Suspension concentrate dispersant

Abstract

A new suspension-type water-borne pesticide formulation is provided, comprising an adjuvant selected from a copolymer dispersant comprising a copolymer of acrylic acid, a hydrophobic monomer, an alkyl acrylate of a monoalkyl polyethylene glycol, and optionally a strong acid derivative of (meth)acrylic acid; a nonionic graft copolymer of an acrylic acid ester and an oxyalkylene; and a hydrophobic solid pesticide active dispersed in an aqueous medium. A concentrate suitable for forming the formulation is also provided. The copolymer combination provides dispersibility for the hydrophobic solid pesticide active in the aqueous medium of the suspension concentrate. The use of the copolymer as a dispersant for the hydrophobic solid pesticide active in a pesticide formulation and a method for treating vegetation to control pests by applying the formulation or a diluted concentrated form of the formulation to the vegetation or surrounding environment are also provided.

Description

Technical Field

[0001] The present invention relates to a polymeric dispersant for suspension-type agrochemical formulations containing hydrophobic solid agrochemical actives, and a method for providing dispersibility in said agrochemical formulations. The present invention also includes a method for treating crops with said formulations.

Background Art

[0002] Agrochemical formulations typically contain dissolved or dispersed components such as actives, and additives or dispersants are often added to the formulations to aid in the dispersion of these components.

[0003] Due to regulations, there is a tendency for water-based systems to increase, and thus problems have arisen in the case of active substances that are not very water-soluble (hydrophobic and poorly soluble). Furthermore, often when more active substances are included in the formulation, this can lead to undesirable crystal growth.

Summary of the Invention

Problems to be Solved by the Invention

[0004] A particular problem with agrochemical formulations is that the dispersion of active substances is becoming increasingly difficult, which is particularly problematic because there is a tendency to use active substances with low solubility or poor solubility. As a result of the tendency to use more hydrophilic active substances, they are more difficult to disperse. These active substances can increase the likelihood of Ostwald ripening and / or crystal growth.

[0005] Crystal growth and aggregation are thought to be caused by the constant collision of fine particles with each other due to van der Waals forces. The fine particles can aggregate and as a result settle like clay. At that stage, it becomes difficult to disperse the aggregates.

[0006] Using certain solvents as stabilizers when preparing suspension-type pesticide formulations is not a solution. These types of solvents can also lead to accelerated crystal growth of the pesticide's active ingredient.

[0007] Therefore, there is a need to find a dispersant that enables the formation of suspensions containing hydrophobic, poorly soluble active substances, thereby completely or substantially reducing the crystal growth and instability of the formulation. [Means for solving the problem]

[0008] The present invention aims to provide a compound suitable for use as a dispersant in agrochemical formulations, and the dispersant can overcome the above-mentioned problems. Furthermore, the present invention aims to provide a dispersant having desirable properties, such as the dispersibility of hydrophobic solid active substances in suspension formulations. The present invention also aims to provide the use of agrochemical concentrates and diluted formulations containing the dispersant. The present invention also aims to provide effective steric stability and electrostatic stability for formulations.

[0009] The present invention provides a suspension-type pesticide formulation prepared by dispersing fine particles of hydrophobic solid pesticides in an aqueous solvent, which helps reduce and / or prevent aggregation and soft aggregation. [Modes for carrying out the invention]

[0010] According to a first aspect of the present invention, i) Copolymer dispersants comprising a copolymer of acrylic acid, a hydrophobic monomer, an alkyl acrylate of monoalkyl polyethylene glycol, and optionally a strong acid derivative of (meth)acrylic acid: and ii) Nonionic graft copolymers of acrylic acid esters and oxyalkylenes: and iii) At least one hydrophobic solid pesticide active substance dispersed in an auxiliary aqueous medium: A suspension-type water-medium agrochemical formulation containing the above is provided.

[0011] According to a second aspect of the present invention, a concentrate formulation suitable for producing the pesticide formulation of the first aspect is provided. Herein, the concentrate formulation includes the following: i) Copolymer dispersants comprising a copolymer of acrylic acid, a hydrophobic monomer, an alkyl acrylate of monoalkyl polyethylene glycol, and optionally a strong acid derivative of (meth)acrylic acid: and ii) Nonionic graft copolymers of acrylic acid esters and oxyalkylenes: and iii) At least one hydrophobic solid pesticide active substance dispersed in an auxiliary aqueous medium:

[0012] According to a third aspect of the present invention, the use of the following combinations is provided: Copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycol, and optionally strong acid derivatives of (meth)acrylic acid: and Nonionic graft copolymers of acrylic acid esters and oxyalkylenes The use of the above combination is provided as a dispersant in a pesticide formulation containing a hydrophobic solid pesticide active substance.

[0013] A fourth aspect of the present invention provides a method for treating vegetation to control pests, comprising applying a formulation of the first aspect and / or a diluted concentrated formulation of the second aspect to the vegetation or the surrounding environment of the vegetation.

[0014] It has been found that a combination of polymers formed from acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycol, and optionally strong acid derivatives of (meth)acrylic acid, when used in suspension-type pesticide formulations containing hydrophobic solid pesticide active substances, provides desirable dispersion properties and significantly reduces crystal growth, in conjunction with nonionic graft copolymers of acrylic acid esters and oxyalkylenes.

[0015] Where used herein, the terms “for example,” “for instance,” “such as,” or “including” mean to provide examples that further clarify a more general subject. Unless otherwise specified, these examples are provided solely to aid in understanding the uses described herein and are not intended to limit anything.

