Emulsifiable concentrates with amide / ester / cosolvent systems

Abstract

An emulsifiable concentrate (EC) is disclosed, comprising one or more biocides, one or more emulsifiers, and a solvent system (S), wherein the solvent system (S) comprises, more preferably, the following: a) one or more amide solvents (S1) having a water solubility of less than 1.50% w / w; b) one or more ester solvents (S2) having a water solubility of less than 1.50% w / w; and c) one or more cosolvents (S3) having a water solubility of greater than 1.50% w / w.

Description

Technical Field

[0001] This invention relates to an emulsifiable concentrate (EC) comprising one or more biocides, one or more emulsifiers, and a solvent system (S) comprising one or more amide solvents, one or more ester solvents, and one or more (partially) water-soluble cosolvents; to an emulsion-in-water (EW) formulation formed from said emulsifiable concentrate (EC); and to the use of ester solvents for improving the stability of EW formulations, wherein the non-aqueous phase contains amide solvents and (partially) water-soluble cosolvents. Background Technology

[0002] When preparing agrochemical formulations, it is typically necessary to dissolve the active ingredient (e.g., one or more pesticides) in a solvent and then dilute it in a larger volume of water so that it can be applied as a fine spray. Alternatively, it may be necessary to dilute the active ingredient in solution and load it onto seeds or a solid carrier. While some agrochemical active ingredients are salts and therefore highly soluble in water, allowing for easy dissolution, many other nonionic agrochemical active ingredients are hydrophobic and completely insoluble in water.

[0003] When the active ingredient is insoluble in water, the formulation is typically dissolved in a water-immiscible solvent with the addition of one or more surfactants, so that when added to water, the solution forms an oil-in-water emulsion. Such formulations are called emulsifiable concentrates (EC) formulations. Alternatively, a water-immiscible solution containing the active ingredient can be pre-emulsified in water in concentrated form. Such formulations are called emulsions-in-water (EW) formulations.

[0004] Solvents that are typically immiscible with water and are used in EC and EW formulations include, but are not limited to, aromatic hydrocarbons such as SOLVESSO. ® Series, alkanes such as EXXSOL ® Product category, ester solvent such as EXXATE ® These include various solvents (all manufactured by ExxonMobil), as well as ester solvents such as methyl oleate. Additionally, solvents immiscible with water at high concentrations include cyclic hydrocarbons such as cyclohexanone and isophorone. Recently, solvents exhibiting improved toxicity and reduced flammability have been used. These solvents include diester solvents of long-chain diacids with 8-16 carbon units (typically methyl ester derivatives) and fatty acid amide solvents (examples of which are C6-C). 16 (Dimethylamide and morpholinamide derivatives of fatty acids).

[0005] While these solvents may offer benefits such as improved emulsion stability, improved solubility properties, and low melting temperatures, few solvents achieve a good balance among all three.

[0006] The ester-based solvents described above exhibit excellent emulsion stability and a moderate melting point range, but typically have poor solubility for the active ingredient. The amide-based solvents described above also exhibit excellent active ingredient solubility and emulsion stability, but their relatively high melting points limit their application as solvents in emulsifiable concentrates that can be stored or used at low temperatures. Finally, solvents that combine reasonable active ingredient solubility with low melting points (such as propylene carbonate) often exhibit very poor emulsion stability, usually due to their undesirably high water solubility.

[0007] While the simplicity of a single solvent system has its advantages, it is very difficult to achieve a balance of all the properties required for an effective emulsifiable concentrate, and highly engineered solvents are often more expensive than the simple solvents described above.

[0008] Therefore, there is a need for more complex solvent systems that can achieve an impressive balance of these properties, preferably using relatively low-cost solvents to achieve high cost efficiency. Summary of the Invention

[0009] The present invention is an emulsifiable concentrate comprising a combination of one or more water-insoluble amide solvents, one or more water-insoluble ester solvents, and one or more (partially) water-soluble co-solvents, achieving a particularly advantageous balance between the solubility of the biocidal agent, emulsion stability, and low-temperature emulsifiable concentrate stability.

