystals of the ingredient grow while smaller crystals dissolve. This results in unacceptable physicochemical properties, such as high viscosity, leading to poor irrigation performance. Large crystals precipitate in the suspension, which can cause liquid-solid phase separation exceeding acceptable industrial standards and result in solid agglomeration at the bottom of the container.

[0007] SC formulations can also exhibit enhanced crystal growth after freeze-thaw cycles. The freeze-thaw process disrupts the balance between the solid, dispersant, and dissolved active ingredient molecules, leading to enhanced crystal growth. Dispersants are typically added to SC formulations because they bind to the solid surface and help suspend it in the liquid phase. Additionally, the surface coverage they provide helps to retard crystal growth. []

[0008] US2015 / 0099637 describes a suspension concentrate composition containing at least one aniline herbicide compound as an active ingredient and at least one carbamate compound as a crystallization inhibitor. US8618022 relates to a method for preparing an aqueous suspension of an organic insecticide compound.

[0009] One object of the present invention is to provide a stable aqueous suspension concentrate composition with low viscosity and minimal crystal growth, even at high active ingredient loadings. Summary of the Invention

[0010] Invention Summary

[0011] The present invention provides a stable agrochemical aqueous suspension concentrate composition, which contains an aniline herbicide as an active ingredient.

[0012] In a first embodiment, the present invention provides an aqueous suspension concentrate composition comprising an aniline herbicide and a dispersant combination, wherein the dispersant combination comprises: a) a grafted or comb-type copolymer comprising a polyalkylene ether portion grafted onto the polymer backbone; b) an anionic dispersant having an SO3 group; and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene. It has been surprisingly found that incorporating this dispersant combination into the aqueous suspension concentrate composition of the aniline herbicide during and after the manufacturing process results in reduced crystal growth.

[0013] In another embodiment, the present invention provides an aqueous suspension concentrate composition comprising an aniline herbicide and a combination of urea and propylene glycol. It has been found that this combination, when used as an antifreeze in an aqueous suspension concentrate composition of an aniline herbicide, imparts physicochemical stability to the composition, particularly after freeze-thaw cycles, and retards crystal growth.

[0014] In another embodiment, the present invention provides an aqueous suspension concentrate composition comprising an aniline herbicide and a dispersant combination, wherein the dispersant combination comprises: a) a grafted or comb copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; and b) a polyethylene oxide-polypropylene oxide block copolymer or an alkyl ether thereof.

[0015] Another aspect of the present invention relates to a method for preparing the suspension of the present invention.

[0016] The present invention further provides the use of the composition of the present invention for controlling unwanted plants. A method for controlling unwanted plants is further provided, comprising contacting an effective amount of the composition of the present invention with the location of the unwanted plants. Implementation

[0017] Detailed Description of Preferred Embodiments [definition] []

[0018] Before detailing the subject matter of this invention, it may be helpful to provide definitions for certain terms used herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the subject matter of this invention pertains.

[0019] As used in this article, the term "water-based" means that the diluent used in the composition is primarily water. Therefore, "water-based" and "water-based" can be considered synonyms.

[0020] Particle size is typically defined as a log-normal distribution with a median diameter, or d50. The term "d50" defines a size where 50% by volume of particles are smaller than a specified value. The term "d90" defines a size where 90% by volume of particles are smaller than a specified value. Particle size distribution can be measured using laser diffraction equipment such as the Malvern Mastersizer 2000 instrument.

[0021] As used herein, the term “stable” when used in conjunction with physical stabilization or in conjunction with a composition means that no obvious crystallization, precipitation and / or thickening has been observed and that the composition remains within acceptable limits for normal use in the formulation.

[0022] As used herein, the term "effective amount" when used in conjunction with an active ingredient or a formulation containing it refers to an amount of the active ingredient that, when ingested, exposed to or sensed, is sufficient to achieve good control or activity against pests, diseases and / or unwanted plants.

[0023] "Active ingredient" is a substance that can control unwanted plants (weeds), plant pests, or plant diseases without causing significant harm to the treated crop. The term "active ingredient" includes (but is not limited to) insecticides, nematicides, herbicides, fungicides, algaecides, animal repellents, or acaricides. Active ingredients are not limited to insecticides but also include, for example, hormones, biostimulants, and plant growth regulators.

[0024] As used herein, the terms "plant," "crop," or "crop plant" include references to whole plants, plant organs (e.g., leaves, stems, branches, roots, trunks, branches, buds, fruits, etc.), plant cells, or plant seeds that have industrial interests, including grasslands and pastures, such as plants intended for human consumption, animal consumption, or other industrial uses. This term also covers crops such as fruits. The term "plant" may also include its propagation material, which may include all reproductive parts of a plant, such as seeds; and vegetative plant material, such as cuttings and tubers, which can be used for plant propagation. It may also include spores, bulbs, tubers, rhizomes, basal buds of new shoots, stolons, and buds, as well as other parts of the plant, including seedlings and young plants transplanted after budding or after sprouting from the soil. As used herein, the term "crop" includes plants that have been modified by breeding, mutagenesis, or genetic engineering. Genetically modified plants are those whose genetic material has been modified using recombinant DNA technology. Typically, one or more genes have been integrated into the genetic material of plants in order to improve certain characteristics of them.