[0016] When describing the number of carbon atoms in a substituent (for example, "C1-C6 alkyl"), it should be understood that this number refers to the total number of carbon atoms present in the substituent, including those arbitrarily present in any branched group. Furthermore, when describing the number of carbon atoms in a fatty acid, for example, this refers to the total number of carbon atoms, including those located in the carboxylic acid and those arbitrarily present in any branched group.

[0017] The copolymer dispersant comprises copolymers of acrylic acid, hydrophobic monomers, alkyl acrylates of monoalkyl polyethylene glycol, and optionally, strong acid derivatives of (meth)acrylic acid.

[0018] The acrylic monomers used to form the copolymer may be selected from (meth)acrylic acid or its salts, (meth)acrylamide, (meth)acrylonitrile, C1-6-alkyl (meth)acrylate, such as ethyl (meth)acrylate, butyl (meth)acrylate or hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc., substituted C1-6-alkyl (meth)acrylate, such as glycidyl methacrylate and acetoacetoxyethyl methacrylate, etc., di(C1-4-alkylamino)C1-6-alkyl (meth)acrylate, such as dimethylaminoethyl acrylate or diethylaminoethyl acrylate, etc., C1-6-alkylamine, amides formed from substituted C1-6-alkylamine, such as ammonium 2-amino-2-methyl-1-propanesulfonate, etc., or di(C1-4-alkylamino)C1-6-alkylamine, and their (meth)acrylic acid and their C1-4-alkyl halide adducts.

[0019] Preferably, the acrylic monomer may be acrylic acid, methacrylic acid, crotonic acid, or a mixture thereof. More preferably, the monomer is acrylic acid.

[0020] The hydrophobic monomer may be selected from any monomer that is water-insoluble. In particular, the hydrophobic monomer may be selected from hydrophobic alkyl (meth)acrylate, styrenes, and vinyl compounds and vinyl aromatic monomers.

[0021] In particular, vinyl aromatic monomers may be preferred in some cases.

[0022] The vinyl aromatic monomer can be styrene itself, or substituted styrene, particularly hydrocarbyl-substituted styrene, preferably alkyl-substituted styrene, and preferably those with substituents on the vinyl group or the aromatic ring of styrene, such as α-methylstyrene and vinyltoluene.

[0023] Suitable vinyl aromatic monomers may preferably contain 8 to 20 carbon atoms, most preferably 8 to 14 carbon atoms. Styrenes and substituted styrenes are preferred, and when substituents are present, the substituents are C1-C6 alkyl groups.

[0024] Examples of vinyl aromatic monomers are styrenes including substituted styrenes, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, α-methylstyrene, and halogenated styrenes.

[0025] The styrene monomer can be or may contain styrene monomers containing strongly acidic substituents, especially sulfonic acid substituents. When present, such strongly acid-modified monomers usually form 1 to 30 mol%, more usually 2 to 20 mol%, preferably 5 to 15 mol% of the styrene monomers in the copolymer.

[0026] Preferably, the hydrophobic monomer can be styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, or a combination thereof. More preferably, the hydrophobic monomer can be styrene.

[0027] The alkyl acrylate of monoalkyl polyethylene glycol may preferably be a nonionic hydrophilic monomer.

[0028] The alkyl group as part of the alkyl acrylate or monoalkyl group may be independently selected from C1-C6 alkyl, and especially C1-C3 alkyl. The alkyl group may preferably be selected from methyl, ethyl, n-butyl, or t-butyl. Preferably, the alkyl group is methyl.

[0029] The number-average molecular weight of monoalkyl polyethylene glycol (i.e., only the PEG chain of monoalkyl polyethylene glycol, and not the entire alkyl acrylate) can range from at least 300 daltons, preferably 350 to 900 daltons, and more preferably 400 to 600 daltons.

[0030] Some of the monoalkyl polyethylene glycols used as initial materials in this invention are commercially available. Thus, methyl ethers with total molecular weights of 500 and 550, commercially known as methoxypolyethylene glycol 550 and methoxypolyethylene glycol 750, respectively, are available on the market.

[0031] Preferably, the alkyl acrylate of the monoalkyl polyethylene glycol is methoxypolyethylene glycol methacrylate (MPEGMA), and more specifically, methoxypolyethylene glycol 500 methacrylate.

[0032] Examples of strong acid derivatives of (meth)acrylic acid include strong acids containing a sulfate group or a sulfonic acid group (or salts thereof). Examples of such monomers include acrylamide methylpropyl sulfonate (AMPS) and (meth)acrylic acid isethionate.

[0033] If present, such strongly acid-modified monomers typically form 1 to 30 mol%, more commonly 2 to 20 mol%, and preferably 5 to 15 mol%, of the acrylic acid monomers in the copolymer.

[0034] The polymer may be formed from hydrophobic monomers and may be a water-soluble polymer. The solubility arises as a result of the neutralization of the polymer.

[0035] As used in this disclosure, the term “copolymer” will be understood to include polymers having two components, terpolymers and tetrapolymers, and generally any polymer having two or three or more components. The copolymer may preferably be a random terpolymer or tetrapolymer, and may optionally have a strong acid derivative of a (meth)acrylic acid monomer.

[0036] Copolymers can be formed by any suitable method, such as free radical solution polymerization or controlled living polymerization. The above monomers can be added simultaneously over a controlled period of time using a suitable initiator.

[0037] The amount of acrylic acid monomer present in the polymer can be in the range of 10% to 90% by mass. Preferably, it is 15% to 60% by mass. More preferably, it is 20% to 50% by mass. Most preferably, it is 30% to 40% by mass.

[0038] The amount of vinyl aromatic monomer present in the polymer can be in the range of 10% to 90% by mass. Preferably, it is 15% to 60% by mass. More preferably, it is 15% to 40% by mass. Most preferably, it is 20% to 30% by mass.