[0010] In a first aspect, the present invention relates to an emulsifiable concentrate (EC) comprising one or more biocides, one or more emulsifiers, and a solvent system (S), the solvent system (S) comprising, more preferably comprising, the following: a) One or more amide solvents (S1) having a water solubility of less than 1.50% w / w; b) One or more ester solvents (S2) having a water solubility of less than 1.50% w / w; and c) One or more cosolvents having a water solubility greater than 1.50% w / w (S3).

[0011] In another aspect, the present invention relates to an emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is an emulsifiable concentrate (EC) of the first aspect.

[0012] In a final aspect, the present invention relates to the use of one or more ester solvents (S2) having a water solubility of less than 1.50% w / w for improving the stability of water-in-oil emulsion formulations, wherein the non-aqueous phase comprises one or more amide solvents (S1) having a water solubility of less than 1.50% w / w and one or more cosolvents (S3) having a water solubility of greater than 1.50% w / w.

[0013] definition

[0014] Emulsifiable concentrates are typically optically transparent, oily liquid formulations prepared by dissolving a certain amount of a biocide in an organic solvent (such as benzene, toluene, xylene, and solvent oils). They may also contain surfactants (i.e., emulsifiers) and other additives. These concentrates are suitable for dispersion in an aqueous phase to form water-in-emulsion formulations. Emulsifiable concentrates must be single-phase, meaning that the biocide and any emulsifier must be completely soluble in the organic solvent at the concentration used.

[0015] An emulsion is a mixture of two or more normally immiscible liquids, in which one liquid forms a dispersed phase, suspended as tiny droplets within the other liquid (called the continuous phase). Emulsions are typically referred to as oil-in-water (i.e., water is the continuous phase) or water-in-oil (i.e., oil is the continuous phase). In the context of agrochemical formulations, oil-in-water emulsions (called water-in-emulsion formulations) are frequently used to disperse hydrophobic pesticides in crop fields.

[0016] The U.S. Environmental Protection Agency (EPA) defines a pest control agent as "any substance or mixture of substances intended to prevent, destroy, repel, or mitigate any harmful organism." Pest control agents can be chemical or biological agents (such as viruses or bacteria) used to combat pests, including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms that compete with humans for food, damage property, spread disease, or are simply unpleasant. In the context of agrochemical formulations, pest control agents are used to actively target harmful organisms (typically fungi, insects, and / or weeds) without unduly harming crop plants.

[0017] In the context of this invention, alkyl refers to straight-chain and branched alkyl chains, while aryl refers to any aromatic carbocyclic system, which is a monocyclic (e.g., phenyl) or fused-ring system (e.g., naphthyl or anthracene). Detailed Implementation

[0018] In a first aspect, the present invention relates to an emulsifiable concentrate (EC) comprising one or more biocides, one or more emulsifiers, and a solvent system (S), the solvent system (S) comprising, more preferably comprising, the following: a) One or more amide solvents (S1); b) One or more ester solvents (S2); and c) One or more co-solvents (S3).

[0019] Solvent system (S)

[0020] An essential component of emulsifiable concentrates (ECs) is the solvent system.

[0021] The solvent system (S) comprises, more preferably consists of, the following: a) One or more amide solvents (S1); b) One or more ester solvents (S2); and c) One or more co-solvents (S3).

[0022] Preferably, the solvent system (S) consists of the following: a) The one or more amide solvents (S1) comprising 1% w / w to 80% w / w, more preferably 10% w / w to 60% w / w, even more preferably 20% w / w to 50% w / w, and most preferably 30% w / w to 50% w / w of the total weight of the solvent system (S); b) The one or more ester solvents (S2) comprising 1% w / w to 80% w / w, more preferably 5% w / w to 60% w / w, even more preferably 5% w / w to 45% w / w, further preferably 5% w / w to 40% w / w, even more preferably 10% w / w to 45% w / w, and most preferably 10% w / w to 40% w / w, relative to the total weight of the solvent system (S); and c) The one or more co-solvents (S3) comprising, relative to the total weight of the solvent system (S), 1% w / w to 80% w / w, more preferably 10% w / w to 60% w / w, even more preferably 15% w / w to 60% w / w, further preferably 15% w / w to 50% w / w, even more preferably 20% w / w to 50% w / w, even more preferably 23% w / w to 60% w / w, and most preferably 23% w / w to 50% w / w. The total amount of components a), b) and c) does not exceed 100%.