[0025] As used herein, the term “location” includes habitats, breeding lands, plants, propagation materials, soils, regions, materials, or environments in which unwanted plants, pests, or diseases are growing or can grow.

[0026] As used herein, the terms “control” or “controlling” or “combatting” refer to preventing the growth of diseases, pests or unwanted plants, protecting plants against diseases or pests, delaying the onset of diseases, and killing pests or reducing the harmful effects of diseases or pests, or killing unwanted plants or reducing the growth of unwanted plants.

[0027] Unless otherwise specified, as used herein, the term "a / an" includes both the singular and plural forms. Therefore, the terms "a / an" or "at least one" are used interchangeably in this application.

[0028] Unless otherwise specified, for the purpose of better understanding the teachings of this invention and without limiting the scope of the teachings in any way, all figures and other numerical values ​​used in the specification and claims to express quantities, percentages or proportions should be understood to be modified by the term "about" in all cases. Therefore, unless stated to the contrary, the numerical parameters described in the following specification and the appended claims are approximate values ​​that may vary depending on the desired characteristics sought to be obtained. At a minimum, each numerical parameter should be understood based on at least the number of significant digits reported and by applying general rounding techniques. In this regard, the term "about" as used herein specifically includes ±10% of the values ​​shown within the range. Furthermore, the endpoints of all ranges for the same component or characteristic herein include endpoints that can be independently combined and include all intermediate points and ranges.

[0029] As used herein, the term "propylene glycol" means propane-1,2-diol. The terms "propylene glycol" and "propane-1,2-diol" are used interchangeably herein. [Composition of the Invention] []

[0030] The present invention provides an aqueous suspension concentrate (SC) composition containing an aniline herbicide. [, <s>< / s> , ]

[0031] As an example, suitable aniline herbicides that can be used in the composition of the present invention may be selected from the group consisting of: chloranocryl, cisanilide, clonprop, cypromid, diflufenican, erlujixiancaoan, etobenzanid, fenasulam, flufenacet, and flufenican. n), triazolam (ipfencarbazone), mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor, picolinafen, chlorpyrifos, sulfurtrazone, and tetflupyrolimet; or the group of aryl alanine herbicides selected from the following compositions. Group: benzoylprop, flamprop, and flamprop-M; or selected from the following chloroacetanilide herbicides: acetochlor, alachlor, amidochlor, butachlor, butenachlor, delachlor, diethatyl, dimethachlor, ethachlor, ethaprochlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prynachlor, terbuchlor, thenylchlor, and xylachlor;Alternatively, select from the following group of thiamethoxam herbicides: benzofluor, cloransulam, diclosulam, dimesulfazet, floraulam, flumetsulam, metosulam, perfluidone, profluazol, pyrimisulfan, and triafamone.

[0032] In a preferred embodiment, the herbicide is an aniline herbicide. The herbicide [N-(3,4-dichlorophenyl)acrylamide] is a PS-II contact herbicide corresponding to the following formula:

[0033] Typically, the composition of the present invention comprises about 10% to 90% by weight, more preferably about 20% to 80% by weight, and even more preferably about 40% to 60% by weight of an aniline herbicide.

[0034] In addition to aniline herbicides, the suspension concentrate composition of the present invention may contain agriculturally acceptable inert additives (also referred to as "co-components"). Such additives are defined herein as any substance that is not itself an active ingredient but is added to the composition to improve its properties. Non-limiting examples of agriculturally acceptable inert additives include surfactants, dispersants, wetting agents, antifreeze agents, thickeners, suspending agents, defoamers, preservatives, antioxidants, binders, buffers, humectants, plant penetrants (or translocators), fertilizers, anti-drift agents, phase inverting agents, soil penetrants, and UV absorbers.

[0035] Preferably, the composition of the present invention comprises a surfactant. As used herein, the term surfactant (including the terms dispersant and wetting agent) means a composition that, when dissolved in water or an aqueous solution, alters the surface tension, or alters the interfacial tension between immiscible liquids or between a liquid and a solid. Suitable surfactants include (but are not limited to) acrylate graft copolymer ethoxylates, cresol-formaldehyde or naphthalene-formaldehyde condensates and their sulfonates, tristyrylphenol ethoxylates, alkylamine ethoxylates, block polymers (such as ethylene oxide / propylene oxide condensates or their ethers); carboxylated alcohols or alkylphenol ethoxylates, alcohol ethoxylates, ethoxylated alkylphenols, glycol esters, polyethylene glycol, polysiloxane-based surfactants, lignin sulfonates; polycarboxylate esters and their derivatives.