[0039] The amount of alkyl acrylate of polyethylene glycol monomer present in the polymer can be in the range of 10% to 90% by mass. Preferably, it is 15% to 60% by mass. More preferably, it is 20% to 50% by mass. Most preferably, it is 30% to 40% by mass.

[0040] If present, such strongly acid-modified monomers typically constitute 1 to 30 mol%, more commonly 2 to 20 mol%, and preferably 5 to 15 mol%, of the acrylic acid monomers in the copolymer.

[0041] Other monomers may include, for example, acidic monomers such as itaconic acid or maleic acid or their anhydrides; strongly acidic monomers such as methallyl sulfonic acid (or its salts); or non-acidic acrylic monomers such as alkyl esters, especially C1-C6 alkyl esters, such as methyl methacrylate, butyl methacrylate, or butyl acrylate; or hydroxyalkyl esters, especially C1-C6 hydroxyalkyl esters, such as hydroxyethyl methacrylate or hydroxypropyl methacrylate; or vinyl monomers such as vinyl acetate. Typically, the proportion of such other monomers is about 10 mol% or less of the total monomers used, usually about 7 mol% or less, and more usually about 5 mol% or less.

[0042] By including monomers having strongly acidic substituents in polymer dispersants, it is possible to improve the dispersion of pesticide formulations in solid granular form when dispersed in hard water, particularly water with hardness exceeding 500 ppm, for example, up to 1,000 ppm, up to 2,000 ppm, and even up to 5,000 ppm.

[0043] The polymer may have a molecular weight of less than 500,000 daltons. Preferably, it is less than 100,000 daltons. More preferably, it is less than 75,000 daltons. The molecular weight may be in the range of 5,000 to 75,000 daltons. More preferably, it is in the range of 10,000 to 60,000 daltons. Even more preferably, it is in the range of 15,000 to 50,000 daltons. Most preferably, it is in the range of 20,000 to 40,000 daltons.

[0044] The polymer can be used as a free acid or salt. In practice, the form present in the formulation is determined by the acidity of the formulation. Preferably, the formulation is nearly neutral, and therefore most of the acid groups will exist as salts. The cations in any such salt can be alkali metals, particularly sodium and / or potassium, ammonium, or amines including alkanolamines such as ethanolamine, particularly triethanolamine. Sodium or potassium salt forms of the stabilized polymer are particularly preferred.

[0045] The degree of neutralization is at least 70%, preferably 75% to 85%. Neutralization with sodium is preferred.

[0046] The pH of the polymer may be in the range of 4.0 to 11.0. More preferably, it is in the range of 5.0 to 10.0. Even more preferably, it is in the range of 5.5 to 9.0. Most preferably, it is in the range of 6.0 to 8.0.

[0047] The formulation contains a nonionic graft copolymer of an acrylic acid ester and an oxyalkylene.

[0048] The acrylic acid ester may be an acrylic acid ester that can be selected from non-acidic acrylic monomers, such as alkyl esters, particularly C1-C6 alkyl esters.

[0049] Preferably, the alkyl ester can be selected from methyl methacrylate, butyl methacrylate, or butyl acrylate. Most preferably, it is methyl methacrylate.

[0050] The number of acrylic acid ester monomer residues in the (poly)acrylic acid ester chain is preferably in the range of 2 to 50, more preferably 5 to 40, and particularly 10 to 30.

[0051] The oxyalkylene group has the chemical formula -(C y H 2yO) - can be selected from the base, where y is an integer selected from 2, 3, or 4. Preferably, y is 2 or 3.

[0052] The oxyalkylene group may be selected from oxyethylene, oxypropylene, oxybutylene, or oxytetramethylene. Preferably, the oxyalkylene group is selected from oxyethylene (EO) and / or oxypropylene (PO).

[0053] When the oxyalkylene chain is a homopolymer, a homopolymer of ethylene oxide or propylene oxide is preferred. More preferably, a homopolymer of ethylene oxide is particularly preferred.

[0054] If there are two or more oxyalkylene groups (i.e., n is 2 or more) and at least two are part of the same oxyalkylene chain, the oxyalkylene groups may be identical or different along the oxyalkylene chain. In this embodiment, the oxyalkylene chain may be a block or random copolymer of different oxyalkylene groups.

[0055] Typically, when copolymer chains of ethylene and propylene oxide units are used, the molar ratio of ethylene oxide units used is at least 50%, and more commonly at least 70%.

[0056] The total number of alkylene oxide residues in the (poly)alkylene oxide chain is preferably in the range of 2 to 50, more preferably 5 to 40, and particularly 10 to 25.

[0057] The molecular weight of nonionic graft copolymers of acrylic acid esters and oxyalkylenes is typically 5,000 to 40,000, particularly 7,000 to 30,000, even more particularly 8,000 to 25,000, and among these, approximately 9,000 to 18,000.

[0058] Any nonionic graft copolymer of acrylic acid esters and oxyalkylenes may be used. Preferably, the copolymer is a nonionic polymethyl methacrylate-polyethylene oxide graft copolymer.

[0059] The agrochemical actives used in the formulations according to the present invention are hydrophobic solid agrochemical actives. These are agrochemically active compounds that are solid at room temperature.

[0060] In agricultural chemistry, the logarithm of the concentration ratio of unionized solutes in two solvents, octanol and water, is used as an indicator of the lipophilicity of pesticides and is known as the octanol / water coefficient, or logP. Pesticides with pesticide activity may have a logP value greater than 2.5. More preferably, it is in the range of 2.5 to 4.5.

