CN117082976A - Stable emulsions - Google Patents

Abstract

An oil-in-water agrochemical suspension comprising (i) an aqueous phase; (ii) A liquid organic phase emulsified in the aqueous phase comprising at least one lipophilic active ingredient; (iii) At least 5w/w% salt relative to the total weight of the final emulsion; (iv) a thickener; (v) A combination of surfactants comprising a polyanionic block copolymer surfactant and a second surfactant; and (vi) a solid active ingredient. The invention further relates to tank mixtures and methods for controlling undesired vegetation, pests or diseases. The invention also relates to an emulsion for preparing said suspoemulsion.

Description

Stable emulsions

Technical Field

The present invention belongs to the field of agricultural chemistry. The present invention relates to stable emulsions and stable suspoemulsions for agricultural applications, to methods for their preparation, and to methods for controlling weeds, diseases and pests in plants.

Background

Emulsions are an important formulation type in agrochemistry. They are versatile formulations that can carry both water soluble and water insoluble components. Creating stable emulsions is challenging. The emulsion must be stable during the emulsification process, during storage, and must be stable upon tank mixing. Common problems include so-called "salting out" of one of the components when a high electrolyte loading is sought in the aqueous phase. Salting out occurs in solutions with high ionic strength, where the component with the smallest solubility precipitates from the aqueous phase. Additional problems arise because salts reduce the repulsion between emulsion droplets, which then coalesce and cause the oil phase to separate. This problem places a limit on the concentration of salts (electrolytes), for example the concentration of active ingredients in the form of electrolytes, and must be considered when designing high-load formulations.

WO 2017/098325 discloses polyanionic polymers and their use for stabilizing lipophilic active ingredients in aqueous dispersions, and agricultural compositions comprising the polyanionic surfactants. The polyanionic surfactants disclosed in WO 2017/098325 comprise an anchor moiety (hydrophobic) and a stabilizing moiety (hydrophilic), the latter typically being made from anionic sulfate monomers, wherein each moiety may be a homopolymer or a copolymer. WO 2017/098325 mentions the use of further common components in agrochemical formulations such as preservatives, rheology modifiers, anti-settling agents, defoamers, buffers, and liquid diluents, or surfactants such as ionic, anionic, nonionic, polymeric/co-polymeric, or non-polymeric/co-polymeric surfactants on page 18. According to WO 2017/098325, the composition using the polyanionic polymer may be an emulsion, a suspension concentrate, a capsule suspension, or a suspension emulsion. Although the polyanionic surfactants disclosed in WO 2017/098325 are mentioned for increasing the stability of agrochemical compositions in high salt environments, further improvements are always desirable.

A suspoemulsion may be manufactured by first separately preparing a concentrated oil-in-water Emulsion (EW) formulation and a Suspension Concentrate (SC) formulation, and then combining them. Creating a stable emulsion (or suspoemulsion) that additionally contains at least one solid active ingredient, i.e., suspoemulsion (suspoemulsion), presents a significant challenge to formulation development chemists. The greater the number and complexity of components, the greater these challenges and the formulation developer must avoid many potential problems. Some of these problems are aggregation of solid particles, crystal growth or coalescence of emulsion droplets, mainly due to ostwald ripening or hetero flocculation.

Disclosure of Invention

The inventors have developed an Emulsion (EW) formulation that is even more stable than those produced using only polyanionic block copolymer surfactants as disclosed in WO 2017/098325.

A first aspect is an oil-in-water agrochemical emulsion comprising:

(i) An aqueous phase, for example between 10w/w% and 90w/w% relative to the total weight of the final emulsion;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1w/w% and 15w/w% of a second surfactant, typically lipophilic, with respect to the total weight of the final emulsion, selected from sorbitan esters of fatty acids;

Polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate.

The emulsions of the present invention are unexpectedly stable, allowing for high salt loadings, even when the ionic strength of the aqueous phase in the formulation is high. As a result, the emulsions disclosed herein can be loaded with high concentrations of hydrophilic active ingredient electrolytes and other salts (e.g., fertilizers). Interactions between the different components of the formulation can be difficult to predict, and finding the proper combination of surfactants in the formulation can be challenging. The inventors have found that the combined use of a specific surfactant (second surfactant) with a polyanionic block copolymer surfactant (typically as those disclosed in WO 2017/098325) provides unexpectedly stable emulsion formulations (EW) even if high concentrations of salt are present in the aqueous phase. The formulation is also stable when diluted in water prior to field application (tank mix). Thus, another aspect of this document is a diluted aqueous tank mix comprising an adjuvant and the emulsion of the invention.

Another aspect of the invention relates to a process for preparing the emulsion of the invention, the process comprising:

(i) Emulsifying an organic phase into an aqueous phase, said organic phase comprising at least one lipophilic active ingredient, optionally a lipophilic organic solvent, and between 0.1 and 15w/w% relative to the total weight of the final emulsion of a second surfactant selected from the group consisting of

Sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from polyalkoxylated polyols or esters thereof, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate;

the aqueous phase comprising water and between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises charged monomers, and wherein the weight percent of charged monomers relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%, the aqueous phase optionally comprising less than 5w/w% salt relative to the total weight of the final emulsion;

(ii) Optionally, mixing the emulsion previously obtained with a first amount of thickener;

(iii) Mixing the emulsion obtained in the previous step with a salt in an amount up to a minimum amount of 5w/w% relative to the total weight of the final emulsion;

(iv) The emulsion obtained in the previous step is mixed with a thickener.

Thus, in the methods disclosed herein, a portion or all of the salt is added after the emulsification step, rather than preparing a premix of the phases containing all of the components prior to emulsification. The inventors have observed that the emulsion formulations obtained in this way are unexpectedly more stable.

The emulsion obtainable following the above-described process shows excellent stability and is also an aspect of the present invention.

Another aspect of the invention is the use of the emulsions of the invention for controlling undesired vegetation, pests or diseases. In another aspect is a method for controlling an undesired plant, pest or disease comprising contacting an effective amount of the emulsion of the present invention or a tank mix thereof with a locus of the undesired plant, pest or disease.

The emulsions of the invention can be used to prepare stable suspoemulsions, and thus another aspect of the invention is a suspoemulsion obtained by mixing the emulsions of the invention with an SC formulation.

Thus, another aspect of the invention is a suspoemulsion formulation comprising:

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%;

-between 0.1 and 15w/w% of a second surfactant selected from the group consisting of

Sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate;

and

(vi) Solid active ingredient.

Further aspects of the invention are:

aqueous tank-mixtures comprising adjuvants and the suspoemulsions of the invention.

A process for preparing the suspoemulsion of the present invention, which comprises mixing an aqueous suspension concentrate (SC formulation) with the emulsion of the present invention.

-a method for controlling undesired plants, pests or diseases, which method comprises contacting an effective amount of the suspension according to the invention or a tank mixture thereof with the locus of said undesired plants, pests or diseases.

Detailed Description

Definition of the definition

Before elaborating on the present subject matter, it may be helpful to provide definitions of certain terms used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present subject matter relates.

As used herein, the term "stable" when used in conjunction with physical stabilization or when used in conjunction with a composition means that no significant crystallization, deposition and/or thickening is observed and that the formulation is always within acceptable limits for normal use of the formulation, e.g., if no significant crystallization, phase separation and/or thickening is observed after storage at a temperature of at least 54 ℃ for 1 day, e.g., after 4 days or after 2 weeks of storage, the formulation is considered physically stable.

As used herein, the term "effective amount" when used in conjunction with an active ingredient or an active ingredient-containing formulation refers to an amount of the active ingredient that is sufficient to achieve good control or activity levels of pests, diseases, and/or unwanted plants when digested, contacted, or sensed.

An "active ingredient" is a substance that is capable of controlling unwanted plants (weeds), plant pests, or plant diseases and that does not cause significant damage to the treated crop plants. The term "active ingredient" includes, but is not limited to, insecticides, nematicides, herbicides, fungicides, algicides, animal repellents or acaricides. The active ingredients are not limited to pesticides, and also include, for example, hormones, biostimulants, and plant growth regulators.

The hydrophilic active ingredient electrolyte may be an acid salt, a basic salt, or a zwitterionic. The salt of the active ingredient may be the result of a neutralization reaction between the acidic groups of the active ingredient and the base, or vice versa between the basic groups of the active ingredient and the acid. Furthermore, depending on the pH of the aqueous phase of the emulsion, the active ingredient electrolyte may be the result of a dissociation reaction of acidic or basic groups in water.

As used herein, the term "high salt environment" means that the emulsion formulation (or a suspoemulsion thereof) contains at least 5w/w% salt relative to the total weight of the final emulsion formulation. For example, at least 7w/w%, preferably at least 10w/w%, more preferably at least 15w/w%, even more preferably at least 18w/w% of salt relative to the total weight of the final emulsion. The formulations described herein may have a salt molar concentration of at least 0.5M, for example above 0.6M or above 0.7M.

As used herein, the term "plant" or "crop plant" includes reference to whole plants, plant organs (e.g., leaves, stems, twigs, roots, trunks, branches, shoots, fruits, etc.), plant cells, or plant seeds of industrial significance, including grasslands and rangelands, such as plants for human consumption, animal consumption, or other industrial uses, for example. This term also encompasses crops, such as fruits. The term "plant" may also include propagation material thereof, which may include all reproductive parts of the plant, such as seeds, and vegetative plant material such as cuttings and tubers, which may be used to proliferate the plant. The term may also include spores, bulbs, rhizomes, sprouts, basal shoots, stolons, and buds as well as other parts of plants, including seedlings and young plants, which will be transplanted after germination or after emergence from soil. As used herein, the term "crop" includes plants that have been modified by breeding, mutagenesis or genetic engineering. A genetically modified plant is a plant whose genetic material has been modified by using recombinant DNA techniques. Typically, one or more genes have been integrated into the genetic material of such plants in order to improve certain characteristics of the plants.

As used herein, the term "locus" includes habitat, breeding area, plant, breeding material, soil, region, material or environment where undesirable plants, pests or diseases are growing or may grow.

As used herein, the term "control" or "controlling" or "combating" refers to preventing disease, pest, or unwanted plant growth, protecting plants from disease or pest, delaying the onset of disease, and killing or reducing the deleterious effects of disease or pest, or killing or reducing unwanted plant growth.

The emulsions of the present invention (or suspoemulsions thereof) may additionally comprise agriculturally acceptable inert additives. These are defined herein as any substance that is not itself an active ingredient but is added to the composition to improve its properties.

The emulsion of the present invention (or a suspension thereof) may be mixed with a tank mix adjuvant solution prior to its application in the field to improve physical properties and efficacy. Some materials may be used as agriculturally acceptable inert additives in the emulsions of the present invention or mixed with the emulsions of the present invention as tank mix additives prior to field application. Tank-mixtures resulting from mixing the emulsions of the present invention (or a suspoemulsion thereof) with one or more tank-mix adjuvant solutions are also an aspect of the present invention.

Non-limiting examples of agriculturally acceptable inert additives and tank mix adjuvants are wetting agents (or spreading agents), adhesion agents, emulsifiers, dispersants, suspending agents, plant penetration agents (or transport proteins), antifreeze agents, preservatives, binders, fertilizers, thickening agents, antioxidants, drift retardants, buffers, inversion agents, soil penetration agents, UV absorbers, protectant binders, defoamers or wetting agents. Preferably, the tank mix comprises at least fertilizer.

The term "lipophilic" or "hydrophobic" refers to having an affinity for organic solvents and therefore being insoluble in water or soluble in negligible amounts.

The term "hydrophilic" or "lipophobic" refers to a substance that has an affinity for water and is therefore insoluble in organic solvents or dissolves in negligible amounts. For example, the lipophilic active ingredient has a solubility in water of less than 1g/L at 20 ℃.

"alkyl" in this document means a straight-chain or branched hydrocarbon chain radical composed of carbon and hydrogen atoms, which is free of unsaturation, having the number of carbon atoms indicated in each case, for example from 1 to 16 carbon atoms (C ₁ -C ₁₆ (-) attached to the rest of the molecule by a single bond. For example, alkyl groups contain 1 to 8 carbon atoms, typically 1 to 4 carbon atoms. Exemplary alkyl groups may be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or n-pentyl.

"aryl" in this document means a radical having in each case the indicated number of carbon atoms, for example from 1 to 16 carbon atoms (C ₁ -C ₁₆ -) aromatic hydrocarbon group attached to the rest of the molecule by a single bond, such as phenyl or naphthyl.

"arylalkyl" in this document means an aryl group, such as benzyl and phenethyl, attached to the remainder of the molecule through an alkyl group.

"alkylaryl" in this document means an alkyl group attached to the remainder of the molecule through an aryl group.

Unless otherwise indicated, alkyl, aryl, arylalkyl, and alkylaryl groups are unsubstituted.

The term "a/an" as used herein includes both the singular and the plural, unless specifically stated otherwise. Thus, the terms "a/an" or "at least one" are used interchangeably herein.

For the purposes of better understanding the present teachings and in no way limiting the scope of these teachings, all numbers expressing quantities, percentages or proportions, as well as other numbers used in the specification and claims, are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In this regard, the term "about" as used herein specifically includes + -10% of the indicated values within that range. In addition, endpoints of all ranges herein directed to the same component or property are inclusive of the endpoints, independently combinable, and inclusive of all intermediate points and ranges.

As used herein, the phrase "block copolymer" means a polymer comprising at least two different polymers bonded by covalent bonds. Each block is typically a homopolymer, but may also be a copolymer having specific unique physical/chemical or functional characteristics (e.g., having one block that is readily soluble in water, while the other block is not soluble in water at all). Thus, the polyanionic block copolymer surfactant comprises a "hydrophilic moiety" and a "lipophilic moiety". Each of these moieties may itself be a homopolymer or a block copolymer.

Emulsion

For the purposes of the present invention, it is understood that an emulsion is a formulation comprising an aqueous continuous phase containing emulsified oil droplets, i.e. an oil-in-water emulsion. In the emulsions of the present invention, the aqueous phase may also contain an active ingredient electrolyte. The oil droplets forming the organic phase comprise an agrochemical lipophilic active ingredient which is preferably liquid at room temperature.

Oil-in-water emulsions are typically prepared by the following process: the respective solutions of the aqueous phase and the oil phase are first prepared and then combined in such a way that the lipophilic phase forms droplets in the continuous aqueous phase. The amount of water in the emulsion of the invention is not particularly relevant and is typically comprised between 5w/w% and 90w/w%, for example between 10w/w% and 80w/w%, or between 15w/w% and 60w/w%, between 20w/w% and 50w/w% with respect to the total weight of the final emulsion. The total amount of aqueous phase is typically comprised between 25w/w% and 90w/w%, for example between 35w/w% and 80w/w%, preferably between 40w/w% and 70w/w%, relative to the total weight of the final emulsion.