[0036] Particularly preferred is that the dispersant composition comprises: a) a grafted or comb-type copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; b) an anionic dispersant having an SO3 group; and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene; or the dispersant composition comprises: a) a grafted or comb-type copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; and b) a polyethylene oxide-polypropylene oxide block copolymer or its alkyl ether. It has been surprisingly found that incorporating this dispersant composition into the aqueous suspension concentrate composition of aniline herbicides during and after the manufacturing process results in reduced crystal growth. This reduction in crystal growth translates into more stable particle size over time and / or less viscosity variation in the formulation.

[0037] Therefore, in one embodiment, the present invention provides an aqueous suspension concentrate (SC) composition comprising an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a grafted or comb copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; b) an anionic dispersant having an SO3 group; and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene.

[0038] In other embodiments, the present invention provides an aqueous suspension concentrate (SC) composition comprising an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a grafted or comb copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; and b) a polyethylene oxide-polypropylene oxide block copolymer or an alkyl ether thereof.

[0039] Grafted or comb-type copolymers comprise polyalkylene ether portions grafted onto the polymer backbone. Preferably, the polyepoxide is a polyC2-C4 epoxy or its ether, such as its mono-C1-C4 alkyl ether. Preferably, carboxylic acid ester groups are attached to the polymer backbone.

[0040] Preferred graft or comb copolymers may polymerize in the form of: (i) at least one C3-C5 monovinyl unsaturated carboxylic acid monomer, such as acrylic acid or methacrylic acid; (ii) at least one monomer having a poly(C2-C4) epoxy alkyl group, the epoxy alkyl group being linked to a polymerizable monovinyl unsaturated double bond via an ester or ether bond; specifically, an ester of polyethylene oxide or polyethylene oxide mono(C1-C4) alkyl ether with a C3-C5 monovinyl unsaturated carboxylic acid monomer (such as acrylic acid or methacrylic acid); and (iii) any Hydrophobic monomers that are selectively present, such as C1-C10 alkyl esters of C3-C5 monovinyl unsaturated carboxylic acid monomers, specifically, C1-C10 alkyl esters of acrylic acid or methacrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate; or vinyl aromatic monomers, such as styrene, or aryl-substituted C3-C5 monovinyl unsaturated carboxylic acid monomers, such as 2-phenylacrylic acid or its esters.

[0041] In a preferred embodiment, the grafted or comb-type polymer contains, or is composed of, methacrylic acid, methyl methacrylate, and polyethylene oxide or its C1-C4 alkyl ethers (e.g., monomethyl ethers thereof) in polymeric form with methacrylic acid, or the like. Such polymers are commercially available, for example as Atlox 4913 (Croda).

[0042] Anionic dispersants having an SO3 group are preferably polymeric dispersants, such as condensates of arylsulfonic acids (e.g., naphthalenesulfonic acid or phenolsulfonic acid) with formaldehyde and, optionally, urea. The arylsulfonic acid can be, for example, unsubstituted or substituted with one or more substituents (such as alkyl groups) of phenolsulfonic acid or naphthalenesulfonic acid. Preferably, the anionic dispersant having an SO3 group is an alkali metal or alkaline earth metal salt of a condensate of naphthalenesulfonic acid and formaldehyde; such polymers are commercially available, for example, as Morwet D-425 (Nouryon).

[0043] In styrene-based phenol polyalkoxyl dispersants, the phenoxy group carries one, two, or three styrene moieties and a polyalkylene ether moieties, typically polyethylene oxide (PEO), polypropylene oxide (PPO), or poly(ethylene oxide-propylene oxide) (PEO / PPO) moieties. The polyalkylene ether moieties typically contain about 5 to 100 epoxy alkyl groups. A preferred surfactant for this group is an ethoxylated tristyrene group; it is commercially available, for example, as Soprophor TS54 (Solvay).

[0044] In a preferred embodiment, the polyethylene oxide-polypropylene oxide block copolymer or its alkyl ether is an alkyl ether, and more preferably, it is a C1-C10 alkyl ether. Particularly preferred is a polyethylene oxide-polypropylene oxide block copolymer butyl ether, which is commercially available, for example, as Atlas G5000 (Croda).

[0045] In a preferred embodiment, the aqueous suspension concentrate (SC) composition comprises an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a grafted or comb-type copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; b) an anionic dispersant having an SO3 group; and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene. Furthermore, the dispersant combination also comprises a polyethylene oxide-polypropylene oxide block copolymer or its alkyl ether, such as its C1-C10 alkyl ether. Preferably, the block copolymer is nonionic. Particularly preferred is a polyethylene oxide-polypropylene oxide block copolymer butyl ether, which is commercially available, for example, as Atlas G5000 (Croda).

[0046] In another preferred embodiment, the aqueous suspension concentrate (SC) composition comprises an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a grafted or comb copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; and b) a polyethylene oxide-polypropylene oxide block copolymer or its alkyl ether, also comprising an anionic dispersant having an SO3 group, or a polyalkoxylated form of styrene, stilbene, or tristyrene.

[0047] The amount of various dispersants present in the composition of the present invention is preferably from about 0.01% by weight to about 20% by weight, more preferably from about 0.01% by weight to about 10% by weight, and even more preferably from about 0.05% by weight to about 5.0% by weight, and most preferably from about 0.2% by weight to about 4.0% by weight.