[0061] In the context of this invention, "pesticide-active substance" refers to a biocide that is a plant protection agent, and more specifically, to a biocide that is a chemical substance capable of killing various forms of organisms used in fields such as medicine, agriculture, forestry, and mosquito control. The group of biocides also includes so-called plant growth regulators.

[0062] The biocides used in the pesticide formulations of the present invention can typically be divided into two subgroups: Pesticides include fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides, and rodenticides. Antimicrobial agents include germicidal agents (germicides), antibiotics, antibacterial agents, antiviral agents, antimicrobial agents, antiprotozoal agents, and antiparasitic agents.

[0063] In particular, biocides selected from insecticides, fungicides, or herbicides may be especially preferred.

[0064] In this invention, the term "hydrophobic solid pesticide" means a substance that is very poorly soluble in water or almost insoluble.

[0065] Typical pesticides used in this invention include the following: Examples of herbicides include flufenacet, bromoxynil octanoate, trifluralin, benfluralin, isouron, metribuzin, daimuron, ametryn, dichlobanil, alachlor, linuron, and diuron. Fungicides include, for example, isoprothiolane and chlorothalonil; azole fungicides include difenoconazole, cyproconazole, prothioconazole, epoxyconazole, tebuconazole, prochloraz, penconazole, flusilazole, metconazole, triadimenol, and hexaconazole. Selected from nazole, flutriazole, and triflumizole: The fenbuco group consisting of nazole, bromconazole, fluquinconazole, azaconazole, triticonazole, triazimephone, and imibenconazole: Strobilurin analogs, such as kresoxim-methyl and pyraclostorubin: Maneb, mancozeb, ziram, thiram: Examples of insecticides include dimethylethylsulfinyl isopropylthiophosphate, metolcarb, phosalone, buprofezin, azoxystrobin, and methyl isothiocyanate. and mixtures thereof.

[0066] Most preferably, the active substance present in the pesticide formulation of the present invention is selected from the following: a herbicide, for example, flufenacet or metribuzin; an azole fungicide, for example, difenoconazole, cyproconazole, or prothioconazole; or an insecticide, for example, buprofezin or azoxystrobin.

[0067] In particular, combinations of active substances such as azoxystrobin with cyproconazole and / or difenoconazole may be preferred.

[0068] Pesticide active compounds, such as insecticides and fungicides, require formulations that allow the active compound to be taken up by plants / target organisms.

[0069] As used herein, the term “agrochemical formulation” refers to a composition comprising an active agrochemical and is intended to encompass all forms of composition, including concentrates and spray formulations. Unless otherwise specified, the agrochemical formulations of the present invention may be in the form of concentrates, diluted concentrates, or spray formulations.

[0070] The dispersant of the present invention may be combined with other components to form a pesticide formulation containing at least one pesticide active substance.

[0071] The formulations of the present invention are aqueous suspension formulations. In concentrated form, these formulations are generally used to disperse water-insoluble active ingredients, either as a dispersion directly present in the aqueous phase, absorbed or adsorbed onto a solid support, or as a liquid or solution in which the active substance is microencapsulated. These are generally known as suspension concentrates (SCs), in which the active compound exists as a solid.

[0072] These aqueous pesticide concentrates are pesticide compositions designed to be diluted with water (or an aqueous liquid) to form the corresponding spray formulation.

[0073] A spray formulation is an aqueous pesticide preparation that contains all the components desired for application to plants or their environment. A spray formulation can be formed by simple dilution of a concentrate containing the desired components (other than water).

[0074] This allows the dispersant to be incorporated into the formulation of the pesticide active compound (in-can / built-in formulation).

[0075] Depending on customer needs, the concentrate thus formed may typically contain up to 95% by mass of pesticide active material. The concentrate can be diluted for use, yielding a diluted composition having a pesticide active concentration of about 0.5% to about 1% by mass. The diluted composition (for example, when spray application rate is 10 to 500 l·ha) -1 In a spray formulation, the pesticide activity concentration may be in the range of approximately 0.001% to approximately 1% by mass of the total sprayed formulation.

[0076] The copolymer dispersant of the present invention is typically used in an amount proportional to the amount of active pesticide in the formulation. In a pesticide formulation concentrate, the proportion of the dispersant depends on the solubility of the components in the liquid carrier. Typically, the concentration of the copolymer dispersant in such a concentrate is from 1% to 20% by mass. Preferably, it is from 1.5% to 10% by mass. More preferably, it is from 2% to 5% by mass.

[0077] Typically, the concentration of the graft copolymer in such a concentrate is 1% to 20% by mass. Preferably, it is 1.5% to 10% by mass. More preferably, it is 2% to 5% by mass.

[0078] The mass ratio of the dispersant to the graft copolymer in the concentrate is preferably about 0.7:1 to about 4:1. More preferably, it is about 0.8:3.5 to about 3.5:1. In particular, the mass ratio of the dispersant to the graft copolymer may be 3:1 to 1:1.

[0079] The mass ratio of the dispersant and graft copolymer to the active pesticide in concentrates and diluted concentrated pesticide formulations is preferably about 0.05:1 to about 0.2:1. More preferably, it is about 0.7:1 to about 0.15:1. This ratio range is generally maintained in concentrated formulations (e.g., when the adjuvant is contained in a dispersible liquid concentrate or a dispersible solid granule formulation) and spray formulations.

[0080] When a concentrate (solid or liquid) is used as a source of active pesticides and / or dispersants and graft copolymers, the concentrate is typically diluted to form a spray formulation. Dilution may involve using 1 to 10,000 times, and especially 10 to 1,000 times, the total weight of the concentrate in water to form a spray formulation.