In addition, if it is desired to improve the solubility of any component in the liquid organic phase, the organic phase may comprise a water-insoluble organic solvent. If an organic solvent is used, it may be selected from the group consisting of alkyl lactate, aromatic naphtha solvents, aromatic or aliphatic ketones, alkylamides, and pyrrolidones such as n-octyl pyrrolidone. For example, the solvent may be selected from the group consisting of ethyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, propyl acetate, amyl acetate, toluene, xylene, limonene, hexane, pentane, heptane, cyclohexane, and mixtures thereof. The solvent must be effective in dissolving the lipophilic active ingredient and is preferably environmentally friendly.

The lipophilic active ingredient in the emulsion or suspoemulsion thereof may be an insecticide, fungicide or herbicide, other active ingredient as described herein.

Exemplary lipophilic insecticides may be selected from the group consisting of: benzofuranyl methyl carbamate insecticides such as benfuracarb, and carbosulfan; oxime carbamate insecticides such as aldicarb; fumigant insecticides such as trichloronitromethane, 1, 3-dichloropropene and bromomethane; juvenile hormone mimics such as fenoxycarb; organic phosphate insecticides such as dichlorvos; aliphatic organic thiophosphate insecticides such as malathion and terbufos; aliphatic amide organic thiophosphate insecticides such as dimethoate; benzotriazine organic phosphorothioates insecticides such as ecosystem phosphorus and bazedox; pyridine organic thiophosphate insecticides such as chlorpyrifos (chlorpyrifos) and chlorpyrifos methyl; pyrimidine organic thiophosphate insecticides such as Diazinon (Diazinon); phenyl organic thiophosphate insecticides such as parathion (parathion) and methyl parathion; pyrethroid insecticides such as bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, zeta-cyhalothrin, alpha-cyhalothrin, beta-cyhalothrin, fenvalerate, and permethrin, and mixtures thereof.

Exemplary lipophilic fungicides in the emulsion or its suspoemulsion may be selected from the group consisting of Aldimorph, difenphos (Dinocap), difenphos (Edifenphos), ethaboxam (ethidazole), fenpropimorph (fenpyromorph), iprobenfos (Iprobenfos), chlorfenapyr (Meptyldinocap), metalaxyl-M, propiconazole (Propiconazole), tributyltin oxide, and mixtures thereof.

Exemplary lipophilic herbicides for use in the emulsion or suspoemulsion thereof may be selected from the group consisting of: amide herbicides such as dimethenamid (dimethenamid) and dimethenamid-p-m-ethyl; anilide herbicides such as propanil (propanil); benzoic acid herbicides such as dicamba (dicamba); chloroacetanilide herbicides such as acetochlor (acetochlor), alachlor (alachlor), butachlor (butachlor), metolachlor (metolachlor) and metolachlor; cyclohexene oxime herbicides such as sethoxydim (sethoxydim); dinitroaniline herbicides such as flumetsulam (benfluralin), cyhalofop-butyl (ethane), pendimethalin (pendimethalin), and trifluralin (trifluralin); nitrile herbicides such as bromoxynil octanoate (bromoxynil octanoate); phenoxyacetic acid herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA, and MCPA-thioethyl; phenoxy butyric acid herbicides such as 4-CPB, 2,4-DB, 3,4-DB, and MCPB; phenoxy propionic acid herbicides such as, for example, chlorprop (clorop), 4-CPP, 2,4-d propionic acid (dichlorprop), fine 2,4-d propionic acid, 3,4-DP, nasal discharge propionic acid (fenoprop), chlorophenoxypropionic acid (mecoprop) and fine chlorophenoxypropionic acid; aryloxyphenoxypropionic acid herbicides such as cyhalofop, fluazifop-P, haloxyfop-P; pyridine herbicides such as aminopyralid (aminopyralid), clopyralid (clopyralid), picloram (picloram), and triclopyr (triclopyr); and triazole herbicides such as amicarbazone (carfentrazone ethyl), and mixtures thereof.

For example, the lipophilic active ingredient is a herbicide selected from the group consisting of: atrazine, bromoxynil, betametham, diflufenican, flufenacet, and the like mefenacet, diuron, fomesafen, ioxynil, isoproturon isoxaben (isoxaben), linuron (linuron), metolachlor (S-metaachlor), pendimethalin (oryzalin), oxyfluorfen (oxyfluorfen), betanin (phenmedipham), prometryn (prometryn) penoxsulam (propyzamide), penoxsulam (pyroxsulam), penoxsulam (quinclorac), simazine (simazine), terbuthylazine (terbuthylazine), terbutryn (terbutryn), trifloxysulfuron (tralkoxydim), flumioxazin (flumidothiazole), flumetsulam (fluvenosum), sulfentrazam (metasultam), dichlorsulfenamide (dichlordosis), cloransulam-methyl (cloransulam-methyl), and mixtures thereof.

A typical example of a lipophilic active ingredient useful in the emulsions disclosed herein is chloroacetamide, for example one selected from the group consisting of: acetochlor (acetochlor), alachlor (allochlor), amidochlor, butachlor (butachlor), butachlor (deltaachlor), ibutchlor (delachlor), acetochlor (diethyl), dimethenamid (dimethchlor), acetochlor (ethane), oxazachlor (ethane), metazachlor (metazachlor), metolachlor (metazachlor), isopropamide (S-metazachlor), pretilachlor (pretilachlor), pretilachlor (protropchlor), isopropamide (promethachlor), propisochlor (prrachlor), terbutachlor (terbutachlor), butachlor (theswhile), and dimethenamid (xyl) are described herein. More preferably, the lipophilic active ingredient is a herbicide selected from the group consisting of dimethenamid-p-ethyl, metolachlor-p-ethyl, and mixtures thereof.

The hydrophilic active ingredient electrolyte used in the emulsion or its suspoemulsion may be a water-soluble insecticidal, fungicidal or herbicidal electrolyte, i.e. a salt of the active ingredient. As previously mentioned, hydrophilic active ingredients are referred to in this document as those having a solubility in ionic water of greater than 1g/L at 20 ℃. The active ingredient electrolyte used in the present invention is typically a salt that dissociates in water, providing very high solubility in ionic water at 20 ℃, for example greater than 10g/L, preferably greater than 30g/L, preferably greater than 50g/L. Thus, the emulsions described herein may comprise salts of any active ingredient capable of forming salts of acids or salts of bases.

Preferably, the hydrophilic active ingredient electrolyte is one selected from the group consisting of salts of organophosphorus herbicides, for example one selected from the group consisting of: the salts of methamidophos (amipro-methyl), amipro (amipro), anilofos (anilofos), triazophos (bensulide), bialaphos (bilanafos), imazalil (butamifos), clomazone (claryfos), 2,4-DEP, DMPA, EBEP, xylophos (fosamine), glufosinate (glufosinate-P), glyphosate (glufosinate), sulben (huangcaaling), piroxicam (piparophos), and dimefos (shangjia canolin).

Preferably, the lipophilic active ingredient is selected from the group consisting of amide herbicides, preferably chloroacetanilide herbicides, preferably one selected from the group consisting of: the compositions may be formulated as, for example, alachlor (alidochlor), amicarbazone, beflubutamid (beflubutamid), beflubutamid (bezedox), benoxamide (benzipram), bromobutamid (bromobutamide), oxazamate (cafenstrole), CDEA, tricyclooxamide (cyprazole), dimethenamid, bezamide (diphenmid), triazolesulfon (epronaz), etniprolid, tetrazolamide (bentazomide), flucarbazone (flucarbazone), flumesafen (fomesafen), flusulfamide (halofan), sulben, oxadiargyl (isopamamide), isoxafen (oxaden), dichlormid (naproxen), naproxen (naproxen) enamine (pethoxamide), penoxsulam (propyzamide), quinipamide (quinonanomid), saflufenacil (saffinacil), forage amine (tebutam), flumetsulam (tifenail), triazolfenamide (triazofenamide), benfurazolidone (chloranthyl), fludioxonil (cicloprazolide), cyclophanamide (cyprodinil), diflufenican (bifenan), dichlornoxamide (erlujicam), acetofenamide (etoben), fensulfenamide (fensulfenamide), flufenacet (flufenacil), flufenacet (triazolfenamide), mefenamide (mefenamide), flufenamide (mefenamide), oxamide (mefenamide), and naprox (naproxide), mechlorethamine (pentanochlor), fluopicolide (picolinafen), propanil (propanil), sulfenamide (sulfenazone), tetflufenuron (tetfluyrolimet), neo-swallow acid, mebendazole (flagrop), mebendazole, acetochlor, alachlor, amidochlor butachlor, acetochlor, dimethenamid, clotrimide, oxadiazon, metazachlor, metolachlor, pretilachlor, metolachlor, propyzamide, terbutachlor, metolachlor, ethaboxam xylylenediamine, benzofluor, clofenacet (cloransulam), diclosulam (dichlorsulfenamide), dimesfozet, florasulam (florasulam), flumetsulam (fluetsulam), sulfentrazam (metasulfenamide), flufenamide (perflupine), flufenacet (profluzol), flusulfenamide (pyrifosfom), fluoroketosulfenamide (triafamone), sulfenamide (asulam), carbosulfuron (carbasul), fennassulfenamide (oryzalin), penoxsulfenamide (pyroxsulam), see also sulfonylurea herbicides, benazolin (bencarbazone), and oxaden (chlorthiamid).

An exemplary hydrophilic insecticide electrolyte may be a salt of an insecticide selected from the group consisting of: arsenic insecticides, plant insecticides, carbamate insecticides, diamide insecticides, dinitrophenol insecticides, fluoride insecticides, formamidine insecticides, fumigant insecticides, inorganic insecticides, insect growth regulators, isoxazoline insecticides, macrolide insecticides, neonicotinoid insecticides, nereistoxin analog insecticides, organochlorine insecticides, organophosphorus insecticides, oxadiazine insecticides, oxadiazolone insecticides, phthalimide insecticides, physical insecticides, pyrazole insecticides, pyrethroid insecticides, pyrimidamine insecticides, pyrrole insecticides, quaternary ammonium insecticides, sulfonylimine insecticides, tetramic acid (tetramic acid) insecticides, tetronic acid insecticides, thiazole insecticides, thiazolidine insecticides, thiourea insecticides, urea insecticides, and zwitterionic insecticides.