[0048] Antifreeze agents that can be used in the compositions of this invention include, for example, monohydric and polyhydric alcohols (as used herein, the term "polyhydric alcohol" refers to an organic compound containing more than one hydroxyl group), such as C1-C4 alkanols and C2-C4 polyhydric alcohols. Suitable examples of C1-C4 alkanols include methanol, ethanol, and isopropanol. Suitable examples of C2-C4 polyhydric alcohols include ethylene glycol, propane-1,2-diol, propane-1,3-diol, and glycerol. Other suitable polyhydric alcohols include polyhydroxylated sugars, such as glucose. Polyalkylene glycols (such as polyethylene glycol and polypropylene glycol) and glycol ethers (such as dipropylene glycol) can also be used as antifreeze agents. Other suitable antifreeze agents include urea or salts, such as NaCl, CaCl2, and Na2SO4.

[0049] As an antifreeze agent, a combination of urea and alkyl glycol, and more specifically, urea and propylene glycol (propane-1,2-diol), is preferred. Although using propylene glycol or urea as the sole antifreeze agent in aniline herbicide suspension concentrate formulations does not yield satisfactory results in terms of viscosity and crystal growth, their combined use has been found to impart physicochemical stability to the composition, with minimal increases in viscosity and particle size, especially after freeze-thaw cycles. Surprisingly, a propylene glycol:urea weight ratio higher than approximately 1:1 resulted in lower viscosity and crystal growth.

[0050] Therefore, in another embodiment, the present invention provides an aqueous suspension concentrate composition comprising an aniline herbicide, urea, and propylene glycol.

[0051] The propylene glycol:urea weight ratio is preferably greater than 1:1 to about 50:1, and more specifically, the ratio is selected from greater than 1.0:1, greater than 1.05:1, greater than 1.1:1, greater than 1.2:1, greater than 1.21:1, or greater than 1.22:1 or greater than 1.4:1; up to a ratio of about 50:1, more preferably about 20:1, 10:1, 5:1 or 2:1. The amount of the antifreeze combination containing urea and propylene glycol is preferably about 0.1% by weight to about 20% by weight, more preferably about 3.0% by weight to about 15% by weight, and even more preferably about 6% by weight to about 15% by weight of the composition of the present invention. The amount of urea is about 0.1% by weight to about 20% by weight of the composition of the present invention, more preferably about 1.0% by weight to about 10% by weight, more preferably about 2.0% by weight to about 8.0% by weight, and even more preferably about 2.5% to about 4%.

[0052] In a preferred embodiment, the present invention provides an aqueous suspension concentrate (SC) composition comprising an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a grafted or comb copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; and b) a polyethylene oxide-polypropylene oxide block copolymer or an alkyl ether thereof; urea and propylene glycol. The propylene glycol:urea weight ratio is preferably greater than 1:1 to about 50:1, and more specifically, the ratio is selected from greater than 1.0:1, greater than 1.05:1, greater than 1.1:1, greater than 1.2:1, greater than 1.21:1, or greater than 1.22:1 or greater than 1.4:1; up to a ratio of about 50:1, preferably about 20:1, 10:1, 5:1 or 2:1. The propylene glycol:urea weight ratio is preferably greater than 1:1 to about 50:1, and more specifically, the ratio is selected from greater than 1.0:1, greater than 1.05:1, greater than 1.1:1, greater than 1.2:1, greater than 1.21:1 or greater than 1.22:1 or greater than 1.4:1; up to about 50:1, more preferably about 20:1, 10:1, 5:1 or 2:1, and the total amount of urea and propylene glycol is about 0.1% by weight to about 20% by weight of the composition, more preferably about 3.0% by weight to about 15% by weight of the composition, and even more preferably about 6% by weight to about 15% by weight of the composition.

[0053] Examples of suitable suspending agents and / or thickeners that may be used in the compositions of this invention include polysaccharides such as alginate, gum arabic, tragacanth, guar gum, soybean gum, carrageenan, saffron gum, cellulose, methylcellulose (MC), sodium carboxymethylcellulose (CMC), hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose, carboxymethyl cellulose; carbomers; or surface-modified silica. The suspending agent and / or thickener are typically present in an amount of about 0.001% by weight to about 2% by weight of the composition.

[0054] Examples of defoamers that can be used in the compositions of this invention include silicone-containing defoamers, such as polydimethylsiloxane, alkylcyclotetrasiloxane, and other polysiloxanes. Typically, such silicone-containing defoamers are commercially available in the form of aqueous emulsions. The defoamer is typically present in an amount of about 0.001% by weight to about 2% by weight of the composition.

[0055] Preservatives such as isothiazolone can be used to prevent components from being damaged by microorganisms.

[0056] Water is used as the continuous phase in the suspension composition of the present invention. It is present in an amount that dilutes the active ingredient to the desired concentration, typically between about 20% and about 80% by weight of the composition, more preferably between about 25% and about 65%, even more preferably between about 30% and about 55%, and most preferably between about 35% and about 50%, and most preferably between about 40% and about 45%.