[0081] When pesticide active substances exist as solid particles in an aqueous end-use formulation, in most cases they exist primarily as active pesticide particles. However, if desired, the active pesticide can be supported on a solid carrier, such as silica or diatomaceous earth, and the solid carrier can be a solid support, filler, or diluent material as described above.

[0082] Spray formulations typically have a pH ranging from moderately acidic (e.g., around 3) to moderately alkaline (e.g., around 10), especially close to neutral (e.g., around 5-8). More concentrated formulations may have similar acidity / alkalinity, but since they are mostly non-aqueous, pH is not always an appropriate measure of their properties.

[0083] A particular problem is crystal growth, such as crystal growth due to "Ostwald aging" of the active ingredient during relatively short-term storage. Crystal growth due to "Ostwald aging" generally occurs when small crystals (with a larger surface area than larger crystals) dissolve in the aqueous phase, and the material is transported through the continuous phase to the nucleation sites of larger crystals. As a result, crystals of the active ingredient may aggregate and settle, leading to a non-uniform formulation: during application, the filters and nozzles of the spraying device may become clogged, and the biological effect may be reduced. In aqueous suspensions and concentrates, the purpose of the dispersant is to prevent an excessive increase in crystal size.

[0084] Surprisingly, it was also found that the combination of dispersants in the present invention has the effect of slowing down and / or stopping crystal growth in the active ingredient that has a tendency to grow crystals through "Ostwald aging".

[0085] In particular, combinations of dispersants are useful for inhibiting crystal growth for certain lipophilic active substances (i.e., hydrophobic and poorly dispersible active substances). In agricultural chemistry, the logarithm of the concentration ratio of unionized solutes in two solvents, octanol and water, respectively, is used as an indicator of the lipophilicity of pesticides and is known as the octanol / water coefficient, Ko / w, or logP. The polymers of the present invention are suitable for the preparation of aqueous pesticide formulations containing 50 to 1100 g / L of at least one pesticide having a logP of -1.5 to +6.

[0086] The risk of crystallization can be predicted by evaluating the parameter Ko / w or logP. Specifically, this risk refers to the occurrence after 7 days when 5 ml of EC or EW is diluted with 95 ml of water and stored in a refrigerator (1°C), and the emulsion is passed through a 5 μm filter. These experimental parameters mainly refer to the preference for solubilization in water or octanol (known as the octanol / water partition coefficient, Ko / w, or logP). The range of logP values ​​for which this invention is effective covers pesticides with logP between 2.5 and 4.5.

[0087] The formulation may also contain additional components selected from pigments, dyes, micronutrients, pesticides, fillers, and combinations thereof.

[0088] The pesticide formulation may include, in conjunction with the primary adjuvant and coadjuvant, a solvent (other than water), such as monopropylene glycol, a vegetable oil or mineral oil, or an oil that may be a spray oil (an oil included in the spray formulation as a non-surfactant adjuvant). When used, such a solvent is typically included in an amount of 5% to 500% by mass, preferably 10% to 100% by mass, based on the mass of the dispersant. Such combinations may also include, for example, salts of ammonium chloride and / or sodium benzoate, and / or urea as a gel inhibitor.

[0089] The pesticide formulation may also contain other ingredients as needed. These other ingredients may be selected from the following: • Binders, especially those that dissolve readily in water and provide low-viscosity solutions at high binder concentrations, such as polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, gum arabic, sugars such as sucrose or sorbitol, starch, ethylene-vinyl acetate copolymer, sucrose, and alginate, etc. • Diluents, absorbents, or carriers, e.g., carbon black; talc; diatomaceous earth; kaolin; aluminum stearate, calcium stearate, or magnesium stearate; sodium tripolyphosphate; sodium tetraborate; sodium sulfate; sodium silicate, aluminum silicate, and sodium silicate-aluminum silicate mixtures; sodium benzoate, etc. • Disintegrants, such as surfactants; materials that swell in water, such as carboxymethylcellulose, collodion, polyvinylpyrrolidone, and microcrystalline cellulose; swelling agents: salts, such as sodium acetate or potassium acetate, sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, ammonium sulfate, and dipotassium hydrogen phosphate, etc. • Wetting agents, such as alcohol ethoxylates and alcohol ethoxylate / propoxylate wetting agents: • Dispersants, such as sulfonated naphthaleneformaldehyde condensates and acrylic acid copolymers, such as comb-type copolymers having capped polyethylene glycol side chains on a polyacrylic acid backbone: • Emulsifiers, such as alcohol ethoxylates, ABA block copolymers, castor oil ethoxylates, etc. • Antifoaming agents, such as polysiloxane antifoaming agents, typically in an amount of 0.005% to 10% by mass of the formulation: • Viscosity modifiers, such as commercially available water-soluble or miscible gums, such as xanthan gum, and / or cellulosic materials, such as carboxy-, methyl-, ethyl-, or propyl-cellulose: and / or • Preservatives and / or antimicrobial agents, such as organic acids or their esters or salts, such as ascorbic acid-based agents, such as ascorbyl palmitate; sorbic acid-based agents, such as potassium sorbate; benzoic acid-based agents, such as benzoic acid, methyl 4-hydroxybenzoate and propyl 4-hydroxybenzoate; propionic acid-based agents, such as sodium propionate; phenol-based agents, such as sodium 2-phenylphenate; 1,2-benzoisothiazolin-3-one; or formaldehyde itself or paraformaldehyde; or inorganic materials, such as sulfites and their salts, typically in an amount of 0.01% to 1% by mass of the formulation.

[0090] The pesticide formulation according to the present invention may also contain components. The surfactant may include a surfactant-type dispersant.