An exemplary hydrophilic insecticide electrolyte may be a salt of an insecticide selected from the group consisting of: (E) -2- (2- (2- (2, 3-dichlorophenylamino) -6-trifluoromethylpyrimidin-4-yloxymethyl) phenyl) -3-methoxyacrylate, 1- (4-chlorophenyl) -3- (2, 6-dichlorobenzoyl) urea, 1, 2-dibromoethane, 1, 2-dichloropropane, 2- (octylthio) ethanol, 2-imidazolidinone, acephate (Acephate), acetamiprid, housefly phosphorus (action), ethyl phosphorus (actionos), acetochlorfenate (acttoprene), activated ester-S-methyl (actrenzol-S-methyl), parthenolide (actrinaphrin), acrylonitrile, actronyr, dipropyl cycloxapride (Afidopyropen) carbofuran (alaycarb), aldicarb sulfone, aldrin (Aldrin), allethrin (Allethrin), carbofuran (alixycarb), alpha-cypermethrin (Alpha-cypermethrin), alpha-endosulfan (Alpha-endosulfan), alpha-hexachlorocyclohexane, aluminum phosphide, aluminum silicate, methiphos (Amitraz), sulfamate (amioflumet), methophos (Amitraz), methiocarb (amiocarb), amitraz (Amiton), amitraz (Amitraz), ammonium acetate, anthracene oil, carbomite (arte), arsenical, profenofos (Aspon), ethide (Athidamate), methidathion (Athidathion), triad (Amidophos), azathioprine (Azamethiphos), yigossypium (Azinphos-ethyl), procyanidin (Azinphos-methyl), azophos (azomethionate), azoxybenzene, benzothiadiate (benlothiaz), oxacarb (Bendiocarb), benfuracarb, thiocarbamate (Bensultap), benzoic acid, benzpyrimoxanil, benzyl benzoate, beta-cyhalothrin (Beta-cyfluthrin), beta-cypermethrin (Beta-cypermethrin), beta-thiodan (Beta-endosulfenate), bifenazate (Bifenazate), bifenthrin (binthoxin), lenacifen (Binapacryl), bioallethrin (Bioallethrin), biochlorethrin (biomethrin), dextromethrin (biomethrin), bifenthrin), bis-chloroethyl (2-chloroethyl) bis-trifluoracer (Bistrifluron), boric acid, brofenflurbendiamide (broflavrilide), bifenthrin (Brofluthrinate), brofenvinfos (Bromfenvinfos), bromoeneoxide (bromocycloen), bromomethane, bromothiophos (Bromophos), ethylbromothiophos, carbofuran (Bufencarb), buprofezin (Buprofezin), bupirifos (Butathiofos), butanone (butocarboxin), butylphosphine (butoxide), mosquito repellent ketone (butopyronoxy), butanone sulfone (butoxycarxin), thiophos (catuvasafos), calcium arsenate, calcium chloride, calcium hydroxide, toxafen (camphechor), potassium salt, chlormevalonate (Carbanolate), carbaryl), furane (carboran), carbon dioxide, carbon disulphide, carbon tetrachloride, phosphorus trisulfide (carbophenomenon), carbosulfan (Carbosulfan), cartap (Cartap), cartap hydrochloride, chlorpyrifos (chinomethoat), chlorramide, chlorantraniliprole (Chlorantraniliprole), chlorpyrifos (Chlorpyrifos), borneol dane (chlorpyricile), chlordane (Chlordane), decachlorone (chlordienone), chlordimidine (chlorimeform) phosphorus oxychloride (chlorthalidone), chlorfenapyr (Chlorfenapyr), tebuconazole (Chlorfenapyr), fenpyr (chlorfenamate), fenpyr (chlorfenacin), chlorfenamate (chlorfenacin), chlorpyrifos (Chlorfenapyr), chlorfluazuron (Chlorfluazuron), phosphorus oxychloride (Chlorpyrifos), chlorobenzene (chlorbenzite), nitromethane (chlorpicrin), prallethrin (chlorprallethrin) propyl ester acaricidal alcohol (Chlorpyrifos), chlorpyrifos (Chlorpyrifos), pyrifos (Chlorpyrifos), chlorpyrifos (Chlorthion), chlorpyrifos (Chlorpyrifos), chromafenozide (Chromafenozide), cis-permethrin (Cispermethrin), carbofuran (Cloethocarb), clothianidin (Clothianidin), copper acetylarsenite copper naphthenate, livestock phosphorus (coumesylate), crotamiton (Crotamiton), sulfoxaflor (cyaniphos), carprofen (Cyantraniliprole), cyantraniliprole (Cyantraniliprole), cyclobrisanmide (cycloprol), cycloprothrin (Cycloprothrin), cyromazine (Cycloprate), cycloprothrin (Cycloprothrin), cyenopyrifern (Cycloprothrin), ethiprole (cyclopyrafen), cymoxanil (cyclopyrafen), fenpyrad (cyclopyrafen), cyflumetofen, cyfluthrin, cyhalodiamide, cyhalothrin, tricyclotin, cyhexatin, cypermethrin, cyphenmethyl, cyromazine, DAEP, dazomet, DCIP, D-D, DDD, DDT, deltamethrin, temephos, oxygen-temephos, thiotepa, endophos-O-methyl-sulfone, endophos-S-methyl endo-S-methylsulfonylmethane (Demeton-S-methyl sulfone), diafenthiuron (Diaffenthiouron), chloriminothiolane (Diadifenos), desmethyl (Diaminophos), diammonium phosphate (Diammonium phosphate), diazinon, dibromochloropropane, dibutyl phthalate, desmethyl, dichlorvos, trichlorethamine (Diclocymet), dicclomazozotiaz, chlorothalonil (Diclotophos), dieldrin (Dieldrin), pyridalyl (Dienochror), penoxsulam (Diethylolmide), flucyclozine (Diflovidazin), diflubenzuron, tetramethrin (Dimefluthrin), carbomethoxy (Dimefoxox), dimethrin (Dimethrin), dimethyl disulfide (Dimethyl disulfide), dimethyl phthalate, methylparaben (Dimethylvinphos), indoxacarb (Dinex-dicylexine), dinotefuran (Dinotefuran), benomyl (Diofenolan), dioxazophos, dioxycarb (Dioxacarb), dichlorphos (dioxyhion), diphenylamine, disodium octaborate tetrahydrate, ethazine (Disulfoton), dixanthogen (Dixanthogen), DNOC ammonium, DNOC potassium, DNOC sodium, dormant oil (dormantol), bifenthrin (Empenthrin), thiodan (Endosulfan), penoxsulam (Endrin), EPN, epothilone (epothilone), epsilon-methyofenothrin-metofluon), epsilon-fluorothrin, homofluorothrin (fenvalerate), homovalerate (fenvalerate) oxforshire propylthiophos (ethaphos), ethioficarb, ethion (Ethion), ethiprole (Ethiprole), yithion, methophos (Ethoprophos), dichloroethane (Ethylene dichloride), ethofenprox (etofenoprox), ethirimos (ethimfos), fatty acids (universal), fenbuconazole (fenzaflor), fenazaquin (Fenazaquin), fenbutatin oxide (Fenbutatin oxide), dermatophaphos (fenpyrophos), penfluramine (Fenfluthrin), fenitrothion (Fenitrothion), carbofuran (fenbucarb), benfuracarb (fenpropacarb), fenoxycarb (fenxycarb), fenxycarb (fenxycarb), prochlorethamate (fenpropithrin), fenpropithrin, fenpropidium, fenpyroximate (Fenpyroximate), feng Suolin (Fensulfhio), phoxim (Fenthion), phoxim sulfoxide (Fenthion sulfoxide), fenvalerate (fenvalinate), fipronil (Fipronil), fipronil (Flometuquorin), flonicamid (Flomefumonimide), fluzaindolizine, flubendiamide (Flubendiamide), fluclobisfenuron (Flucofuron), flucyclourea (Flucoxuron), fluvalinate (Flucothrinate), bifenazate (Fluenet), pyriminox (flufenpropium), flufenoxuron (Flufenoxuron), trifluofenamide (Flufenox), butene Fipronil (Flufenomide), fluxaprop (Fluoben), fluxamide (Fluoracetamide), fluentfanox, flupirone (Fluovalinate), fluvalinate (Flufenoxuron), flufenoxuron (Flufenox), flufenoxuron (Flufenofos) valproamidine (formamidine), valproamidine hydrochloride, amomum (formarionate), carbofuran (formaranate), fenphos (Fosthiazate), fosfopristine (Fospirate), fosthiazate (Fosthiazate), furtebufenozide (Fufenozide), furfurofuran (furthiaocarb), anticoccidial (furothrin), gamma-cyhalothrin, penflufen (Guadipyr), benzyl mite ether (Halfenprox), chlorfenozide (halofuran), heptachlorpyrifos (hepatachlor), heptazophos (heptazophos), hexachlorocyclohexane, hexadecanoic acid, hexaflumuron (hexafluvaluron), flumetsulam, quin (Hydroprene), quinoline (hydraprene), quinoline (hydracryl), and philtin (carfribin), imidacloprid (Imidacloprid), cimetidine (Imidacloprid), prochloraz (Imiprothrin), indoxacarb (Indexacrb), iodiphos (Iodofenphos), methyl iodide, IPSP, isamidofos, chlorzophos (Isazofos), carbochlorpyrin (Isobenzan), fenphos (Isocarbophos), isocycloseram, isoacquired agent, iso Liu Lin (Isofenphos), methyliso Liu Lin (Isofenphos-methyl), isocable (Isolan), isoprocarb (Isoprocarb), isoxazophos (Isothioate), isoxazophos (Isoxathon), kadethrin (Kadethrin), kaolin (Kaolin), calcined Kaolin, kappa-bifenthrin (Kappa-bifenthrin), kappa-tefluthrin (Kappa-tefluthrin), chlorovalerate (Keppa-tefluthrin) alkeneyne (Kinoprene), lambda-cyhalothrin, lavender senecide (Lavandulyl senecioate), lead arsenate, bromophenyl (Leptophos), lime sulfur (Lime sulfophur), lindane (Lindane), sulfonated perfluorooctane lithium, lufenuron (Lufenuron), thiazolium (Lythiion), magnesium phosphide, marathon (Malatino), propafenon (Malonoben), azido phosphorus (Mazidox), M-isopropylmethyl carbamate (M-cumenyl methylcarbamate), aphaphphos (Mecarbam), tetramethyl phosphorus (Mecarbhon), aphphos (Menazol), chlorofluorothrin (Meperfluthrin), dithium (Mephosfolan), mercuric chloride (Mercurous chloride), cyflumizone (Metaflumizon), metam-potassium, metam-sodium, metnasal discharge (Metepa), chlorfenphos (Methacross), methamidophos, methidathion (Methidathion), methiocarb (Methiocarb), methiopal (Methioepa), ethiprole (Methorotops), methidathion (Methorotops) Methomyl, methoprene, methoxam, methoxyfenozide, methyl isothiocyanate (Methyl isothiocyanate), methofloxuron, methocarb, oxadiazon, carboxin, carbocycle, and carbo Mevinphos (Mevinphos), carboxim (Mexacarbate), propafenofos (Mipafox), benomyl (Mirex), momfluorothrin (Monocrotophos), cyclomethion (morph), dibromophosphorus (Naled), nano silver particle pesticides, nitenpyram (nitenpyrram), nitroethylurea thiazole (Nithiazine), pentacarbofuran (nitalaharb), N-methyl neodecanoamide (N-methyl neodecanoamide), N-nitrosodimethylamine (N-nitrodimethyl amine), nornicotine (nornicote), fluoroureide (Novaluron), polyfluoropuride (Noviflumuron), O, O ' -DDT, O, P ' -DDT, omethoate (Ommethod), oxamyl, oxazosulfanyl, sulfone phosphorus (Oxydemethon-methyl), phosphorous (Oxydeprofos), sulfone phosphorus (Oxydediulfoton), P, P ' -DDT, cycloxapridine (Paichongding), ethyl Parathion (Parath-ethyl), methyl Parathion (Parath-methyl), pentachlorophenol (Pentachlorphenol), permethrin (Permethrin), ethyl acetate (Perthane), fenthion (Phenkapton), phenothrin (Phenochrin), phenthoate (Phenthonate), phorate (phosphate), vophos (phoslone), thiocyclophos (Phosfolan), iminothiolate (phosphate), p-chlorophosphine (phospor), phosphamine (phosphophamine), phosphine (Phosphine), phoxim (Phoxim), piperonyl sulfoxide (Piperonyl sulfoxide), pirimiphos (Pirimicarb), ethylpyriphos (Pirimiphos-methyl), pirimiphos-methyl, triclosamide (plainate), propithrin (Prallethrin) Profenofos (Profenofos), profenothrin (Profluthrin), pyrifos (promaceyl), carbofuran (Promecarb), profenofos (profaphos), pyrimidyl (profetafos), propoxur (profenoxur), ethiona (prothiorion), profenofos (Profenofos), profenofos (prothioate), propylfenthrin (prothioate), tebufenpyrad (proflubulide), parvalinate (pymezzine), pyraclonil (Pyraclofos), pyripyroxafen (pyrafluron), pyrimidyl (pyramate), pyridaben (Pyridaben), pyridaphos (pyridafen), pyridazol (pyridazin), pyriproxyfezil (pyridazol), fluaziquan (pyrifluzon), pyrimethanil (pyrifluazuron), pyriproxyfen (Pyriproxyfen), QRD-460, quinophos (quinallophos), bronzin (Quinothion), quinophos (quintofos), renofluthrin, methothrin (Resmethrin), octamethiphos (Schradan), monocarboxamide hydrochloride (Semiamitraz hydrochloride), silafluofen (Silafluofen), silica, S-methoprene (S-methoprene), sodium tetraborate pentahydrate (Sodium tetraborate pentahydrate), spinetoram (Spinetoram), spirodiclofen (Spirodiclofen), spiromesifen (Spiromesifen), spirotetramat (strobetan), sulfenpyrad (sulfofluid), sulfotep (Sulfotep), sulfoxaflor (Sulfoxaflor), sulfenpyrad (Sulfuryl fluoride), thiophos (sulfoprofos) Tau-fluvalinate, tebufenozide, butyl pyrimidyl phosphate (Tebupirimfos), flubenuron (tebubenzuron), tefluthrin (Tefluthrin), dithiophosphate (tebufos), cycloprothrin (tebufos), tebufos (Terbufos), set Luo Lin (tebufenphos), trichlorfon sulfone (tebufos), tetraethyl pyrophosphate, tetramethrin, tebufenthrin (tebumethfos), flucyantraniliprole (tebufenofos), flubenflumorph (tebufenofos), methimazole (Tebufenozide), thiacloprid (Thiopride), thiamethoxam (thiomethoxam), thiopropionitrile (Thiaprocil), carboxin (thiocarboxin), thiocyclam (thiazate), thiocyclam (84), thiocyclam (oxalate), thiodicarb, mevalonate, methyiethylphos, thiophos (thionapzin), cyromazine (thioquin), dimefluthrin (thiofluthrin), dimefluthrin (perpethrin), dimefluthrin (tefluthrin), tolfenpyrad (Tolfenpyrad), deltamethrin (tranexamin), tolfenpyrad (tranetthrin) Triarathene, triazamate, triazophos, trichlorfon, chlorpyrifos (trichlorate), snail, chlorpyrifos (Trifenmorph), trifloxystrobin (Trifenofos), trifloxystrobin (triflumizopyrim), triflumuron (Trifluuron), triamcinolone (Trimethacarb), pyrithione (tricrene), urea, triamcinolone (Vamidothion), triamcinolone, XMC, methidathion (Xylecarb), and Zeta-cypermethrin (Zeta-cypermethrin).

An exemplary hydrophilic fungicide electrolyte may be a salt of a fungicide selected from the group consisting of: aliphatic nitrogen fungicides, amide fungicides, antibiotic fungicides, aromatic fungicides, arsenic-containing fungicides, arylphenyl ketone fungicides, benzimidazole precursor fungicides, benzothiazole fungicides, plant fungicides, bridged diphenyl fungicides, carbamate fungicides, conazole fungicides, copper fungicides, cyanoacrylate fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamic acid ester fungicides, dithiolane fungicides, fumigant fungicides, hydrazide fungicides, imidazole fungicides, inorganic fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, organotin fungicides, oxathiadiene fungicides, oxazole fungicides, polysulfide fungicides, pyrazole fungicides, pyridazine fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, tetrazole fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, and zinc fungicides.