[0057] Preferably, the pH of the suspension concentrate composition of the present invention is higher than 7, and more specifically, between about 7 and 14; more preferably between about 8 and 11, and even more preferably between about 8.5 and 10.5. It has been found that the composition is advantageous in terms of viscosity and crystal growth at alkaline pH. The pH of the composition can be adjusted by adding an alkali (such as sodium hydroxide).

[0058] The suspension concentrate composition of the present invention exhibits excellent stability in terms of viscosity and particle size after 8 weeks at 40°C. In a preferred embodiment, after 8 weeks at 40°C, the suspension concentrate composition of the present invention has a D(90) particle size of less than 30 µm, preferably less than 27 µm, less than 25 µm, or even less than 20 µm (when measured on a Malvern Mastersizer 2000, as described below). In a preferred embodiment, after 8 weeks at 40°C, the suspension concentrate composition of the present invention has a viscosity of less than 2500 cP, preferably less than 2000 cP, less than 1800, 1600, 1400, 1200, 1100, or even less than 1000 cP (when measured using a Brookfield LV viscometer, as described below).

[0059] Viscosity can be measured at 12 rpm using a Brookfield LV viscometer at a temperature of 25.0°C with rotor 62 (rotor 63 for viscosities above 2000 cP). []

[0060] Particle size can be measured using a Malvern Mastersizer 2000 instrument equipped with a small sample dispersion unit. Measurement parameters are selected such that the residual and weighted residual values ​​are between 0.8 and 1.3, for example, the sample's refractive index is set to 1.632 and its absorptivity in red and blue light measurements is set to 0.01. Background sampling time is 20 seconds with 20,000 background measurement images. Sample sampling time is 10 seconds with 10,000 sample measurement images. Both background and sample measurements are performed using defoamed water. At room temperature (at atmospheric pressure, 20-27°C), with stirring at 800 rpm, the formulation is added dropwise to the water in the unit until the turbidity is between 15% and 25% and remains stable (+ / - 5% turbidity) for at least 2 minutes. Measurements are then performed.

[0061] In one particular embodiment, the present invention provides a herbicide suspension concentrate composition having, after 8 weeks at 40°C, a particle size of a) less than 30 µm, preferably less than 27 µm, less than 25 µm, or even less than 20 µm (when measured on a Malvern Mastersizer 2000); or b) a viscosity of less than 2500 cP, preferably less than 2000 cP, less than 1800, 1600, 1400, 1200, 1100, or even less than 1000 cP (when measured using a Brookfield LV viscometer).

[0062] The suspension concentrate composition of this invention can be diluted with water or mixed with a tank mixing adjuvant solution before application to the field to improve its physical properties and efficacy. Some substances, such as plant penetrants (or translocators), fertilizers, anti-drift agents, or soil penetrants, can be used as agriculturally acceptable inert additives in the composition of this invention, or mixed with the composition of this invention as tank mixing additives before application to the field. Diluting the composition of this invention with water or mixing the composition with one or more tank mixing adjuvant solutions to obtain a tank mixture is also a form of this invention. [Preparation Method of Suspension Concentrator Composition] []

[0063] Another aspect of the present invention relates to a method for preparing the suspension of the present invention. The method includes the following steps: a) adding a co-component other than the active ingredient and suspending agent and / or thickener (if present) to water and stirring until completely dispersed / dissolved; b) adding the active ingredient and homogenizing; c) grinding to the desired particle size; d) optionally adding the suspending agent and / or thickener; and e) optionally adjusting the pH by adding a base or acid.

[0064] Homogenization is typically performed using a high-shear homogenizer (such as the Ultra Turrax). Zirconia beads are used for grinding. For example, WAB laboratory research instruments can be used. [Methods and Applications] []

[0065] This article discloses a method for controlling unwanted plants, comprising contacting an effective amount of the suspension concentrate composition of the present invention or its diluted tank mix with the location of the unwanted plant.

[0066] The methods disclosed herein refer to herbicides that have known activity against any non-desirable plant. Similarly, the methods disclosed herein refer to herbicides that have known protective activity against any crop. The methods disclosed herein apply to any crop plant, including (but not limited to) monocotyledons such as sugarcane, cereals, rice, and corn; or dicotyledonous crops such as sugar beets (such as sugar beets or forage beets); fruits (such as pome, stone fruits, or soft fruits, such as apples, pears, plums, peaches, apricots, cherries, strawberries, raspberries, or blackberries); legumes (such as beans, lentils, peas, or soybeans); and oil plants (such as rapeseed, mustard, poppies, olives, sunflowers, coconuts, castor oil plants, cocoa beans, or...). Peanuts); cucumber plants (such as zucchini, cucumber, or melon); fiber plants (such as cotton, flax, hemp, or jute); citrus fruits (such as oranges, lemons, grapefruits, or tangerines); vegetables (such as spinach, lettuce, kale, carrots, tomatoes, potatoes, gourds, or peppers); Lauraceae (such as avocados, cinnamon, or camphor); tobacco; nuts; coffee; tea; vines; hops; durian; bananas; natural rubber plants; and ornamental plants (such as flowers, shrubs, broad-leaved trees, or evergreens, such as conifers).