[0091] Other adjuvants, such as surfactant adjuvants, may be included in the compositions and formulations of the present invention and in the compositions and formulations used in the present invention. Examples include alkyl polysaccharides (more appropriately called alkyl oligosaccharides): fatty amine ethoxylates, such as coconut alkylamine 2EO: and derivatives of alkyl (alkenyl) succinic anhydrides, particularly those described in International Publications WO94 / 00508 and WO96 / 16930.

[0092] The formulation may contain at least one nutrient. Nutrients refer to chemical elements and compounds that are desirable or necessary to promote or improve plant growth. Nutrients are generally described as macronutrients or micronutrients. Nutrients suitable for use in the concentrate according to the present invention are micronutrient compounds, which are preferably solid at room temperature or partially soluble.

[0093] Micronutrients typically refer to trace metals or trace elements and are often administered in low doses. Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum, and manganese. The dispersant of the present invention is expected to have broad applicability to all types of micronutrients.

[0094] Micronutrients may be in soluble form, or they may be included as insoluble solids, or they may be in the form of salts or chelates. Preferably, the micronutrients are in the form of carbonates or oxides.

[0095] Preferably, the micronutrients may be selected from zinc, calcium, molybdenum or manganese, or magnesium. Particularly preferred micronutrients for use in the present invention may be selected from zinc oxide, manganese carbonate, manganese oxide, or calcium carbonate.

[0096] The amount of micronutrients in the concentrate is typically 5% to 40% by mass, more commonly 10% to 35% by mass, and especially 15% to 30% by mass, based on the total mass of the concentrate.

[0097] Typically, when mixed into the formulation during manufacturing, the average particle size of the solid pesticide is 50 μm to 100 μm, but the formulation is typically wet-milled after mixing to reduce the average particle size to 1 μm to 10 μm, more preferably 1 μm to 5 μm.

[0098] The formulations of the present invention may also contain at least one macronutrient. Macronutrients typically refer to those containing nitrogen, phosphorus, and potassium, and include fertilizers, such as ammonium sulfate, and water conditioners. Suitable macronutrients include fertilizers and other nitrogen, phosphorus, or sulfur-containing compounds, as well as water conditioners.

[0099] Appropriate fertilizers include inorganic fertilizers that provide nutrients such as nitrogen, phosphorus, potassium, or sulfur. Examples of such fertilizers are listed below: In the case of nitrogen as a nutrient: nitrates and / or ammonium salts such as ammonium nitrate (including combinations with urea). For example, uranium-type materials, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium phosphate, especially ammonium phosphate, diammonium phosphate and ammonium polyphosphate, ammonium sulfate, and less commonly used calcium nitrate, sodium nitrate, potassium nitrate and ammonium chloride: In the case of phosphorus as a nutrient: for example, phosphorus in acidic forms such as phosphoric acid, pyrophosphate, or polyphosphate, but more commonly in salt form, such as ammonium phosphate, especially ammonium phosphate, diammonium phosphate, and ammonium polyphosphate, and potassium phosphate, especially potassium dihydrogen phosphate and potassium polyphosphate. For sulfur as a nutrient: mixed sulfates of ammonium sulfate and potassium sulfate, for example, magnesium.

[0100] Biostimulants can enhance metabolic or physiological processes, such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or combinations thereof. Non-exclusive examples of biostimulants include seaweed extracts (e.g., Ascophyllum nodosum), humic acids (e.g., potassium humate), fulvic acid, myo-inositol, glycine, and combinations thereof.

[0101] The present invention further includes a method for treating plants using a formulation according to the first embodiment.

[0102] Therefore, the present invention further includes methods of use, including the following: A method of killing or suppressing vegetation by applying a spray formulation containing at least one dispersed-phase pesticide and an adjuvant of the first embodiment to vegetation or the surrounding environment of vegetation, such as the soil around plants: and / or A method for killing or suppressing plant pests by applying a spray formulation containing one or more types of pesticides, such as insecticides, fungicides, or acaricides, and an adjuvant according to the first embodiment, to plants or the surrounding environment of plants, such as the soil around the plants.

[0103] As used herein, the terms “dispersant” or “dispersive” refer to compounds that, when added to a pesticide formulation, improve the desired effect of the pesticide. Dispersants may affect diluents, mixtures, active substances, or targets by improving the performance of the active substance.

[0104] Preferably, when formulated directly into pesticide concentrates, the dispersant of the present invention may be used as either the sole component or the primary dispersing agent.

[0105] The materials of the present invention are more readily diluted in agricultural concentrates and exhibit lower fluid viscosity in aqueous systems when diluted in concentrates or with water before spraying. This behavior provides improved ease of use, particularly in cold water, both during the preparation and dilution of products containing them. Reduced foam stability is also observed, thereby decreasing the need for foam control agents. The dispersants of the present invention can be added to pesticide formulations without undesirable thickening or destabilization.

[0106] Dispersion involves solid particles with low water solubility, and therefore, particle size and distribution are factors that reflect the stability of the dispersion. To ensure dispersion stability over long periods, uniform particle distribution is crucial. Furthermore, effective dispersants prevent particle clumping and phase separation. Therefore, dispersions with small particle size, uniform particle distribution, and limited particle size growth over time are likely to be more stable.

[0107] In the form of particle size distribution, particles have a median volume particle diameter value. The median volume particle diameter will be understood as the equivalent diameter of a sphere corresponding to a point on the distribution that exactly bisects the population. This point corresponds to 50% of the volume of all particles and is read in a cumulative distribution curve relating volume percentages to particle diameters; that is, 50% of the distribution is above this value and 50% is below it. This value is called the "D(v,0.5)" value and is determined as described herein.