[0023] Particularly preferred amounts of the one or more amide solvents (S1), the one or more ester solvents (S2), and the one or more co-solvents (S3) are given in Table A:

[0024] A particularly preferred range combination is #29, namely 10% w / w to 60% w / w (S1), 5% w / w to 45% w / w (S2), and 15% w / w to 60% w / w (S3).

[0025] The solvent system (S) preferably comprises an amount in the range of 1% w / w to 90% w / w relative to the total weight of the emulsifiable concentrate (EC), more preferably in the range of 10% w / w to 85% w / w, and most preferably in the range of 25% w / w to 80% w / w.

[0026] In the context of this invention, the solvent system is a combination of all solvents present in the emulsifiable concentrate (EC). In other words, the emulsifiable concentrate cannot contain any solvents other than those in the solvent system (S). In embodiments in which the solvent system (S) consists of a specific combination of solvents, only those solvents may be present in the emulsifiable concentrate (EC).

[0027] The solvent system (S) has a particularly advantageous balance of properties (of the emulsion formed by the solvent system), namely, a balance that is difficult to achieve with only one or two solvents, including the solubility of the biocides, melting point and emulsion stability.

[0028] The components of the solvent system (S) are described in more detail below.

[0029] The one or more amide solvents (S1)

[0030] An essential component of the solvent system (S) is one or more amide solvents (S1).

[0031] The one or more amide solvents (S1) each have a water solubility of less than 1.50% w / w.

[0032] Preferably, at least one of the one or more amide solvents (S1), more preferably each of the one or more amide solvents (S1) has a water solubility of less than or equal to 1.00% w / w.

[0033] Further preferably, at least one of the one or more amide solvents (S1), more preferably each of the one or more amide solvents (S1) has a water solubility of less than or equal to 0.50% w / w.

[0034] Preferably, at least one of the one or more amide solvents (S1), more preferably each of the one or more amide solvents (S1) has a melting temperature in the range of -100°C to 20°C, more preferably in the range of -60°C to 15°C, and most preferably in the range of -40°C to 10°C.

[0035] Preferably, at least one of the one or more amide solvents (S1), more preferably each of the one or more amide solvents (S1) has a pour point in the range of -100°C to 20°C, more preferably in the range of -60°C to 15°C, and most preferably in the range of -40°C to 10°C, as determined according to DIN ISO 3016.

[0036] Preferably, the combined one or more amide solvents (S1) have a pour point in the range of -100°C to 20°C, more preferably in the range of -60°C to 15°C, and most preferably in the range of -40°C to 10°C, as determined according to DIN ISO 3016.

[0037] Preferably, at least one of the one or more amide solvents (S1), more preferably each of the one or more amide solvents (S1) has 7 to 20 carbon atoms, more preferably 9 to 17 carbon atoms, and most preferably 11 to 15 carbon atoms.

[0038] Preferably, at least one of the one or more amide solvents (S1), more preferably each of the one or more amide solvents (S1) has a flash point of at least 40°C, more preferably at least 50°C, and most preferably at least 60°C as determined according to ISO 2719.

[0039] In a particularly preferred embodiment, the one or more amide solvents (S1) are selected from the group consisting of: dimethylhexanoamide, dimethylheptanoamide, dimethyloctanoamide, dimethylnonanoamide, dimethyldecanoamide, dimethylundecanoamide, dimethyldodecanoamide, dimethyltridecanoamide, dimethyltetradecanoamide, dimethylpentadecananoamide, dimethylhexadecanoamide, dimethylheptadecanoamide, dimethyloctadecanoamide, dimethylnonadecananoamide, dimethyleicosanoamide, and their unsaturated variants, such as dimethylsoybean oleamide, dimethyllower erucic acid rapeseed oleamide, and dimethyloleamide, as well as mixtures of fatty acid dimethylamides, such as C6-C10 Fatty acid dimethylamide and C 12 -C 18 Fatty acid dimethylamide, and any combination thereof.