[0067] Depending on the specific active ingredient used, the target crop, and the unwanted plants, pests, or diseases to be controlled, the suspension compositions disclosed herein (whether in pure or barrel-mixed form) are applied to the field in varying amounts. In some embodiments, the active ingredients are each applied at amounts from about 1 g / ha to about 1500 g / ha or from 300 g / ha to about 1300 g / ha.

[0068] The suspension composition disclosed herein may be applied before, during, or after planting.

[0069] The invention is further illustrated by the following non-limiting examples. [Example] [] [method:] []

[0070] [Preparation of the formulation] [:] The formulations (formulation ag) in the following examples were prepared according to the following general procedure: For each formulation, all co-forming agents (except Kelzan) were added to water and stirred until completely dispersed. Then, herbicide was added and the solution was homogenized for 3 minutes at approximately 12-14 k rpm using an Ultra Turrax (high-shear homogenizer). The suspension was then ground using 0.3 mm ZrO₂ ceramic beads using a WAB laboratory research instrument until the desired particle size was achieved. Subsequently, Kelzan was added and stirred until completely dispersed. The pH was adjusted by adding NaOH solution.

[0071] [Freeze-thaw experiment]: Each freeze-thaw cycle was performed as follows: 40 ml vials of the preparation were taken and placed in a freezer (-18°C) until the suspension was frozen, typically for several days. The suspension was then allowed to thaw at room temperature for 1 day.

[0072] [Viscosity] was measured at 25.0°C using a Brookfield LV viscometer with rotor 62 (rotor 63 for viscosities above 2000 cP) at 12 rpm. []

[0073] [Particle size] was measured using a Malvern Mastersizer 2000 instrument equipped with a small sample dispersion unit. Measurement parameters were selected such that the residual and weighted residual values ​​were between 0.8 and 1.3; for example, the sample's refractive index was set to 1.632 and its absorptivity in red and blue light measurements was set to 0.01. Background sampling time was 20 seconds with 20,000 background measurement images. Sample sampling time was 10 seconds with 10,000 sample measurement images. Both background and sample measurements were performed using defoamed water. At room temperature (at atmospheric pressure, 20-27°C), the preparation was added dropwise to the water in the unit with a stirring speed of 800 rpm until the turbidity was between 15% and 25% and remained stable (+ / - 5% turbidity) for at least 2 minutes. Measurements were then performed. [Material:] []

[0074] [] Atlox 4913: Ethoxylated (methyl methacrylate / methacrylic acid) graft polymer Soprophor TS54: Tristyrylphenol ethoxylates (54 ethoxylates) Morwet D-425: Sodium salt of naphthalenesulfonate formaldehyde condensate Silicaid AF-100: Dimethyl polysiloxane emulsion / water Atlas G5000: Nonionic block copolymer polypropylene oxide (PPO) / ethylene oxide (PEO) butyl ether Agnique PG 9116:C9-11 polyalkyl glycoside Hi-Sil™ 233: Smoky Silicon Dioxide Pluronic PE 10400: Nonionic triblock copolymer, PEO / PPO / PEO (MW 3000 PPO), 40% PEO PVP K-30: Poly(vinylpyrrolidone) XIAMETER ACP-1500: Polydimethylsiloxane emulsion Proxel GXL: 1,2-Benzisothiazolin-3-one + NaOH Kelzan, Kelzan AP-AS: Three Immortals Gel [Example] [1 -] [Different antifreeze systems] []

[0075] Herbicide suspension concentrates (SC) formulations a through e, each containing a different antifreeze system, were prepared; the formulations are shown in Table 1 below. All formulations had a pH of 9 and an initial particle size (D90) of 7 µm.

[0076] In the first group of formulation samples, particle size was measured after three freeze-thaw cycles, and viscosity was qualitatively examined by visual inspection. In the second group of formulation samples, particle size and viscosity were examined after four days at 40°C. The results are summarized in Table 2 below.

[0077] It can be observed that although the formulations containing urea or propylene glycol as the sole antifreeze agent become viscous and show a significant increase in particle size after three freeze-thaw cycles, the formulation containing a combination of propylene glycol and urea (propylene glycol:urea weight ratio greater than 1:1) (formulation b) shows only a slight increase in viscosity and minimal particle growth after three freeze-thaw cycles. [surface] [1] [Element] [(g / L)] [Ingredients] [a] [Ingredients] [b] [Ingredients] [c] [Ingredients] [d] [Ingredients] [e] weed killer 488.1 488.1 488.1 488.1 488.1 Atlox 4913 35.5 35.5 36.0 36.0 36.0 Soprophor TS54 11.8 11.8 12.0 12.0 12.0 Morwet D-425 4.9 4.9 5.0 5.0 5.0 Aqueous solutions of 2.5 w / w% Kelzan and 1.7 w / w% Proxel GXL 79.0 79.0 79.0 79.0 79.0 NaOH 15% 2.0 2.0 2.0 2.0 2.0 Silicaid AF-100 3.0 3.0 3.0 3.0 3.0 water 463.1 398.9 449.9 449.9 449.9 [Urea] [49.3] [49.3] [60.0] [-] [30.0] [Propylene glycol] [-] [60.0] [-] [60.0] [30.0] [surface] [2] [] [Ingredients] [a] [Ingredients] [b] [Ingredients] [c] [Ingredients] [d] [Ingredients] [e] [pH] 9 9 9 9 9 [Initial Granularity] [(D90)] [,] [µm] 7 7 7 7 7 [exist]