[0108] Furthermore, also known as the "D(v,0.9)" value, this value represents the equivalent spherical diameter corresponding to 90% of the volume of all particles, and is read in the cumulative distribution curve that correlates the volume percentage with the particle diameter. In other words, these are the points where 10% of the distribution is above this value and 90% is below it.

[0109] The particle size values ​​used to determine the D(v,0.5) and D(v,0.9) values ​​are measured by techniques and methods described in more detail herein. It will be understood that the particle size values ​​defined below are based on a dispersant and graft copolymer totaling 4.82% by mass, as shown in the examples.

[0110] It is generally known that a particle size of 1 to 10 μm is preferable to obtain a dispersion with desirable properties.

[0111] initial The particles present in the dispersant of the present invention may have an initial D(v,0.5) value in the range of 2.5 μm to 8.0 μm over 0 days. Preferably, it is in the range of 3.0 μm to 7.0 μm. More preferably, it is in the range of 3.2 μm to 6.0 μm. Most preferably, it is in the range of 3.3 μm to 6.0 μm.

[0112] The particles present in the dispersant of the present invention may have a D(v,0.9) value in the range of 5.0 μm to 14.0 μm over 0 days. Preferably, it is in the range of 5.5 μm to 12.0 μm. More preferably, it is in the range of 6.0 μm to 11.0 μm.

[0113] At 54℃ The particles present in the dispersant of the present invention may have a D(v,0.5) value within the range of 1.0 μm to 20.0 μm after 7 days and at 54°C. Preferably, it is within the range of 2.0 μm to 18.0 μm. More preferably, it is within the range of 3.0 μm to 15.0 μm. Most preferably, it is within the range of 3.5 μm to 13.0 μm.

[0114] The particles present in the dispersant of the present invention may have a D(v,0.9) value within the range of 5.0 μm to 75.0 μm after 7 days and at 54°C. Preferably, it is within the range of 6.0 μm to 65.0 μm. More preferably, it is within the range of 7.0 μm to 62.0 μm. Most preferably, it is within the range of 9.0 μm to 60.0 μm.

[0115] The particles present in the dispersant of the present invention, when maintained at 54°C, exhibit a change of 150% or less in either or both of D(v,0.5) and D(v,0.9) between day 0 and day 7, preferably 130% or less, and most preferably 110% or less.

[0116] As a result, the dispersant of the present invention provides a good particle size and particle size distribution within a desirable range for the emulsion concentrate. In addition, the emulsion of the present invention maintains a desirable particle size and particle size distribution under storage conditions over time.

[0117] All features described herein may be combined in any combination with any of the above embodiments.

[0118] To make the present invention easier to understand, the following description is provided as an example.

[0119] It should be understood that all tests and physical properties described herein were determined at atmospheric pressure and room temperature (25°C), unless otherwise stated in this document or in the referenced test methods and procedures.

[0120] The performance of the adjuvant composition was determined using the following test methods.

[0121] Examples The formulations were tested and evaluated as follows after being stored at room temperature (RT) for 24 hours, and after being stored at 54°C for 7 and 14 days: - Visual evaluation of separation - pH (undiluted) - Viscosity (undiluted, Brookfield viscosity, 10 rpm and 100 rpm) - Particle size distribution (PSD, Malvern Mastersizer, Watercell SM200) - Suspension ratio (CIPAC MT 180) - Microscopic examination (10% dilution, Olympus B51 microscope, 20x magnification with polarization)

[0122] After heat storage, the separated samples were rolled for approximately 15 minutes (60 rpm, benchtop roller) before completing the tests. Furthermore, the rheological properties of the samples on day 1 and day 14 were also evaluated (TA Discovery DHR-3 rheometer, DIN concentric cylinder, vibration, creep, flow).

[0123] The following materials were used in the examples.

[0124] Dispersant Copolymer dispersant - D1-MPEG-MA, AMPS, acrylic acid, and styrene copolymer Nonionic graft copolymer - D2-methacrylic acid-containing methyl methacrylate polymer and methoxypolyoxyethylene methacrylate

[0125] Other substances Flufenaacet - Active Substance (Glentham Life Science) Silcolapse 5020 - Antifoaming agent Pricerine 9091 - Antifreeze Proxel GXL - Biocide Kelzan RD - Rheology Modifier

[0126] Formed formulation 15% of the total surfactant load relative to the active substance was used in a 3:1 ratio (dispersant:wetting agent). The dispersant, wetting agent, and water were combined and mixed until completely solubilized (low shear mixing, 500 rpm). All other components were added and mixed by hand with a spatula to dissolve them.

[0127] The formulation was mixed at high shear for 2 minutes (Ultra Turrax, 13500 rpm). The formulation was ground until the desired particle size d0.9 < 10 μm was obtained (Eiger Mini Mill, 3000 rpm). This was achieved by grinding the formulation for approximately 10 minutes.

[0128] Xanthan gum was prepared in a separate vial using 10% aqueous phase and pricerine, and then homogenized into a mixture after grinding.

[0129] The following formulations were manufactured, with A1 and A2 being comparative formulations and C1 and C2 being the formulations of the present invention.

[0130] C1 has a copolymer dispersant-to-graft copolymer ratio of 1:1, while C2 has a copolymer dispersant-to-graft copolymer ratio of 3:1.

[0131] [Table 1]

[0132] result The following results were obtained for the concentrated formulations shown in Table 1.

[0133] [Table 2]

[0134] Here, st stands for separation, PSD for particle size dispersion, D1 for 1 day, D14 for 14 days, RT for room temperature, and 54 for 54°C.