An exemplary hydrophilic fungicide electrolyte may be a salt of a fungicide selected from the group consisting of: (R) -flutriafol, (R) -hexaconazole, (S) -flutriafol, (S) -hexaconazole, 10' -oxo-phenoxarsine, 2- (thiocyanomethylthio) benzothiazole, 2-dibromo-3-nitrilopropionamide, 2,4, 5-trichlorophenol, 2, 4-dimethylphenol, methyl 2, 5-dichlorobenzoate, 2, 6-dichloro-N- ((4- (trifluoromethyl) phenyl) methyl-benzamide, 24-tenascin (24-epinasolide), 2-allylphenol, 2-aminobutane, 2-methoxyethyl mercury acetate, 2-methoxyethyl mercury chloride, 2-phenylphenol, 8-hydroxyquinoline, activated ester-S-methyl Aldimorph, ametoctradin, amisulbrom (Amisulbrom), ammonium acetate, ammonium carbonate, aminophosphonic acid (amipropylfos), diuron (Anilazine), anthracene oil, thiram (asamate), azaconazole (Azaconazole), thiram (azithiamine), tolylene (Azoxystrobin), barium polysulfide, benalaxyl (Benalaxyl), benalaxyl (Benalaxyl-M), benalaxyl (Benalaxyl), benomyl (Benomyl), dizohydrazone (Benquinox), propiuron (benalauron), benthiavalicarb (bentavalicarb), isopropylthiamine (Benthiavalicarb isopropyl), benzalkonium chloride (Benzalkonium chloride), benzamacroil, isobutylbenzyl acid (Benzamacril isobutyl), antibacterial (Benzamorf), benzoic acid, penflufen (Benzovindrifipyr), bethoxazin, lenacil (Binapacryl), biphenyl, bis (methylmercury) sulfate, thiabendazole (bisthiazol), bis-trichloromethyl sulfone, bitertanol thiobis dichlorophenol, bixafen, borde mixture, boric acid, white cocoa (Boscalid), furfuryl azole, bronopol, bupirimate, ding Liuding (Buthiobat), calcium carbonate, calcium chloride, calcium cyanamide, calcium hydroxide calcium phosphate, captan (Captafol), captan (Captan), moldavica (carbomorph), carbendazim (Carboxin), carboxin (Carboxin), cyproconazole (carboximidamid), fenamic acid (chinomethoate), pyrimethanil (chlorbentazone), bisaminone (chloraniforme), benzoquinone tetrachloride (Chloranil), erigerone (chlordane), phenylimidazole bacterium (Chlorfenazole), triclosan (Chloranil), chlorothalonil (chlorodimethanol), chloroxylenol (Chloroxylenol), chloroquine (chloroquin), ethiol (chlorozolate), cis-propiconazole (Cis-proconazole), chloromyclobazole (cimazole), cuprous oxide (1), copper pine, copper bis (3-phenylsalicylic acid), copper II acetate, copper II carbonate, copper II chloride, copper II hydroxide, copper naphthenate, copper oxychloride, copper sulfate, COS-OGA, azoxystrobin (Coumoxystrobin), coumoxystrobin (Coumoxystrobin), thiazate (Cufraneb), thiram, cyazofamid (Cyazofamid), cycloheximide, cyflufenamid (Cyflufenamid), cymoxanil (Cymoxanil), cypendazole, cyproconazole (cyprocarbazole), cyprodinil (cyprodil), esterquat (Cyprofuram), dazomet, D-D, prochloraz (Debacarb), decaphosphotin (Decantin), dehydroacetic acid, ethylenebis (dithiocarbamic acid) diammonium, dibromochloropropane, dichlobenazol, dichlofluanid (Dichlofluanid) Dichloronaphthoquinone (dichlorne), dichlorophenol (dichlorphen), benzyl chlorotriazole (dichlormid), triclopyr (dichlorprop), pyridazinone (dichlormazine), chloronitramine (dichloran), didodecyl dimethyl ammonium chloride, diethofencarb (dichlorfenamic), difenoconazole (Difenoconazole ), difenoconazole (Difenzoquat metilsulfate), fluoxastrobin (Difenoconazole), dimethachlon (dimetazole), dimetidine (dimetimol), dimethomorph (Dimethomorph), dimethachlon (Dimoxystrobin), diniconazole (Diniconazole), diniconazole-M (Diniconazole-M), flucycloxaprop (dinobutyronidazole), difenoconazole (Diniconazole), difenoconazole-4, dimetoram (Difenoconazole-4), difenacet-6, adjacent enemy mite-eliminating (Dinocton), nitrovalerate (Dinocyton), nitrooctyl (Dinosulfon), diphenylamine, dipometrone, dithiopyridine (Dipyrithione), disodium octaborate tetrahydrate, disodium phosphonate, triazophos (Ditalimfos), dithianon (Dithianon), DNOC ammonium, DNOC potassium, DNOC sodium, molinate (Domorph), molinate (Dodemorph acetate) acetate, dodine (Dodine), dimoxystrobin (Drazoxolone), kewensan (Edibofephos), enoximate (Enoxatrobin), epoxiconazole (Epoxiconazole), epoxiconazole (Etazozole), thiosulfenmide (Ethodim), ethaboxam (Ethomole), elon (Ethoxyquin), ethylene bis-sulfide, thiodicarboxamide (Ethoxyquin) Ethylicin (Ethylicin), ethylmercuric bromide, terrapin (ethyldiazole), famoxadone (Famoxadone), fatty acid (general), fenamidone (Fenamidone), sodium diutanoate (fenminosulf), enoximide (fenamistrobin), imipramil (fenopanil), fenrimol (fennarimol), fenbuconazole (Fenbuconazole), formamide (Fenfuram), fenhexamid (Fenhexamid), seed coat (Fenitropan), fenhexamid (Fenoxanil), fenpropidium (Fenpropimorph), fenpropimorph (fenpyr), triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide (Fenpropimorph), feram), florixamid, fluazinam, flufenamide (Flubenznamide), fluvalicazine, flufenamide (Flubenzimine), fludioxonil (Flubenzil), flufenamate (Flubenztron), flufenazazole (Fluxitrobin), flucanpyr, flumorph (Flusfaph), fluopicolide (Fluopicolide), fluoroetheramide (Fluofenamide), flupyrimide (Fluofenam), fluclomazone (Fluofenamide), triflumizole (Fluofenamide), fluxazoxystrobin (Fluofenamid), fluxazoxystrobin (Fluofenazole), flufenazole (Flusflufenazole), sulfenamid (Flusfamide), fluzonil (Fluofenamide), flufenamide (Fluofluvalil), flufenamide (Fluofomide), fluxazole (Fluofenamide), fluxazole (Fluoxamide) and fluxazole (Fluofenamide). Folpet (Folpet), formaldehyde, ethylphosphonic acid (Fosetyl), ethylphosphonic acid-aluminum (Fosetyl-aluminum), fuberidazole (Fuberidazole), furalaxyl (Furazazolyl), furalaxyl (Furazolidyl-M), furametpyr (Furazatuyl), furazoles (Furconazole), cis-furazoles (Furconazole-cis), furfural (Furfural), seed dressing amine (Furmecyllox), furyloxymethyl (Furyoxyfen), glutaraldehyde, chloroquine (Glyodin), griseofulvin (Griseofulvin), biguanide (Guazatine), quinoline acrylate (Halacite), hexachlorobenzene, hexachlorophene (Hexachloromycetin), hexaconazole (Hexaconazol), cyclohexophos (Hexyl), cycloxazole (Huanjo), myclobutanil (Hymeuzole), oxazine (hydrogen peroxide), hydrogen peroxide (Mefaxine), imazalil (Imazalil), iminoctadine (imazatadine), iminoctadine triacetate (Iminoctadine triacetate), iminoctadine tris (alkylbenzenesulfonate) (Iminoctadine tris (albesilate)), benfurazol (Inezin), ipconazole (ipconazol), iptriflumizole (ipfenoxazole), ipfluquin (Ipflufenoquin), iprobenfos (iprobofos), iproviolin (iproviolone), iprovalicarb (iproviolone), valicarb (Iprovalicarb), isobutyric acid, iprovalicarb (isofomesamine), iprovalicarb (isothiophanate), isopyrazamide (Isopyrazam), isothiamine (isotophan), ipzophos (ipzofoms), kresoxim (Kresoxim-methyl), and mixtures thereof Mancozeb (mancoppers), mancozeb (Mancozeb), tolfenpyr (mandestreobain), mandipyr (mandipropamide), maneb (Maneb), ortho-amide (Mebenil), benzocarb (mecarbizid), pencycurol (mefenoxam), mepanipyrim (Mepanipyrim), methoxam (Mepanipyrim), nifedipine (Meptyldinocap), mercury oxide, mercurous chloride, metalaxyl, mefenoxam, potassium metabisulfate, sodium metabisulfuron (metazoxolone), metconazol (metazole), sulfenpyrad (metacarbab), furbenomyl (metafuroxam), methyl isothiocyanate, methyl arsine sulfide (Methylarsenic sulphide), dithiocyano methane (Methylene bisthiocyanate), metiram (iram), phenoxypenoxsulam (metominotrbin), metrafenone (metafenone), thiabendazole (Metsulfovax), tetrazolidone (metatetraprole), mucic anhydride, myclobutanil (Myclobutanil), methimazole (Myclobutanil), N- (3-chloro-2, 6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furyl) acetamide, zin (Nabam), bis (dimethyldithiocarbamate) nickel, molluscicide (Niclosamide), phthalimid (Nitrothal isopropyl), fluorobenzol (Nuarimol), xin Saitong (octylinone), furoxamide (oxafurac), oryzalin (oryzalin), oxazopyr (oxazosulfanyl), quinoline copper (oxazil-copper), imidazole (oxathiols), oxazoxazosin (CAS), oxaziridine (oxazoxazosin), oxazamate (pazole) (52), and Paclobutrazol (CAS) and (oxazalin) wax (oxacarrier) (52). 72623-86-0), paraffin oil (CAS number 647-46-7), paraffin oil (CAS number 97862-82-3), chlorophenylpyridine (Parinol), penconazole (Penconazol), pencycuron (Pencycuron), penflufen (Penflufen), pentachlorophenol, penthiopyrad (Penthioprad), peracetic acid, phenylmercuric acetate, phenylmercuric chloride, phenylmercuric nitrate, phosphorus oxychloride (Phosdiphen), tetrachlorophthalide (Phthaide), and combinations thereof, tetrazolium picolinate (picarbazox), picoxystrobin (Picoxytrobin), pipropylum (Picoralin), potassium bicarbonate, potassium iodide, potassium phosphonate, potassium thiocyanate, probenazole (Probenazole), prochloraz (Prochloraz), procymidone (Prochloraz), propamidine (Propamidine), propamocarb (Propamocarb), propamocarb hydrochloride, propiconazole (Propiconazole), propineb (Propineb), propionic acid, propionioquinoline (Proquinazine), thiodicarb (Prothiocarb), prothioconazole (Prothioconazole), fluzoacyl hydroxylamine (Pydiflumevalonate), pyranyl (Pyrazoloplumetone), pyraclostrobin (Pyrazolyl), pyraclostrobin (Pyramoxymethyl), pyraclostrobin (Pyrazolyl), pyriproxyfen (Pyrazol), picolide (Propofectide) Bizoxamine (Pyrazinflumid), piroxicam (Pyrazolephos), piroxicam (Pyribenzarb), fluorobenzylpyridazine (Pyridachlormethyl), boscalid (Pyridinitril), pyripyroxim (Pyrifenox), pyrimethanil (Pyriferanil), pyrimorph (Pyriferph), pyrithione (Pyriferone), pyrithione (Pyriferol), fluquindox (Pyriferol), fluquintozene (Quinofil), benzoquinone (Quinoxyfen), pentachloronitrobenzene (Quintozene), thiocopper (Saentomong), fluzoxamine (Sedaxane), silthiopham (Siltufa), simeconazole (sodium, sodium carbonate, sodium bicarbonate, sodium hypochlorite, sodium metabisulfate), spiroxamine (Spiropine), the composition comprises sulfuryl fluoride, sulfur, tebuconazole (Tebufluquin), iso Ding Yiyang quinoline (Tebufloquin), phyllotoxin (Teclomazam), chloronitrobenzene (Tecnazene), tetraconazole (Tetraconazol), thiabendazole (Thiobenazol), thiabendazole (Thiofan), thifluzamide (Thiofluzamide), thimerosal (Thiomersal), thiabendazole (Thiophanate), thiophanate (Thiomethyl), kresoxim-methyl (Thioquinx), thiram (Thiovalinate), thiabendazole (Tiadinil), tolclofos (Tolclofos-methyl), tolfenpyr (Tolfenpyrad), triflumuron (Tolfenfant), tranexamine (Thioxazole), triazolone (Trimerozol), triazophos (Trifluvalinate), triclophate (Trifloxazole (Triflozin), triclopyr (Trifloxaprop), trivalexazole (Triflozin), trivalproate (Trifloxaprop) and Trivalicarb (Triflozin), trivalproate (Trifloxaprop) and (Triflozin).

An exemplary hydrophilic herbicide electrolyte may be a salt of a herbicide selected from the group consisting of: amide herbicides, aromatic acid herbicides, aroyl cyclohexanedione herbicides, arsenic-containing herbicides, benzofuranyl alkyl sulfonate herbicides, benzothiazole herbicides, carbamate herbicides, carbonate herbicides, cyclohexene oxime herbicides, cyclopropyl isoxazole herbicides, dicarboximide herbicides, dinitroaniline herbicides, dinitrophenol herbicides, diphenyl ether herbicides, dithiocarbamic acid herbicides, fumigating agent herbicides, haloaliphatic herbicides, imidazolinone herbicides, imide herbicides, inorganic herbicides, nitrile herbicides, organophosphorus herbicides, oxadiazolone herbicides, oxazole herbicides, phenoxy herbicides, phenylenediamine herbicides, pyrazole herbicides, pyridazinone herbicides, pyridine herbicides, pyrimidine diamine herbicides, pyrimidone herbicides, quaternary ammonium herbicides, thiocarbamate herbicides, thiocarbonate herbicides, thiourea herbicides, triazine herbicides, triazinone herbicides, triazolone herbicides, uracil herbicides, urea herbicides, and urea herbicides.