[40] [Duration at ℃] [4] [Grain size after the first day] [(D90)] [,] [µm] 14.4 13.9 15.3 24.6 twenty three [3] [Second-rate] [Particle size after freeze-thaw cycle] [(D90)] [,] [µm] 64 11.6 100 187 163 [exist]

[40] [Duration at ℃] [4] [Qualitative viscosity after 1 day] liquid liquid liquid viscous liquid viscous liquid [3] [Qualitative viscosity after one freeze-thaw cycle] viscous liquid liquid viscous liquid viscous liquid viscous liquid [Example] [2 -] [Different types of propylene glycol] [ / ] [Urea ratio] []

[0078] Herbicide suspension concentrates (SC) containing different ratios of urea and propylene glycol as antifreeze systems were prepared from f to g; the concentrates are shown in Table 3 below.

[0079] After three freeze-thaw cycles and 8 days at 40°C, the viscosity and particle size of the formulation were measured. The results are summarized in Table 4 below. [surface] [3] [Element] [(g / L)] [Ingredients] [f] [Ingredients] [g] [Ingredients] [l] [Ingredients] [m] [Ingredients] [n] weed killer 488.1 488.1 489.7 489.7 489.7 Atlox 4913 35.5 35.5 35.8 35.8 35.8 Soprophor TS54 11.8 11.8 11.8 11.8 11.8 Morwet D-425 4.9 4.9 4.7 4.7 4.7 Atlas G5000 11.4 11.4 11.5 11.5 11.5 Aqueous solutions of 2.5 w / w Kelzan AP-AS and 1.7 w / w Proxel GXL 79.0 79.0 80.24 80.24 80.24 NaOH 15% 2.0 2.0 2.4 2.4 2.4 Silicaid AF-100 3.0 3.0 1.8 1.8 1.8 water 389.9 359.9 420.3 418.1 388.4 [Urea] [49.3] [49.3] [38.1] [36.3] [34.7] [Propylene glycol] [60.2] [90.2] [68.7] [72.7]

[0104] [surface] [4] [Initial viscosity] [(cP)] [Initial Granularity] [d(90) (µm)] [initial] [pH] [exist]

[40] [at ℃] [store] [8] [week] [freeze] [ / ] [Circulation] [After storage] [pH] [Viscosity after storage] [(cP)] [Granularity after storage] [d(90) (] [µm] [)] [3] [Viscosity after the next cycle] [(cP)] [3] [Granularity after the next iteration] [d(90)]( [µm]) [Ingredients] [f] 1370 3.1 9.05 8.99 1650 14.7 1130 4.9 [Ingredients] [g] 1375 3.1 9.05 9.07 1800 9.7 1150 3.1 [Ingredients] [l] 1720 6.8 1140 16.1 2570 13.6 [Ingredients] [m] 1760 6.8 1150 14.6 2470 11.8 [Ingredients] [n] 1560 6.8 1110 13.9 2780 16.6 [Example] [3 -] [different] [Ph] []

[0080] Herbicides SC formulations h to i were prepared. The final pH was then adjusted by adding a small amount of 45 w / w% NaOH solution. Both formulations had an initial particle size of 7 µm and a viscosity of 1500 cP. After 4 days at 40°C, the particle size and viscosity were measured again; the results are shown in Table 5. [surface] [5] [Element] [(g / L)] Mixture h Mixture i weed killer 485.8 485.8 Atlox 4913 35.5 35.5 Soprophor TS54 11.8 11.8 Morwet D-425 4.9 4.9 urea 49.3 49.3 Aqueous solutions of 2.5 w / w% Kelzan and 1.7 w / w% Proxel GXL 79.0 79.0 SILICAID AF-100 3.0 3.0 water 465.6 465.6 Final pH 5.4 8.5 Initial PS (D90), µm 7 7 Particle size (D90) (µm) after 4 days at 40°C 20 12 Initial viscosity (cP) 1500 1500 Viscosity (cP) after 4 days at 40°C >2500 1500 [Example] [4] [-] [Different Dispersant Systems] []

[0081] Herbicides SC formulations j to k were prepared (see Table 6). Their viscosity and particle size were measured at room temperature and after 8 weeks at 40°C. The results are shown in Table 7.