[0135] Table 2 shows synergistic improvements in dispersion performance and slower crystal growth (smaller increase in PSD) in the formulations over 14 days at both room temperature and high temperature. C1 and C2 show better particle size control with little to no decrease in suspension, in contrast to the comparative formulations.

[0136] Crystal growth results Next, the concentrates shown in Table 1 were diluted, and the particle size dispersion was measured again over 7 days at low and high temperatures. The results of the particle size dispersion are shown in Table 2.

[0137] [Table 3]

[0138] Table 3 shows the crystal growth results for all tested formulations. The results clearly demonstrate that formulation (A2) of the present invention exhibits good particle size dispersion over 7 days, thereby providing good suppression of crystal growth. This indicates that the crystal growth suppression effect is observed even when the stock solution is diluted to 5%.

[0139] It should be understood that the present invention should not be limited to the details of the embodiments described above merely as examples, and that many variations are possible.

Claims

1. i) a copolymer dispersant comprising a copolymer of an acrylic acid monomer selected from (meth)acrylic acid or a salt thereof, (meth)acrylamide, (meth)acrylonitrile, C1-6-alkyl (meth)acrylate, butyl (meth)acrylate or hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, substituted C1-6-alkyl (meth)acrylate, and di(C1-4-alkylamino)C1-6-alkyl (meth)acrylate; a hydrophobic monomer; an alkyl acrylate of a monoalkyl polyethylene glycol; and optionally a strong acid derivative of (meth)acrylic acid; ii) nonionic polymethyl methacrylate-polyethylene oxide graft copolymer; and iii) at least one hydrophobic solid pesticidal active dispersed in the auxiliary aqueous medium; Including, the hydrophobic monomer is a vinyl aromatic monomer selected from styrene or alkyl-substituted styrene, and the strong acid derivative of (meth)acrylic acid is a strong acid containing a sulfate group or a sulfonate group, or a salt thereof; A water-borne suspended pesticide formulation, wherein the ratio of said copolymer dispersant to said nonionic graft copolymer is 3:

1.

2. 10. The formulation of claim 1, wherein the acrylic acid monomer is acrylic acid, methacrylic acid, crotonic acid, or a mixture thereof.

3. 3. The formulation of claim 1 or 2, wherein the hydrophobic monomer is a vinyl aromatic monomer selected from styrene or alkyl-substituted styrene.

4. The formulation of any one of claims 1 to 3, wherein the alkyl acrylate of monoalkyl polyethylene glycol is methoxypolyethylene glycol methacrylate (MPEGMA).

5. The formulation according to any one of claims 1 to 4, wherein the strong acid derivative of (meth)acrylic acid is selected from acrylamidomethylpropylsulfonate (AMPS) or (meth)acrylic acid isethionate.

6. A formulation according to any one of claims 1 to 5, wherein the molecular weight of the nonionic graft copolymer of acrylic ester and oxyalkylene is between 5,000 and 40,000.

7. 7. A formulation according to any one of claims 1 to 6, wherein the hydrophobic solid pesticidal active substance is selected from the herbicides flufenacet or metribuzin; the azole fungicides difenoconazole, cyproconazole, prothioconazole; or the insecticides buprofezin or azoxystrobin.

8. A concentrated formulation suitable for producing the pesticide formulation according to any one of claims 1 to 7, i) a copolymer dispersant comprising a copolymer of an acrylic acid monomer selected from (meth)acrylic acid or a salt thereof, (meth)acrylamide, (meth)acrylonitrile, C1-6-alkyl (meth)acrylate, butyl (meth)acrylate or hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, substituted C1-6-alkyl (meth)acrylate, and di(C1-4-alkylamino)C1-6-alkyl (meth)acrylate; a hydrophobic monomer; an alkyl acrylate of a monoalkyl polyethylene glycol; and optionally a strong acid derivative of (meth)acrylic acid; and ii) nonionic polymethyl methacrylate-polyethylene oxide graft copolymer; and iii) at least one hydrophobic solid pesticidal active dispersed in the auxiliary aqueous medium; Including, the hydrophobic monomer is a vinyl aromatic monomer selected from styrene or alkyl-substituted styrene, and the strong acid derivative of (meth)acrylic acid is a strong acid containing a sulfate group or a sulfonate group, or a salt thereof; A concentrated formulation wherein the ratio of the copolymer dispersant to the nonionic graft copolymer is 3:

1.

9. Copolymers of an acrylic monomer selected from (meth)acrylic acid or a salt thereof, (meth)acrylamide, (meth)acrylonitrile, C1-6-alkyl (meth)acrylate, butyl (meth)acrylate or hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, substituted C1-6-alkyl (meth)acrylate, and di(C1-4-alkylamino)C1-6-alkyl (meth)acrylate; with a hydrophobic monomer; with an alkyl acrylate of a monoalkyl polyethylene glycol; and optionally with a strong acid derivative of (meth)acrylic acid, as dispersing agents in pesticide formulations containing hydrophobic solid pesticide actives; and nonionic polymethyl methacrylate-polyethylene oxide graft copolymer; The use of a combination of the hydrophobic monomer is a vinyl aromatic monomer selected from styrene or alkyl-substituted styrene, and the strong acid derivative of (meth)acrylic acid is a strong acid containing a sulfate group or a sulfonate group, or a salt thereof; The ratio of said copolymer to said nonionic graft copolymer is 3:

1.

10. 10. A method for treating vegetation to control pests, comprising applying to the vegetation or to the surrounding environment of the vegetation a pesticide formulation according to any one of claims 1 to 7 and / or a diluted concentrate formulation according to claim 8.

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