An exemplary hydrophilic herbicide electrolyte may be a salt of a herbicide selected from the group consisting of: (4-chlorophenoxy) acetic acid, 2,3, 5-triiodobenzoic acid, 2,3,6-TBA, 2,4, 5-trichlorophenol, 2,4, 5-trichlorophenoxyacetic acid, 2,4-D, 2,4-DB, 2, 4-D-dimethylammonium, 2,4-DEP, 2-ethylaminoethyl caproate, 2-hydrazinoethanol, 2-naphthyloxyacetic acid, ACC, acetic acid, acetochlor, acifluorfen (aciflufen), acifluorfen-sodium, benfuracarfen (Aclonifen), acrolein (Aclofenamide), alachlor (Allidochlor), graminezine (Alloxydime), allyl alcohol, alac, terfenadone (ambrinone), amethone (ambyn), terfenacet (Amlazine), amicarbazin (Ambrozine), amicarbazone (Amlazine) Amidocarpronic acid (Amidosulfuron), aminopyrimidic acid (Aminopyraclonil), aminopyralid (Aminopyraclonil), methamidophos (Amiprofos-methyl), acifluorfen (Amitrole), ammonium carbonate, ammonium sulfamate, anilofos (Anilofos), solenofen (Anisuron), anthracene oil, arsenical acid, sulbenazol (Asulam), sulbenazolin sodium (Asulam sodium), atraton (atlanto), atrazine (Atrazine), carfentrazone (Azafenidin), tetrazolsulfuron (Azimsulfuron), azido (Aziprozone), avena (Barban), fluoxastrobin (Beflubutamid), benazolin (Benazolin), ethylbenazolin (Benazol), benazolin (Bezasulfuron), benfluralin (Benfluralin), furben-zamate (benfuroate), bensulfuron-methyl (bensulfurol), bensulfuron-methyl (Bensulide), bentazone (bensulfydryl), fluazifop-methyl (Benzadox), amicarbazone (Benzadox ammonium), benzachlor (benzfeld), benoxamide (benziram), bicyclozin (benzobicycloon), pyrimidone (benzofenop), benzofluor (Benzofluor), neo-trospic (Benzoylprop), neo-ethyl (Benzoylprop), benzosulfuron (benzthizuron), flupyrazone (biclopyrne), carboxin (binox), bispyribac-sodium (Bispyribac-sodium), bronzadine (bronzadine) Bromoxynil (Bromobonil), bromobutamide (Bromobutide), bromophenoxime (bromonoxim), bromoxynil (Bromoxynil), bromoxynil butyrate (Bromoxynil butanoate), bromoxynil heptanoate (Bromoxynil heptanoate), bromoxynil octanoate (Bromoxynil octanoate), bromothalonil (Brompyrazon), tribromoron (Bromuron), buminafos, butachlor (Butachlor), flumetsulam (Butafenacil), imazalil (Butamifos), butachlor (butenamine), ding Saimi oxazin (buthizome), buthizome (Buthiuron), butralin (tralin), butachlor (butrydim), propargyl (bututuron), ding Caodi (butyalate), dimethylarsinic acid, flumetsulam (Canstrole), calcium methyl arsenate, calcium arsenate, calcium carbonate, calcium cyanamide, calcium hydroxide, calcium phosphate, cambendiolar, potassium octoate, diuron (carbasulim), bispyribac-sodium (carbotamide), carboxazole, carfentrazone (Carfentrazone), ethylcarfentrazone-ethyl, methoxyfenoxan (chlorpyrifos), chloral hydrate, dicamba (chlor), butyramide (chlorantyl), propargyl (Chlorazifop), propargyl-propargyl (Chlorazifop propargyl), colazine (Chlorazine), chlorbromoron (Chlorimuron), chlorpropham (Chlorpropham), furazolidone (chlorrette), chloreturon, varrozic (Chlorfenac), oat ester-methyl (chlorpropup-methyl), fluazifop (chlorfluorenol) methylchlorofluorene (Chlorflurenol methyl), chlorben (chlordazon), chlorimuron-ethyl (Chlorimuron), triclopyr (chlorponin), chlortoluron (chlortoluron), cumarone (chlorxuron), hydroxydiuron (chlorxynil), tribenuron (chlorpanium), tributyl chlorobenzyl chloride (Chlorphonium chloride), pyrifos (chlorpicron), chlorpropham (chlorrppham), chlorsulfuron (chlorrsulfuron), dimethyl chlorate (chlorrthamimid), chlorthiodicamine (chlorthimid), indomethacin (Cinidon-ethyl), cycloheptane (cinmethenyl), ether sulforon (cinofungin), cinofungin (ciprofungin), and clofos (ciprofos), clethodim, ioxydim, cloioxydim ester, cloiodate, clodinafop, propargyl Clodinafop-propargyl, clofibrate, clofop, isobutyl grass propionate, clomazone, clodroxamide, clomiprop, cyclohexenone, clopyralid, dimonium dichloride (Clopyralid dimethylammonium), clopyralid methyl (Clopyralid methyl), clopyralid ethanolamine (Clopyralid olamine), clopyralid potassium (Clopyralid potassium), clopyralid triisopropanolamine (Clopyralid tripromine), clomesalamine-methyl (Cloranssulim-methyl) fruit acid (cloxyfona), chlorbenzuron (Cridazine), cloxydim (Cumyluron), cymoxanil (Cyanatr-yn), cyanazine (Cyanazine), cybutaline (Cybutazine), cycloxaprine (Cyprazine), ciclopiramide (Cyclopyralid), ciclopirox (Cyclopyramid), cyclosulfamuron (Cycloxydim), thioxanthone (Cycloxydim), cycloatrane (Cyclorion), cyhalofop-butyl, forage (Cyhalofop-butyl), prazite (Cyperquat), praziram (Cyperquat chloride), cyprazine (Cypromid), diuron (Daimuron), cumquat (Dalapon), sodium (Dalapon-sodium), dazomet-sodium, dazomet-D, D-D, non-benazolin (Defenuron), butachlor (Delachlon), betametham, dichlormid (Desmeton), oat dichlormid (Di-alalate), dicamba (Dicamba), dichlormid (Dichlorobenil), 2, 4-d-propionic acid, 2-ethylhexyl-2, 4-d-propiophen, benazolin-methyl, diclosulam (Diclosulfam), didodecyl dimethyl ammonium chloride, licorice lock (Diethasection), pennogen (Difenoxaten), penoxsulam (Difenopen), penoxsulam-ethyl (Difenopenten ethyl), difenoxuron (Difenoxuron), difenoconazole (Difenozoquat), difenoxyfop (Difenzoquat metilsulfate), fluvalicamide (Difluzopyr), diflufon (Difluzopyr), difenoxyfop (Diflufen), oxamide (Diflufenoxaprop-methyl), dimethicone (Difenoxaprop-ethyl), penoxsulam (Difenoxaprop-ethyl), penfen (Difenoxaprop-4-methyl), penoxsulam (Difenoxaprop-ethyl), penfen (Difenoxaprop-ethyl), difenoxyfop (Difenoxyfop-methyl), difenoxyfop-ethyl (Difenoxyfop-84, difenoxyfop-methyl, difenoxyfop-ethyl (Difenoxyfop-methyl), difenoxyp-methyl (Difenoxyp-methyl), dipenmid (Difenoxyp-ethyl) and Difenoxyp-methyl (Difenoxap-ethyl (Dipenp-ethyl), deleylphenol triethanolamine (Dinoseb trolamine), terfenadine (Disterb), terleylphenol acetate (Disterb acetate), bispyribac-sodium (diphenomid), dillenaline (Dipropalin), prometryn (Diprotryn), diquat (Diquat), diquat dibromide (Diquat dibromide), diquat dichloride (Diquat dichloride), disodium methyl arsonate, disodium octaborate tetrahydrate, triamcinolone (Disu), triamcinolone-sodium (Disu-sodium), dithionite (Dithiopyr), diuron (Diuron), dixanthogen (DNOC, DNOC ammonium, DNOC potassium, DNOC sodium, glycyrrhizin-ethyl (Eglinzine-ethyl), polyacids (endothoal), propiolactone (epothilone), EPTC; suaeda (Erbon), penoxsulam (Esprocarb), vinyl silicon (Ethaselasil), ethambutol (Ethalfluralin), ethametsulfuron-methyl (Ethametsulfuron-methyl), glyoxal (Ethanedil), thidiazuron (Ethodimu), buprofezin (Ethiozin), ethofumesate (Ethofumete), fluorolactofen (Ethoxyfen) fluorolactofen-ethyl (Ethoxyfen ethyl), ethoxysulfuron (Ethoxysulfuron), nitrophenol (ethiofen), fatty acids (general), fenosulam, benazol-ethyl (fenhloraz-ethyl), nasal-discharge propionic acid (Fenoprop), nasal-discharge propionic acid Ding Yangyi propyl (Fenoprop-butometyl), nasal-discharge propionic acid ethyl (Fenoprop-butotyl), butyl (fenoprof-butyl), isooctyl (fenoprof-isoctyl) nasal discharge propionate, methyl (fenoprof-methyl), potassium (fenoprof-potssaum) nasal discharge propionate, t Ding Yangzhi (fenoprof-terboxyl), fenoxaprop-ethyl (Fenoxaprop-methyl), fenoxaprop-P-ethyl (Fenoxaprop-P), fenoxaprop-ethyl (Fenoxaprop-P-methyl), benzenesulfonyl (fenoxasulfane), fenquizalofone (fenquitrione), ethaboxam (Fenthiazamide), ethaboxam-ethyl (Fenthiaprop ethyl), fentrazamide (Fentazamide), fenoron (Fenuron), fenoxaprop-TCA, mebendazole-methyl Focus-isopropyl (Flamp-M-isopropyl), flazasulfuron (Flazasulfuron), florasulam, flurbiproflumilast (Florpyraxin), flurbiproflumilast (Florpyraxin-benzyl), fluazifop-butyl (Fluazifop-butyl), fluazifop-P-ethyl, fluazifop-butyl, isopropyrroate (Fluazolate), fluazifop-sodium (Flucarbazone-sodium), fluazifop-sodium (Fluoreturon), fluazifop-ethyl (Fluchlorethamine), flufenamid (Flufenacet), fluidazin-ethyl (Flufenpyr-ethyl), fluazifop-butyl (Fluazifop-butyl), fluazifop-pentyl (Flufenac-penyl), fluazifop-butyl (Fluazifop-butyl), flumipropy, flubenuron (Fluoxytube), sucralfate (Fluotidmid), trinitrotoluene (Fluodrifen), fluorooxyfluoride (Fluodrifen), fluoroglycofen-acid (Fluodrifen), carfentrazone (Fluodridine), fluthioron (Fluodriron), flufenamid (Flupox), fluoxastrobin (Fluprochol), sodium tetrafluoropropionate (Fluprofate-solid), fluflazasulfuron (Flupyrsulfuron), fluflazasulfuron-methyl-sodium (Flupyrsulfuron-methyl), fluazinone (Fluodridone), fludioxonil (Fluodridone), fluroxypyr (Fluodridone-meptyl), furazolone (Fluodrine), fluazinam (Fluor), fluazinam (Fluthiacet methyl), flucarbazin (Fomesafen) Formylaminosulfuron (Formosulfuron), xylocidal (Fosamine), xylocidal ammonium (Fosamine ammonium), furben-thiourea (Fuphenthiourea), furoxan, glufosinate, glyphosate (Glyphosate trimesium), glyphosate isopropylamine salt, glyphosate potassium salt, glyphosate (Glyphosine), fluclopyralid (haloxifen), fluclopyralid-methyl (haloxifen-methyl), flusulfamide (halospafen), halosulfuron-methyl (Halosulfuron-methyl), fluazinam (Haloxydine), fluhaloxyfop (Haloxyfop), fluhaloxyfop-ethyl (Haloxyfop-ethyl), fluhaloxyfop (Haloxyfop-P-methyl), oxime (hepopargil), hexachloroacetone (hexachloroethyl), potassium hexafluoroarsenate (hexafluoride), hexazinone (Hexazinone), imazamozin (imazabenz), imazamox (imazamezen-methyl), imazamox (Imazamox), imazethapyr (Imazapic), imazaquin (Imazaquin), imazethapyr (Imazethapyr), zopyr (Imazosulfuron), imazopyr (Imazosulfuron), trinexade (inabine), indenofloxacin (indianfan), indenofloxamine (indazaflam), iodobonil, ioiodized acid (Iodosulfuron), methyl-sodium (iodofurol-methyl-sodium), iofensulfuron, iofensulfuron sodium, ioxybenzonitrile (ioxynitrile), ioxynitrile (ioxynitrile) Xin Xiandian benzonitrile (Ioxynil octanoate), sodium Ioxynil (Ioxynil sodium), triazoxamide (ipfenarbazone), ferric sulfate (ironsulfophate), ding Mi amide (isoxarobamide), isoxaben (isosil), buprofezin (isothiozin), isoxaben (isooruron), isoprinate, isopropenyl (Isoproturon), isoprotyryl clomazone (isoxaron), clomazone (Isoxaben), clomazone (isoxachlor), clomazone (Isoxaflutole), clomazone (isoxapyrifos), clomazone (Karbutilate), lactofen (Lactofen), cycloxaprine (Lenacil), linuron (Linuron), prosulfocarb, MCPA-thioethyl, MCPB, chlorophenoxypropionic acid (Mecoprop), finely chlorophenoxypropionic acid, medinoterb, medinoterb acetate, mefenacet (Mefenacet), sulfenamide (mefiuidide), mepiquat chloride (Mepiquat), des She Yalin (Merphos), mesosulfuron (Mesosulfuron), mesosulfuron-methyl (Mesosulfuron-methyl), mesotrione (Mesotrione), oxazoxamide (metafop), oxazinone (metatron), sodium metabisulfuron, mezachlor (metachlor), metazosulfuron, mebendazole (Methabenzthiazuron), imazachlor (methazol), mesosulfuron (methamidon), mesosulfuron (methaquan), methimazole (Methizozoline), methimazole (Methizil), methoprene (Methiuron), methoprene (Methiprozone) methyl acetate, methyl isothiocyanate, methyl arsonic acid, methyl diuron (methyl ymron), pyrone (Metobenzuron), bromuron (Metobromiron), metolachlor, sulfentrazone (Metosulam), methoxon (Metosuron), metribuzin (Metribuzin), mesotrione-methyl (Metsulfuron), molinate-methyl (Metsulfuron-methyl), molinate (Molinate), pimentol (Monolide), lupulon (Monoliron), monosodium methyl, monosulfuron (Monosulfuron), bupirimate-methyl (Monosulfuron-methyl), mesotrione (Monuron), vaquorin (Morfamquat), vaquorin dichloride (Morfamquat dichloride), naproxen amine (Naproanlide), dichlormid (Napromimide), molinate amine, naptalam (Naptalam), cycloron (Neburon), nicosulfuron (Nicosulfuron), mesotrione (Nitra), herbicidal ethers (Nitrofen), fluramid (Norfluazinam), diuron (Noruron), O, O-dimethyl alpha- (2, 4-dichlorophenoxyacetoxy) ethyl phosphonate, turf (Orbencarb), pyriminobac-methyl (Orthosulfenamide), sulfamethoxazole (Oryzalin), oxadixyl (Oxadiaryl), oxadixyl (Oxadiazon), bentazone (Oxopyrazon), bentazone-dimoxamide, bentazone-sodium (Oxopyrazon-sodium), epoxysulfuron (Oxazosulfuron), oxazinone (Oxazinone), oxyfluorfen (Oxyfluorofen), paraquat (Paraquanil), dichloro-Paraquat (Paraquat dichloride), oxadixyl (Pentium), pelargonic acid, pendimethalin (Pentadine), penoxsulam (Penoxsulam), penoxsulam (Pentazin), penoxsulam (Pentamide), oxamide (Phthalamide-Phthalamide), phthalamide (Phthalamide-Phthalamide), picloram-triethanolamine (Picloram-trolamine), fluopyram (Picolinafen), pinoxaden (Pinoxaden), pipradrol (pipriophos), pipradrol (piprocyan), pipradrol (picctanyl), pipradrol bromide (Piproctanyl bromide), pretilachlor (Pretilachlor), primisulfuron (Primisulfuron), primisulfuron-methyl (Primisulfuron methyl), trifluralin (Prodiamine), fluxazin (Profluazol), ciprofloxacin (Profluralin), cyclophanone (Profoxydim), promethazine (proglin), promethazine (Proglinazine ethyl), prometan (Prometryn), prometryn (Prometryn), oxicam (Propaner), propanil (Propanil), oxazil (Propazide), promuzzard, prometryn (promazine), prometryn (Propazine) anilamide (Propham), isopropamide (Propisochlor), propylsulben-methyl (Propoxycarbazole), propylsulben-sodium (Propoxycarbazole-sodium), propyrisulfuron (Propyrizofuron), propargyl-oxamide (Propyzamide), prosulfocarb (Prosulfocarb), flucarbazin (Prosulfuron), oxamyl (Proximpham), propynoxamide (Prynachlor), pradazole (Pydannon), pyraclonil (Pyraclonil), pyriproxyfen (pyrafung), pyraclonil-ethyl (pyrafung), pyrazosulfuron-ethyl (Pyrazoxyfen), pyrazosulfuron-ethyl (pyrazofuron-ethyl), benzol (Pyrazoxyfen), pyriproxyfen (pyracle-pyriproxyfen), pyriproxyfen (pyrafung-propyl), pyribenzoxim (Pyribenzoxim), chlorpyribenzoxim (pyrimidafol), pyridate (pyrimidate), pyriftalid (Pyriftalid), pyriminobac-methyl (Pyriminobac-methyl) Pyricularia sulfenamide (Pyrimidosulfan), pyrithiobac-sodium (Pyridinothiobac-sodium), pyrifos (Pyroxasulfuron), pyroxsulam (Pyroxsulam), pyribac-sodium (Quinclorac), pyribac-sodium (Pyroxsulam-sodium), pyrifos-sodium (Pyroxsulam-sodium), pyrithiobac-sodium (Pyroxsula barnyard grass-dimethyl ammonium (Quinclorac-dimethyl ammonium), cloquintocet-mexyl acid (Quinmerac), chlorfenapyr (Quinclorac), quizalofop-ethyl (Quizalofop-ethyl), quizalofop-ethyl (Quizalofop-P-ethyl), quizalofop-P-tefuryl, rimsulfuron (Rimsulfuron) Saflufenacil, terbuzin, zhong Dingtong (secbumet), sethoxydim, cyclosulfuron (siluron), simazine, simetryn (Simetryn), prim (S-metachlor), sodium arsenite, sodium carbonate, sodium chlorate, sodium chloride, sodium monochloroacetate, sulcotrione (sulfozone), lawrenate (sulfofamate), sulfentrazone (Sulfometuron), sulfometuron-methyl (Sulfometuron-methyl), sulfosulfuron (sulfuric acid, SYP-1924, TCA-sodium, tebuchlor (Tebutam), tebuuron (tebucuron), furfuryltrione), cyclosulfamone (temcotrione), pyranone (Teanode), and pyriftime, terbutadine (Terbacil), terbutamine (terbuchol), terbutaline (terbuchanon), terbuchanin (terbuchanin), tetracyclozole (terciclaceis), ethaboxam (thienchloride), thifluzafipron (thiazafilon), thiazopyr (Thiazopyr), thiabendazole (Thiazopyr), thidiazuron (thiazuron), thioketosulfuron-methyl (thicarbazone-methyl), thifensulfuron (thifluzasulfuron-methyl), thiosulfuron (thiobacil), thiofide (Thiobencarb), fluoxastrobin (timonail), secondary pill (tioxaprop), pyracle (topirate), toprazone (tozodone), benzodiazuron (trazodone), benzodiazepine (trioxymethyl) Fluongoxsulam (Triafamone), dicamba (Tri-allate), imazalil (triamcinolone), cinosulfuron (Triasulfuron-methyl), tribenuron-methyl (Triasulfuron-methyl), de-She Lin (Tribufos), triclopyr (Triclopyr), butoxyethyl Triclopyr (Triclopyr butotyl), triclopyr (Triclopyr triethylammonium), benazoline (triphane), bentazone (triatazine), trifloxysulfuron (Trifloxysulfuron), trifloxysulfuron-sodium (Trifloxysulfuron-sodium), triflusulfuron (triflusuron-methyl), triflusulfuron-methyl (triflusuron-methyl), triflusulfuron-oxime (trisrufin), trifloxysulfuron (Tritosulfuron), urea sulfate, molinate (Vernolate), dithiacet (Xylachlor), and zinc oxide.