[0082] After 8 weeks at 40°C, the viscosity of formulation j, which contains the dispersant combination of Atlox 4913, Morwet D-425 and Soprophor TS54, remained unchanged, while the viscosity of formulation k increased significantly. [surface] [6] [Ingredients] [j] [] [Ingredients] [k] [Element] [quantity] [(g / L)] [] [Element] [quantity] [(g / L)] weed killer 479.8 weed killer 479.7 Atlas G-5000 11.4 Agnique PG 9116 7.3 Atlox 4913 35.5 Tetrasodium ethylenediaminetetraacetic acid dihydrate 2.7 Kelzan AP-AS 2 Hi-Sil™ 233 8.5 Morwet D-425 4.9 Kelzan 2.2 Propylene glycol 70 85% phosphoric acid solution 8.5 Proxel GXL 1.3 Pluronic PE 10400 20.6 Silicaid AF-100 3 Propylene glycol 47.2 45% sodium hydroxide 2 Proxel GXL 1.1 Soprophor TS54 11.8 PVP K-30 1.2 Urea granules 49.3 XIAMETER ACP-1500 2.2 water Add to 1L Zochem Grade 104 Zinc Oxide Powder 58.1 water 561.58 [surface] [7] [Ingredients] [RT] [exist]

[40] [Duration at ℃] [8] [week] [granularity] [d(90), µm] [pH] [Viscosity,] [cP] [Viscosity,] [cP] [granularity] [d(90)] [,] [µm] [pH] k 6.2 8.18 1300 2302 33.3 8.11 j 7 8.95 1050 1050 12.1 9.21

Claims

1. An aqueous suspension concentrate composition comprising an aniline herbicide and a dispersant combination, the dispersant combination comprising: a) a graft or comb copolymer comprising a polyalkyl ether portion grafted onto the polymer backbone; and b) a polyethylene oxide-polypropylene oxide block copolymer or an alkyl ether thereof.

2. An aqueous suspension concentrate composition comprising an aniline herbicide and a dispersant combination, wherein the dispersant combination comprises: a) a grafted or comb-type copolymer containing a polyalkyl ether portion grafted onto the polymer backbone; b) an anionic dispersant having an SO3 group; and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene.

3. The composition of claim 1 or 2, wherein the graft or comb copolymer comprises, in polymeric form, methacrylic acid, methyl methacrylate, and esters of polyethylene oxide or its C1-C4 alkyl ethers with methacrylic acid.

4. The composition of claim 2, wherein the anionic dispersant having an SO3 group is a naphthaldehyde condensate sulfonate or a salt thereof.

5. The composition of claim 2, wherein the polyalkoxylation of monostyrene, stilbene, or tristyrene is a tristyrene ethoxylation.

6. The composition of claim 2 further comprises a polyethylene oxide-polypropylene oxide block copolymer or an alkyl ether thereof.

7. A composition as claimed in claim 1 or 6, wherein the polyethylene oxide-polypropylene oxide block copolymer or its alkyl ether is a polyethylene oxide-polypropylene oxide block copolymer butyl ether.

8. An aqueous suspension concentrate composition comprising an aniline herbicide, urea, and propane-1,2-diol, wherein the composition comprises propane-1,2-diol:urea in a weight ratio of more than 1:1 to about 50:

1.

9. The composition of claim 1 or 2 further comprises urea and propane-1,2-diol.

10. The composition of claim 9, wherein the composition comprises propane-1,2-diol:urea in a weight ratio of more than 1:1 to about 50:

1.

11. A composition of any one of claims 1, 2 and 8, wherein the pH of the composition is between 7 and 14.

12. A composition of any one of claims 1, 2 and 8, wherein the aniline herbicide is propanil.

13. The composition of any one of the claims 1, 2 and 8, wherein after 8 weeks at 40°C: a) D(90) particle size (when measured on a Malvern Mastersizer 2000) is less than 27 μm, or b) viscosity (when measured using a Brookfield LV viscometer, with a rotor 62, at 12 rpm at 25.0°C) is less than 2500 cP.

14. A composition as claimed in claim 2 or 8, comprising: an aniline herbicide; a dispersant combination comprising a) a grafted or comb copolymer containing a polyalkylene ether portion grafted onto the polymer backbone, b) an anionic dispersant having an SO3 group, and c) a polyalkoxylated form of monostyrene, stilbene, or tristyrene; and a combination of urea and propane-1,2-diol.

15. A method for preparing a composition as claimed in any one of claims 1 to 14, the method comprising: a) Add the co-components, excluding the active ingredient and suspending agent and / or thickener (if present), to the water and stir until completely dispersed; b) Add the active ingredient and homogenize; c) Grind to the desired particle size; d) Optionally add the suspending agent and / or thickener; and e) Optionally adjust the pH by adding an alkali or acid.

16. A method for controlling unwanted plants, the method comprising contacting an effective amount of a composition of any one of claims 1 to 14 with the location of the unwanted plants.

17. A herbicide suspension concentrate composition wherein, after 8 weeks at 40°C: a) D(90) particle size (measured on a Malvern Mastersizer 2000) is less than 27 μm, or b) viscosity (measured at 12 rpm using a Brookfield LV viscometer with a rotor 62 at 25.0°C) is less than 2500 cP.