For example, the hydrophilic active ingredient electrolyte is one selected from the group consisting of: 2,4-DB, 2, 4-DB-dimethyl ammonium, 2, 4-DB-sodium, 2, 4-D-dimethyl ammonium, 2, 4-D-diethanolamine, 2, 4-D-isopropyl ammonium, 2, 4-D-triisopropanolamine, 2, 4-D-triethanolamine, 4-aminopyridine, 8-hydroxyquinoline sulfate, abscisic acid, acephate, acifluorfen-sodium, acrolein, acrylonitrile, graminetin-sodium, alpha-chloroethanol, aminopyralid, carfentrazone-ethyl (amitrole), carfentrazone-ethyl, sulfamate, aminopyralid-sodium, elvan hydrochloride (aviglycine hydrochloride), bentazone-sodium, flupiroxicone (biscyclopyr), biala-sodium (bilafos-sodium), bispyrifos-sodium, bordeaux mixture, polo-sodium, pyribenzoxim bromoxynil-potassium, bronopol, bupropion, butylamine, dimethylarsinic acid, cartap hydrochloride, acetamiprid hydrochloride, chlormequat chloride (chlormequat chloride), chloroacetic acid, tributyl chloride benzyl phosphonium chloride, chlorsulfuron, clethodim, bendazinate-potassium (clofenacet-potassium), clopyralid-ethanolamine, copper sulfate pentahydrate, cyanamide, chlorpyrifos, cyhalofop-butyl, coumarone-sodium, butyryl hydrazine, sulfolane-S-methyl, dicamba-sodium, fine 2,4-D propionic acid, 2,4-D propionic acid-potassium, gramet, paraquat, difenoate-sodium, dimetiln, dipotassium phosphate, diquat dibromide, disodium octaborate, cyproconazole-sodium, DSMA, chlorpyrifos-dipotassium, ethephon (ethphon), ethyl formate, fenoxaprop-p-ethyl, ferrous sulfate, florasulam, clopyralid, trifluoracene, sodium tetrafluoropropionate, formaminosulfuron, formaldehyde, valicamidine hydrochloride, carboximide-ammonium, ethanamine-aluminum, furfural, glufosinate, glyphosate-isopropylammonium, glyphosate-monoammonium, glyphosate-potassium, glyphosate-sodium (glyphosate-sequisodium), glyphosate, fluazifop-p-ethyl, fluazifop-p-butyl, aminopyralid, hexafiuoroarsine, hymexazol (imazamox) imazamox (imazamox), imidazoquinolinic acid-ammonium, imidazocyclopphos, iminoctadine triacetate, methyl iodosulfuron-methyl, ioxynitrile-potassium, ioxynitrile-sodium, isoxaflutole hydrochloride (kasugamycin hydrochloride hydrate), proscenium, MCPA-sodium, MCPB, chlorophenoxypropionic acid-potassium, chlorophenoxypropionic acid-sodium, fluorosulfonamide-diethanolamine, sulfenamide-potassium, mepiquat chloride, mepiquat penta-borate, mercuric chloride, carb-mu sodium, metamifen, methamidon, methoprene, methamidon, fast-clomazone (E) -isomer, monocrotophos, dipotassium phosphate, MSMA, mancozeb sodium, naproxen-sodium, nicotine, nitenpyram, the composition comprises thiamethoxam, omethoate, carboxin, sulfone, paraquat dichloride, thiocyclophos, phosphonic acid, picloram-potassium, picloram-triisopropanolamine, polyoxin B (polyoxin B), potassium bicarbonate, potassium cyanate, propamocarb hydrochloride, chlorfenapyr (proxan), sulfonyloxapyrazole (pyrasulfotole), clomequintocet acid, (Z) -3-sodium chloroacrylate, sodium 2-phenylphenol, sodium 5-nitroguaiacol (sodium 5-nitroguaiaclate), sodium bicarbonate, sodium chlorate, sodium chloroacetate, sodium o-nitrophenolate, sodium p-nitrophenolate, sodium selenate, spiroxamine, sulcotrione, TCA-sodium, cyclosulfamide, cycloxapriate, benzofuranone, trichlorfon, trin, trinexapac-ethyl, validamycin, triamcinolone, warfarin sodium.

For example, the emulsion may comprise

At least one lipophilic active ingredient selected from dimethenamid, metolachlor, and mixtures thereof; and

at least one hydrophilic active ingredient electrolyte selected from glyphosate or glufosinate salts.

The high concentration of polyanionic block copolymer surfactant is not required in the emulsion and the combination of about 0.1w/w%, 0.5w/w%, 1.0w/w%, 1.5w/w%, 2.0w/w%, 3.0w/w%, 4.0w/w%, 5.0w/w% or 6.0w/w% of the polyanionic block copolymer surfactant with the second surfactant will greatly improve stability. Typically, the concentration of polyanionic block copolymer surfactant in the emulsion is between 0.5w/w% and 12w/w%, preferably between 1w/w% and 11w/w%, preferably between 1.5w/w% and 10w/w%, preferably between 2w/w% and 9w/w%, preferably between 2.5w/w% and 6w/w%, preferably between 2w/w% and 8w/w%, preferably between 3w/w% and 7w/w%, relative to the total weight of the final emulsion.

The concentration of the second surfactant in the emulsion is typically between 0.5w/w% and 12w/w%, preferably between 1w/w% and 11w/w%, preferably between 1.5w/w% and 10w/w%, preferably between 2w/w% and 6w/w%, preferably between 2.5w/w% and 5w/w%, preferably between 2w/w% and 4w/w%, preferably between 1.5w/w% and 6w/w%, relative to the total weight of the final emulsion.

The emulsions of the present invention may be stable even at high loadings of salts such as hydrophilic active ingredient electrolytes. For example, the concentration of the hydrophilic active principle electrolyte in the emulsion is higher than 10w/w%, preferably higher than 12w/w%, preferably higher than 15w/w%, relative to the total weight of the final emulsion. Thus, for example, the emulsion may comprise between 5w/w% and 50w/w%, for example between 5w/w% and 30w/w%, between 7w/w% and 25w/w%, between 8w/w% and 22w/w%, between 9w/w% and 20w/w%, or between 10w/w% and 18w/w% of the hydrophilic active ingredient electrolyte relative to the total weight of the final emulsion. Illustrative non-limiting examples of the concentration of hydrophilic active ingredient electrolyte in the emulsion are above 120g/L, preferably at least 150g/L, or between 120g/L and 500g/L or between 150g/L and 300 g/L.

In the emulsions of the invention, the total loading of salt may be very high, for example, between 5w/w% and 50w/w%, for example between 10w/w% and 40w/w%, between 12w/w% and 35w/w%, and between 15w/w% and 30w/w%, relative to the total weight of the final emulsion. The salts may include the hydrophilic active ingredient electrolytes already mentioned, but may also include other salts, such as fertilizers. The fertiliser may be added to the emulsion disclosed in this document or as part of a tank mix.

The emulsions of the present invention may be stable even at high loadings of lipophilic active ingredients. Thus, for example, the emulsion may comprise between 25w/w% and 80w/w% of a lipophilic active ingredient, relative to the total weight of the final emulsion, for example between 30w/w% and 70w/w%, between 32w/w% and 65w/w%, between 35w/w% and 60w/w%, or between 37w/w% and 40w/w% of a lipophilic active ingredient, relative to the total weight of the emulsion. For example, the emulsion may contain between 200g/L and 1000g/L of lipophilic active ingredient. Illustrative non-limiting examples of the concentration of lipophilic active ingredient in the emulsion are above 200g/L, preferably at least 300g/L, or between 250g/L and 1000g/L or between 300g/L and 800 g/L.

The emulsions of the present invention comprise at least one lipophilic active ingredient and may therefore comprise additional lipophilic active ingredients. The organic phase may consist of one or more lipophilic active ingredients that are liquid at room temperature, or if any lipophilic active ingredients are solid at room temperature, an organic solvent may be added to dissolve the solid and provide a liquid organic phase that can be emulsified in the aqueous phase. The emulsions of the present invention further comprise one or more hydrophilic active ingredient electrolytes dissolved in the aqueous phase. Thus, the aqueous phase comprises a polyanionic block copolymer surfactant and at least one hydrophilic active ingredient. Although high concentrations of electrolyte were produced, salting out of the polyanionic block copolymer surfactant was not observed, and the emulsions of the present invention were unexpectedly stable even more stable than those using the polyanionic block copolymer surfactant alone. It has even been observed that additional electrolytes (e.g. fertilizers) can be added without significantly affecting the stability of the emulsion.

The emulsions of the present invention comprise a thickener. The particular type of thickener is not particularly relevant and those known in the art may be used. Thickeners are typically water soluble polymers that exhibit suitable plastic properties in aqueous media. Suitable thickeners may be compounds that affect the flow behaviour of the emulsion and may assist in its stabilisation against caking. Mention may be made, for example, of commercial thickeners based on polysaccharides, such as methylcellulose, carboxymethylcellulose, hydroxypropyl cellulose, xanthan gum, synthetic polymers, such as acrylic acid polymers, polyvinyl alcohol or polyvinylpyrrolidone, silicic acid or phyllosilicates, such as montmorillonite, attapulgite and bentonite, which may be hydrophobized. Xanthan gum is preferred. The concentration of thickener in the final emulsion is generally not more than 2w/w% based on the total weight of the final emulsion, and preferably ranges from 0.01w/w% to 2w/w%, especially from 0.02 wt% to 1.5 wt% and especially from 0.1w/w% to 1w/w% based on the total weight of the final emulsion.

Polyanionic block copolymer surfactants

Preferably, at least 90w/w% of the hydrophobic portion in the polyanionic block copolymer surfactant comprises a hydrophobic monomer. In some cases, a small amount of hydrophilic monomer (i.e., less than 10% of the amount of monomer) may be incorporated into the hydrophobic moiety. For example, the hydrophobic monomer is selected from the group consisting of an acrylate or derivative thereof, a methacrylate or derivative thereof, styrene or derivative thereof, and any combination thereof.

Alkyl acrylate monomers such as methyl acrylate, ethyl acrylate, or butyl acrylate are one exemplary embodiment in this regard. For example, the hydrophobic monomer is selected from the group consisting of: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and mixtures thereof, for example, the hydrophobic monomer is ethyl acrylate.

The hydrophilic portion of the anionic surfactant may be a hydrophilic block copolymer. The hydrophilic moiety comprises at least 60w/w%, such as at least 70w/w%, or at least 80w/w%, or at least 90w/w% of charged monomer. In one embodiment, 100w/w% of the hydrophilic moieties are made from charged monomers. Exemplary amounts of charged monomer relative to the hydrophilic moiety are 68w/w%, 77w/w%, 83w/w%, or 88w/w%.

In addition, the polyanionic block copolymer surfactant comprises at least 35w/w% charged monomer relative to the total weight of the polyanionic block copolymer surfactant, preferably at least 45w/w%, or 55w/w%, e.g., 58w/w% charged monomer relative to the total weight of the anionic surfactant.

The charged monomer of the anionic surfactant may be a zwitterionic monomer, for example an anionic monomer. Thus, it is preferred that at least 60% of the monomers in the hydrophilic portion are anionic monomers, typically sulfonate groups, such as 2-acrylamido-2-methylpropane sulfonate (AMPS). Thus, less than 40w/w% of the monomers in the hydrophilic portion are neutral hydrophilic monomers, such as one selected from the group consisting of N-vinyl pyrrolidone, ethylene oxide, glycoside acrylate, acrylamide, and mixtures thereof.

Typically, the weight percent of hydrophilic moieties relative to the total weight of the polyanionic block copolymer surfactant is at least 50w/w%, preferably from 65w/w% to 90w/w%, for example from 70w/w% to 85w/w%.

The polyanionic block copolymer surfactant typically comprises up to 150 monomers, or up to 85 monomers, for example 63 monomers, relative to its total weight. Thus, the weight of the polyanionic block copolymer surfactant can be up to 100,000g/mol, typically up to about 31,000g/mol, e.g., about 17,000g/mol, about 12,000g/mol. Alternatively, the weight of the polyanionic block copolymer surfactant may be 8,000 to 50,000g/mol, for example 10,000 to 25,000g/mol.

The hydrophilic portion may have a weight of 5,000 to 100,000g/mol, typically 6,000 to 50,000g/mol. Preferably, the hydrophilic moiety has a weight of 7,000 to 30,000g/mol, e.g. 8,000 to 12,000g/mol.

The weight of the hydrophobic portion may be 500 to 5,000g/mol, typically 1,000 to 4,000g/mol. For example, the hydrophobic portion comprises an alkyl acrylate monomer, preferably an ethyl acrylate monomer, and the weight of the hydrophobic portion is 1,000 to 4,000g/mol, for example 1,500 to 3,500g/mol, preferably 1,500 to 3,000g/mol.

Therefore, it is preferable that the molar ratio of the hydrophobic moiety to the hydrophilic moiety is 1:2-4. For example, the weight ratio between the hydrophobic portion and the hydrophilic portion ([ hydrophobic portion ]: [ hydrophilic portion ]) is typically less than 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.3, or less than or equal to 0.2. Typically, the weight ratio between the hydrophobic portion and the hydrophilic portion ([ hydrophobic portion ]: [ hydrophilic portion ]) is between 0.01 and 0.6, for example between 0.1 and 0.3.

Typical compositions of the polyanionic block copolymer surfactants used in the emulsions (or suspoemulsions thereof) disclosed herein include:

(A) A hydrophobic moiety obtained by polymerization of at least one hydrophobic monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate and 2-ethylhexyl methacrylate, in particular from the group consisting of methyl acrylate, ethyl acrylate and butyl acrylate; the hydrophobic portion comprises at least 90wt% of its units derived from the hydrophobic monomer, and the hydrophobic portion has a molecular weight ranging from 1,000 to 4,000g/mol, e.g., from 1,500 to 3,500g/mol, e.g., from 1,500 to 3,000 g/mol; and a first aspect is an oil-in-water agrochemical emulsion comprising:

(i) An aqueous phase, for example between 10w/w% and 90w/w% relative to the total weight of the final emulsion;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1w/w% and 15w/w% of a second surfactant, typically lipophilic, with respect to the total weight of the final emulsion, selected from sorbitan esters of fatty acids;

a polyalkoxylated alcohol selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C4-C30 aliphatic alcohols; and

Aliphatic or aromatic sulfates or sulfonates selected from the group consisting of alkyl sulfates, alkylaryl sulfates, arylalkyl sulfates, aryl sulfates, alkyl sulfonates, alkylaryl sulfonates, arylalkyl sulfonates and aryl sulfonates, preferably having molecular weights ranging from 8,000 to 50,000g/mol, for example from 10,000 to 25,000g/mol.

The polyanionic block copolymer surfactant is optionally neutralized with a basic compound. The basic compound may be any basic compound known in the art capable of neutralizing anionic surfactants. Basic compounds include, for example, inorganic bases, C _8-18 Alkylamine polyalkoxylates, alkanolamines, alkanolamides, and mixtures thereof.

Exemplary inorganic bases include ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, and mixtures thereof. C (C) _8-18 The alkylamine polyalkoxylate may be, for example, C _8-18 Alkylamine polypropoxylates and/or C _8-18 Alkylamine polyethoxylates. Exemplary C _8-18 Alkylamine polyalkoxylates include tallow amine polyalkoxylate, coco amine polyalkoxylate, oleylamine polyalkoxylate, and stearyl amine polyalkoxylate. C (C) _8-18 The alkylamine polyethoxylates can have from about 2 to about 50 moles of ethylene oxide per molecule, more preferably from about 2 to about 20 moles of ethylene oxide per molecule. Exemplary C _8-18 Alkylamine polyethoxylates include tallow amine ethoxylate (2 moles EO or 8 moles EO), coco amine ethoxylate, oleyl amine ethoxylate, and stearyl amine ethoxylate. Exemplary alkanolamines include diethanolamine and triethanolamine. Exemplary alkanolamides include oleic acid diethanolamide and linoleic acid diethanolamide, among others C _8-18 Diethanolamide of fatty acid.

A second surfactant

The second surfactant is one selected from the group consisting of:

sorbitan esters of fatty acids, preferably C ₆ -C ₃₀ Fatty acids, e.g. C ₁₀ -C ₂₄ A fatty acid;

polyalkoxy radicalsAn alkoxylated alcohol selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate.

Preferably the second surfactant is selected from the group consisting of: polyalkoxylated sorbitan or esters thereof, e.g. polyethoxylated sorbitan having formula (I)

Wherein the method comprises the steps of

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ And R is ₈ Each of which is independently selected from hydrogen and C ₁ -C ₃ Alkyl groups;

Y ₁ 、Y ₂ and Y ₃ Each of which is independently selected from hydrogen and C ₁ -C ₃ Alkyl groups, preferably hydrogen;

R ₉ is C ₁ -C ₃₀ Alkyl or C ₂ -C ₃₀ Alkenyl groups; and is also provided with

Each of x, y, z, and w is a natural number comprised between 0 and 20.

Another preferred secondary surfactant is a polyalkoxylated C having formula (II) ₄ -C ₃₀ Aliphatic alcohols

R _a O(CH(R _b )-C(H)(R _c )O) _n H

(II)

Wherein the method comprises the steps of

R _a Is C ₄ -C ₃₀ Alkyl, alkenyl or alkynyl; and is also provided with

R _b And R is _c Each of (3)Independently selected from hydrogen and C ₁ -C ₃ Alkyl groups.

For example, the second surfactant may be an aliphatic (unsubstituted) or aromatic (unsubstituted) sulfate or sulfonate selected from the group consisting of: alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate, with alkyl sulfate being preferred. Such compounds are, for example, sulfuric acid esters of the formula (IIIa)

R ₁₀ -(O) _x -SO ₃ ^- M ⁺

Or, for example, a sulfonate of formula (IIIb)

R ₁₀ -SO ₃

Wherein R is ₁₀ Selected from the group consisting of: unsubstituted C ₁ -C ₂₀ Alkyl, unsubstituted C ₇ -C ₃₀ Alkylaryl, unsubstituted C ₇ -C ₃₀ Arylalkyl and unsubstituted C ₆ -C ₃₀ An aryl group;

x is 0 or 1; and is also provided with

M ⁺ Is a monovalent cation, preferably a basic cation, such as one selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium, preferably lithium, sodium, or potassium.

Examples of emulsion compositions

Thus, in view of the above, exemplary oil-in-water agrochemical emulsions described herein may comprise

(i) An aqueous phase, for example between 10w/w% and 90w/w% relative to the total weight of the final emulsion;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1w/w% and 15w/w% of a second surfactant, typically lipophilic, with respect to the total weight of the final emulsion, selected from sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and an aliphatic or aromatic sulfate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, and aryl sulfate.

Alternatively, it may be a formulation comprising:

(i) An aqueous phase, for example between 10w/w% and 90w/w% relative to the total weight of the final emulsion;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1w/w% and 15w/w% of a second surfactant, typically lipophilic, with respect to the total weight of the final emulsion, selected from sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and aliphatic or aromatic sulfonates selected from the group consisting of alkyl sulfonates, alkylaryl sulfonates, arylalkyl sulfonates, and aryl sulfonates.

Alternatively, it may be a formulation comprising:

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in an aqueous phase, comprising between 25 and 50w/w%, preferably between 25 and 40w/w%, of a lipophilic active ingredient and optionally a lipophilic organic solvent, relative to the total weight of the final emulsion;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 1.0w/w% and 10w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises charged monomers comprising sulfate groups, and wherein the weight percentage of charged monomers relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1w/w% and 10w/w% of a surfactant soluble in the liquid organic phase, selected from sorbitan esters of fatty acids, relative to the total weight of the final emulsion;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; aliphatic or aromatic sulfateOr a sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate and aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate and aryl sulfonate.

Another exemplary oil-in-water agrochemical emulsion described herein may comprise

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in an aqueous phase, the liquid organic phase comprising between 25w/w% and 40w/w% of a lipophilic active ingredient and optionally a lipophilic organic solvent, relative to the total weight of the final emulsion;

(iii) At least 5w/w% relative to the total weight of the final emulsion of a salt comprising a hydrophilic active ingredient;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 1.0w/w% and 10w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises charged monomers comprising sulfonate groups, and wherein the weight percentage of charged monomers relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1w/w% and 10w/w% of a surfactant soluble in the liquid organic phase, selected from sorbitan esters of fatty acids, relative to the total weight of the final emulsion;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and aliphatic or aromatic sulfates or sulfonates selected from the group consisting of alkyl, alkylaryl, arylalkyl and aryl sulfates, alkyl, alkylaryl, arylalkyl and aryl sulfonates.

Another exemplary oil-in-water agrochemical emulsion described herein may comprise

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in an aqueous phase, the liquid organic phase comprising between 25w/w% and 40w/w% of a lipophilic active ingredient and optionally a lipophilic organic solvent, relative to the total weight of the final emulsion;

(iii) At least 5w/w% relative to the total weight of the final emulsion of a salt comprising a hydrophilic active ingredient;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 1.0w/w% and 10w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises charged monomers comprising sulfate groups, and wherein the weight percentage of charged monomers relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

Between 0.1 and 10w/w% relative to the total weight of the final emulsion of a surfactant soluble in the liquid organic phase, said surfactant being a polyethoxylated sorbitan of formula (I)

Wherein the method comprises the steps of

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ And R is ₈ Each of which is independently selected from hydrogen and C ₁ -C ₃ Alkyl groups;

Y ₁ 、Y ₂ and Y ₃ Each of which is independently selected from hydrogen and C ₁ -C ₃ Alkyl groups;

R ₉ is C ₁ -C ₃₀ Alkyl or C ₂ -C ₃₀ Alkenyl groups; and is also provided with

Each of x, y, z, and w is a natural number comprised between 0 and 20.

Another exemplary oil-in-water agrochemical emulsion described herein may comprise

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in an aqueous phase, the liquid organic phase comprising between 25w/w% and 50w/w% of a lipophilic active ingredient selected from the group consisting of dimethenamid-p-ethyl, metolachlor, and mixtures thereof, and optionally a lipophilic organic solvent, relative to the total weight of the final emulsion;

(iii) Between 5w/w% and 30w/w% of a hydrophilic active ingredient electrolyte selected from the group of organophosphorus herbicides, for example, one selected from the group consisting of salts of methamidophos, amifos, anilofos, triazophos, bialaphos, imazalil, clomazone, 2,4-DEP, DMPA, EBEP, xylocidal, glufosinate, glyphosate, sulbenazolin, pirimiphos, and meglumine-phoxim, relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 1.0w/w% and 10w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer comprising sulfate groups (such as 2-acrylamido-2-methylpropane sulfonate), and wherein the weight percentage of charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

between 0.1 and 10w/w% relative to the total weight of the final emulsion of a surfactant soluble in the liquid organic phase, said surfactant being a polyethoxylated sorbitan of formula (I)

Wherein the method comprises the steps of

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ And R is ₈ Each of which is independently selected from hydrogen and C ₁ -C ₃ Alkyl groups;

R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ and R is ₈ Each of which is independently selected from hydrogen and C ₁ -C ₃ Alkyl groups;

R ₉ is C ₁ -C ₃₀ Alkyl or C ₂ -C ₃₀ Alkenyl groups; and is also provided with

Each of x, y, z, and w is a natural number comprised between 0 and 20.

Method for preparing Emulsion (EW) disclosed in this document

The preparation of an oil-in-water emulsion typically involves preparing an aqueous phase and an organic phase, followed by mixing the two so that the organic phase is emulsified in the aqueous phase. For example, EW formulations can be prepared by adding a surfactant to the aqueous phase, and then adding the organic phase and subjecting to high shear.

In addition to the usual methods for preparing EW formulations, the inventors have found that improvements to this method provide emulsions with improved stability. It also includes preparing an organic phase and an aqueous phase. However, in this improved process, the premix does not contain a fully loaded salt (typically no salt). After emulsification, the entire amount of salt is added to the emulsion, preferably by the first amount of thickener. Thus, the steps of this method can be summarized as follows:

-preparing a premix of an oil phase and an aqueous phase. In the case of the aqueous phase, only a partial load of the salt of the final composition to be made into an emulsion is used. For example, 50w/w%, or 40w/w%, or 20w/w% (typically none (i.e., 0 w/w%)) of the salt of the final composition that will be made into an emulsion.

-mixing a premix of the aqueous phase and the oil phase such that the oil phase is emulsified in the aqueous phase.

-optionally, adding a first amount of a thickener. For example, 10w/w%, 30w/w%, or 50w/w%, or 40w/w%, or 20w/w% of the thickener of the final composition to be made into an emulsion.

The emulsion obtained in the preceding step is then mixed with the salt in an amount that complements the total amount in the composition. Preferably, all the salt is added in this step, especially in the case of hydrophilic active ingredient electrolytes, so that no salt is present during emulsification.

Finally, a second amount of thickener is added. This second amount complements any amount of thickener not added before, for example 90w/w%, 70w/w%, or 50w/w%, or 60w/w%, or 80w/w% of the thickener of the final composition to be made into an emulsion, or if no thickener has been added before, all of the thickener in the final emulsion.

The salts contained in the emulsions disclosed herein typically comprise a hydrophilic active ingredient electrolyte, preferably a salt of glufosinate or glyphosate. Thus, the method preferably comprises:

(i) Emulsifying an organic phase into the aqueous phase, the organic phase comprising between 0.1w/w% and 75w/w% of a lipophilic active ingredient, optionally a lipophilic organic solvent, relative to the total weight of the final emulsion, and between 0.1w/w% and 15w/w% of a second surfactant, typically insoluble in water, relative to the total weight of the final emulsion, the second surfactant being selected from sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from polyalkoxylated polyols or esters thereof, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate and aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate and aryl sulfonate;

The aqueous phase comprises water and between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percent of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%;

(ii) Optionally, mixing the emulsion previously obtained with a first amount of thickener;

(iii) Mixing the emulsion obtained in the previous step with 5w/w% or more of a hydrophilic active ingredient electrolyte, preferably glufosinate or glyphosate salt, relative to the total weight of the final emulsion;

(iv) The emulsion obtained in the previous step is mixed with a thickener.

The suspoemulsion of the invention

In addition to the advantages exhibited by the emulsions described herein, the inventors have also found that emulsions can be used to prepare unexpectedly stable suspoemulsions. The suspoemulsion may be prepared by mixing the EW formulation (in this case, the emulsion according to the invention) and the SC formulation. Alternative methods for preparing a suspoemulsion do not necessarily involve separately preparing two formulations:

1) All co-formulations except the organic phase and thickener are added, including those that will constitute SC.

2) Mix until the dissolvable material has dissolved.

3) The organic phase is added (optionally together with a surfactant).

4) High shear or standard mixing.

5) A thickener is added.

The resulting SE formulation is a formal mixture of the SC formulation and the components that will make up the EW formulation of the present invention.

As a result, a suspoemulsion is a formulation comprising an aqueous continuous phase containing emulsified oily droplets and solids in suspension. In the case of the present invention, a high loading of dissolved salts is also contained. The combination of stable emulsions with stable aqueous suspensions (such as SC formulations) does not guarantee the production of stable suspoemulsions, which presents its own specific difficulties. Thus, it is unexpected that the use of the emulsion of the present invention (or components thereof mixed with SC formulations) also provides a stable suspoemulsion.

The suspoemulsions of the present invention may be prepared by mixing the emulsions according to the present invention with SC formulations. SC formulations are aqueous formulations in which the active ingredient is suspended in solid form.

The ratio between the SC formulation and the EW formulation may vary, for example, from 1:50 to 50:1 (SC: EW) by weight, for example, between 1:30 and 10:1, or between 1:20 and 1:1. The suspoemulsions obtainable by the above-described process are unexpectedly stable and are therefore an aspect of the present invention.

Just as the emulsion, the suspoemulsion of the present invention may comprise an agriculturally acceptable inert additive. These may be from emulsions disclosed herein or may be incorporated into SC formulations.

The suspoemulsion of the present invention may be mixed with a tank mix adjuvant prior to its application in the field to improve physical properties and efficacy. Some materials may be used as agriculturally acceptable inert additives in the suspoemulsions of the present invention or mixed with the suspoemulsions of the present invention as tank mix additives prior to field application. Tank-mixtures resulting from mixing the suspoemulsions of the present invention with one or more tank-mix adjuvants are also an aspect of the present invention.

Non-limiting examples of agriculturally acceptable inert additives and tank-mix adjuvants are surfactants, wetting agents (or spreaders), adhesion agents, emulsifiers, dispersants, suspending agents, plant penetration agents (or transporters), antifreeze agents, preservatives, binders, fertilizers, thickeners, antioxidants, drift retardants, buffers, transforming agents, soil penetrating agents, UV absorbers, protectant binders, defoamers or wetting agents, such as those already disclosed elsewhere in this document.

The suspoemulsion of the present invention may comprise an additional surfactant selected from the group of alkyl polyglucosides. For example, the suspoemulsion may comprise a combination of alkyl sulfate, a polyanionic block copolymer surfactant, and an alkyl polyglucoside.

Method and application

This document discloses a method for controlling undesired vegetation, pests or diseases which comprises contacting an effective amount of an emulsion of the invention with the locus of the undesired vegetation, pest or disease.

The methods disclosed in this document are applicable to any undesired plant, pest or disease for which herbicides, insecticides or fungicides have known activity. In the same way, the methods disclosed in this document are applicable to any crop for which herbicides, insecticides or fungicides have known protective activity. The methods disclosed in this document are applicable to any crop plant, including but not limited to monocotyledonous plants, such as sugarcane, cereal, rice, maize (corn); or dicotyledonous plant crops such as beetroot (such as beet or fodder beet); fruits (such as pomes, stone fruits, or soft fruits, e.g., apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, or blackberries); leguminous plants (such as beans, lentils, peas, or soybeans); oil crops (such as rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, or peanuts); cucumber plants (such as cucurbits, cucumbers or melons); fiber plants (such as cotton, flax, hemp, or jute); citrus fruit (such as orange, lemon, grapefruit, or tangerine); vegetables (such as spinach, lettuce, cabbages, carrots, tomatoes, potatoes, cucurbits, or peppers); lauraceae (such as avocado, cinnamon, or camphor); tobacco; nuts; coffee; tea; vine; lupulus seed; durian; bananas; natural rubber plants; and ornamental plants (such as flowers, shrubs, broad-leaved trees, or evergreen trees, e.g., conifers).

The emulsions disclosed in this document (whether neat or as a tank mix) are applied to the field in varying amounts depending on the particular active ingredient used, the target crop and the unwanted plant, pest or disease to be controlled. In some embodiments, the active ingredients are each applied in an amount from about 1g/ha to about 1000g/ha, or from 100g/ha to about 700 g/ha.

The emulsions disclosed in this document may be applied before, at the time of, or after planting.

Experiment

SLES: sodium lauryl ether sulfate

Nansa 63B: sodium alkylbenzenesulfonate

PolyAgro A: as described in example 1 below

Soprophor 3D33: polyanionic surfactants. 2,4, 6-tris (1-phenethyl) polyoxyethylated phosphate.

Soprophor 4D348: ethoxylated tristyrylphenol sulfate (16 units)

AF-100: silica dioxide

Zoharpon SLS powder: sodium lauryl sulfate. Ionic surfactants

Agnique PG 9116: alkyl polyglycosides. Nonionic surfactant

Kelzan AP-AS: xanthan gum. Thickening agent

ATLOX 4913: graft copolymers of PMMA backbone with PEO chains grafted to the backbone.

AGRILAN 755: acrylic ester copolymer

ATLOX 4917: styrene acrylic acid copolymer

ATLOX 4919: d-glucopyranose, oligomerization

Example 1: preparation of the polyanionic Block copolymer surfactant used in the emulsion of the present invention

Samples of the polyanionic block copolymer surfactant as used in this document were prepared according to example 1 of WO 2017/098325 A1 (pages 46 to 48): polyarro a.

PolyAgro A is a diblock copolymer, the total weight of which is 17000g/mol, consisting of a hydrophobic part and a hydrophilic part. The hydrophilic portion was made from sodium 2-acrylamido-2-methylpropane-1-sulfonate (AMPS) monomer, which represents 77w/w% of the total weight of the copolymer. The other 23w/w% of the copolymer corresponds to the hydrophobic portion made of ethyl acrylate monomer. The total amount of monomers in the copolymer (degree of polymerization, DPn) was 85 monomers.

PolyAgro A was obtained according to the following procedure:

to a 2L double jacketed reactor equipped with a mechanical stirrer and reflux condenser were added 11.26g O-ethyl-S- (1-methoxycarbonylethyl) xanthate (CH 3CH (CO 2CH 3)) S (c=s) OEt), 264.08g ethanol and 356.32g deionized water and 1400g AMPS (Na) solution (50% active) and 1.52g 4,4' -azobis (4-cyanovaleric acid). The reactor contents were heated to 70 ℃ with stirring and nitrogen. The reaction mixture was aged at 70 ℃ for an additional hour, then cooled to ambient temperature and discharged. The solids content was measured to be 37.6% (115 ℃ C., 60 minutes). GPC Mals: mn=16300 mw=2600ip=1.6.

2127g of the above solution and 330g of deionized water were added to a 5L, double jacketed reactor equipped with a mechanical stirrer and a reflux condenser. The reactor contents were heated to 70 ℃ with stirring and a nitrogen flow. Once 70 ℃ was reached, 106.67g of Ethyl Acrylate (EA) was added over 2 hours and 37.37g of a 10wt% solution of 4,4' -azobis (4-cyanovaleric acid) was concomitantly added over 2.5 hours. After the addition of the initiator solution was completed, the reaction solution was further aged for one hour. After this time 44.85g of 10w/w% 4,4' -azobis (4-cyanovaleric acid) solution was added in one portion and the mixture was aged at 70 ℃ for an additional hour, then cooled to ambient temperature and discharged. The solids content was measured to be 40.0% (115 ℃ C., 60 minutes). Ethanol was removed from the polymer solution using a rotary evaporator. Water was added to obtain a final solids content of 40.4% polymer solution.

2600g of polymer solution was placed in a 5L double-jacketed reactor equipped with a mechanical stirrer and a reflux condenser. The pH of the solution was increased to 8.5 using 50% NaOH solution. The mixture was heated to 70℃with stirring, followed by the addition of 48.4g of 30w/w% hydrogen peroxide solution over 1 hour. At the completion of the addition, the solution was aged for a further 3 hours, then cooled and discharged.

Residual monomer was measured by HPLC and GC (amps=22 ppm, ea=2 ppm). The measured solids content was 37.5%. The polymer was used in the formulation according to the following example from a ready-made aqueous polymer solution at a concentration of about 30% w/w.

Example 2: stability of EW formulations comprising polyanionic Block copolymer surfactants

5 wt% (relative to the weight of EW) of anionic surfactant was dissolved in the aqueous phase. Glufosinate was added and dissolved. The organic phase was added to the aqueous phase and emulsified using IKA Ultra Turrax T10 for 15 seconds.

The stability of each formulation was checked by visual inspection after 0.5 hours, 1 hour, 2 hours and 24 hours. The results are summarized in table 1 below.

TABLE 1

PolyAgro A performed better than any of the other anionic surfactants, consistent with the results described in WO 2017/098325A 1. PolyAgro A did not show any separation on top, unlike all other anionic surfactants tested. A small phase separation was visible at the top after 24 hours. To further improve the stability of the formulation, the inventors tested the addition of a second surfactant, typically a surfactant soluble in the organic phase.

Example 3: stability test of emulsions containing different surfactants soluble in liquid organic phases

PolyAgro A as prepared in example 1 was dissolved in the aqueous phase. 5% of the oil-soluble surfactant was dissolved in the organic phase. The organic phase was added to the aqueous phase and emulsified using IKA Ultra Turrax T10 for 15 seconds. Xanthan gum is added to increase the emulsion viscosity. Glufosinate was added and mixed until dissolved. The results are shown in Table 2.

TABLE 2

Not all surfactants improve the stability of the formulation. For example, the use of atlax 4914 (polyisobutylene succinic anhydride-polyethylene glycol) resulted in immediate phase separation. On the other hand, atlax 4838B (calcium alkyl-arylsulfonate) and Genapol X060 (isotridecyl alcohol polyglycol ether) further improved the stability of the formulation relative to the formulation containing polyarro a alone. Ecosurf EH 3 (2-methyl hexanol polyethylene oxide/polypropylene oxide) also provides a more stable formulation, but presents some mixing problems. The best overall results were obtained with the following polysorbates: span 20 (sorbitan laurate), tween 20 (polysorbate polyethoxylate) or atlax 4916 (sorbitol ethoxylate).

The positive effect was demonstrated with polysorbates with different levels of ethoxylation.

Example 4: preparation of the suspoemulsion according to the invention

SC (SC 1) formulations having the components indicated in table 3 were prepared by mixing the components in the indicated amounts.

TABLE 3 Table 3

Following the procedure described in example 2, EW formulations can be prepared and then mixed with formulation SC described above to provide SE formulations having the components indicated in table 4

TABLE 4 Table 4

Alternatively, different components of the EW formulation may be added to the SC1 formulation of table 3 without formally preparing the EW formulation. Specifically, all aqueous components (including SC, i.e., all components except metolachlor) may be mixed until all soluble components are dissolved. Then, the organic phase (i.e. metolachlor) is added and mixed. Finally, the thickener Kelzan was mixed to form the SE formulation.

Example 5: stability of the suspoemulsion according to the invention

The stability of this formulation relative to similar formulations was tested using different tests. In the first set of experiments, zoharpon SLS was replaced with a different surfactant as indicated in table 5. The stability of the resulting formulation was tested as follows: (i) after 4 days at room temperature; (ii) after 4 freeze/thaw cycles; and (iii) after 4 days at 54 ℃. Based on the results of the 3 experiments, the overall stability in each case was determined.

TABLE 5

As indicated by the results, zoharpon SLS, sodium lauryl sulfate (unsubstituted C according to the invention ₁₂ Alkyl sulfate) is the only surfactant that provided overall good results in all stability tests (formulations 1 and 2). Geropon T/77 (amide substituted sulfonate) or ETA 70 (ethoxylated alkyl sulfate) with taurate structure did not perform well in all stability tests, which made formulation 3-formulation 6 unsuitable.

Additional experiments were performed to test the effect of polyarro a. In the SE formulation of example 4, the polyarro a was replaced or simply removed with other surfactants. The stability of the resulting formulation was tested as follows: (i) after 1 day at room temperature; (ii) after 1 freeze/thaw cycle; and (iii) after 1 day at 54 ℃. Based on the results of the 3 experiments, the overall stability in each case was determined. The results are shown in table 6 below.

TABLE 6

Only SE formulations containing polyarro a provided good stability in all tests (formulation 8). The results were remarkable in the case of atlax 4917 (modified styrene acrylic polymer) which was put on the market for improved static and steric repulsion, and in the case of atlax 4919 which was specifically designed for high electrolyte content according to the supplier.

Claims (14)

1. A suspoemulsion formulation comprising:

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener;

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%;

-between 0.1 and 15w/w% of a second surfactant selected from the group consisting of

Sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

An aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate;

and

(vi) Solid active ingredient.

2. The suspoemulsion of claim 1, comprising: a polymeric nonionic surfactant selected from the group of alkyl polyglucosides.

3. A suspension according to any one of the preceding claims, wherein the salt comprises a hydrophilic active ingredient electrolyte.

4. The suspension emulsion of any of the preceding claims, wherein the charged monomer comprises an anionic sulfonate group.

5. The suspension emulsion according to any of the preceding claims, wherein the second surfactant is selected from the group of alkyl sulfates.

6. An aqueous tank mix comprising an adjuvant and the suspoemulsion of claim 1.

7. A method for controlling undesired vegetation, pests or diseases, which comprises contacting an effective amount of the suspoemulsion as defined in claim 1 or the tank mixture as defined in claim 6 with the locus of the undesired vegetation, pest or disease.

8. An oil-in-water agrochemical emulsion comprising

(i) An aqueous phase;

(ii) A liquid organic phase emulsified in the aqueous phase, the liquid organic phase comprising at least one lipophilic active ingredient and optionally a lipophilic organic solvent;

(iii) At least 5w/w% salt relative to the total weight of the final emulsion;

(iv) A thickener; and

(v) A combination of surfactants comprising:

-between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety, relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percentage of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%; and

-between 0.1 and 15w/w% of a second surfactant selected from the group consisting of

Sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from the group consisting of esters of polyalkoxylated polyols, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

An aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate.

9. Emulsion according to claim 8, wherein the sum of the concentrations of the salt components (iii) is between 5w/w% and 50w/w%, relative to the total weight of the final emulsion.

10. Emulsion according to claim 9, wherein the concentration of the hydrophilic active ingredient electrolyte is between 5 and 50w/w% relative to the total weight of the final emulsion.

11. An aqueous tank mix comprising an adjuvant and the emulsion of any one of claims 8 to 10.

12. A method for preparing the emulsion, the method comprising

(i) Emulsifying an organic phase into the aqueous phase, said organic phase comprising at least one lipophilic active ingredient, optionally a lipophilic organic solvent, and between 0.1w/w% and 15w/w% relative to the total weight of the final emulsion of a second surfactant selected from sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from polyalkoxylated polyols or esters thereof, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate;

the aqueous phase comprises water and between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percent of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%, the aqueous phase optionally comprising less than 5w/w% of a salt relative to the total weight of the final emulsion;

(ii) Optionally, mixing the emulsion previously obtained with a first amount of thickener;

(iii) Mixing the emulsion obtained in the previous step with a salt in an amount up to a minimum amount of 5w/w% relative to the total weight of the final emulsion;

(iv) The emulsion obtained in the previous step is mixed with a thickener.

13. The method as claimed in claim 12, comprising:

(i) Emulsifying an organic phase into an aqueous phase, the organic phase comprising between 0.1w/w% and 75w/w% of at least one lipophilic active ingredient, optionally a lipophilic organic solvent, relative to the total weight of the final emulsion, and between 0.1w/w% and 15w/w% of a second surfactant, relative to the total weight of the final emulsion, the second surfactant being selected from sorbitan esters of fatty acids;

polyalkoxylated alcohols selected from polyalkoxylated polyols or esters thereof, and polyalkoxylated C ₄ -C ₃₀ Aliphatic alcohols; and

an aliphatic or aromatic sulfate or sulfonate selected from the group consisting of alkyl sulfate, alkylaryl sulfate, arylalkyl sulfate, aryl sulfate, alkyl sulfonate, alkylaryl sulfonate, arylalkyl sulfonate, and aryl sulfonate;

the aqueous phase comprises water and between 0.1w/w% and 15w/w% of a polyanionic block copolymer surfactant comprising a hydrophobic moiety and a hydrophilic moiety relative to the total weight of the final emulsion, wherein at least 60w/w% of the hydrophilic moiety comprises a charged monomer, and wherein the weight percent of the charged monomer relative to the total weight of the polyanionic block copolymer surfactant is at least 35w/w%;

(ii) Optionally, mixing the emulsion previously obtained with a first amount of thickener;

(iii) Mixing the emulsion obtained in the previous step with 5w/w% or more of a hydrophilic active ingredient electrolyte relative to the total weight of the final emulsion; and

(iv) The emulsion obtained in the previous step is mixed with a thickener.

14. Use of an emulsion according to any one of claims 8 to 10 for the preparation of a stable suspension as defined in claim 1.