[0040] The total amount of the one or more amide solvents (S1) is preferably in the range of 1% w / w to 80% w / w, more preferably 10% w / w to 60% w / w, even more preferably 20% w / w to 50% w / w, and most preferably 30% w / w to 50% w / w relative to the total weight of the solvent system (S).

[0041] The total amount of the one or more amide solvents (S1) is preferably in the range of 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w relative to the total weight of the emulsifiable concentrate (EC).

[0042] The one or more ester solvents (S2)

[0043] Another essential component of the solvent system (S) is one or more ester solvents (S2).

[0044] Each of the one or more ester solvents (S2) has a water solubility of less than 1.50% w / w.

[0045] Preferably, at least one of the one or more ester solvents (S2), more preferably each of the one or more ester solvents (S2) has a water solubility of less than or equal to 1.00% w / w.

[0046] Further preferably, at least one of the one or more ester solvents (S2), more preferably each of the one or more ester solvents (S2) has a water solubility of less than or equal to 0.50% w / w.

[0047] Preferably, at least one of the one or more ester solvents (S2), more preferably each of the one or more ester solvents (S2) has a melting temperature in the range of -100°C to 40°C, more preferably in the range of -80°C to 20°C, and most preferably in the range of -70°C to 10°C.

[0048] Preferably, at least one of the one or more ester solvents (S2), more preferably each of the one or more ester solvents (S2) has a pour point in the range of -100°C to 40°C, more preferably in the range of -80°C to 20°C, and most preferably in the range of -70°C to 10°C, as determined according to DIN ISO 3016.

[0049] Preferably, the combined total of the one or more ester solvents (S2) has a pour point in the range of -100°C to 20°C, more preferably in the range of -80°C to 15°C, and most preferably in the range of -70°C to 10°C, as determined according to DIN ISO 3016.

[0050] Preferably, at least one of the one or more ester solvents (S2), more preferably each of the one or more ester solvents (S2) has 2 to 25 carbon atoms, more preferably 4 to 22 carbon atoms, and most preferably 7 to 20 carbon atoms.

[0051] Preferably, at least one of the one or more ester solvents (S2), more preferably each of the one or more ester solvents (S2) has a flash point of at least 40°C, more preferably at least 50°C, and most preferably at least 60°C as determined according to ISO 2719.

[0052] In a particularly preferred embodiment, the one or more ester solvents (S2) are selected from the group consisting of: methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl dodecanoate, methyl tridecanoate, methyl tetradecanoate, methyl pentadecanoate, methyl hexadecanoate, methyl heptadecanoate, methyl heptadecanoate, methyl octadecanoate, methyl nonadecanoate, methyl eicosanoate, methyl isononanoate, 1-ethylhexyl palmitate, caprylic / decanoic acid triglyceride, propylene glycol dicaprylate / didecanoate, propane-1,2,3-triyl-2-ethylhexanoate, 2,2-bis[(octanoyloxy)methyl]butyl decanoate, trimethylolpropane trioleate, 2-ethylhexyl acetate, dibutyl adipate, and 2-ethylhexyl cocoate, and their unsaturated variants, such as methyl soybean oleate, methyl rapeseed oil with low erucic acid, and methyl oleate, and mixtures of fatty acid methyl esters, such as C6-C 10 Fatty acid methyl esters and C 12 -C 18 Fatty acid methyl esters, and combinations thereof.

[0053] The total amount of the one or more ester solvents (S2) is preferably in the range of 1% w / w to 80% w / w relative to the total weight of the solvent system (S), more preferably 5% w / w to 60% w / w, even more preferably in the range of 5% w / w to 45% w / w, further preferably in the range of 5% w / w to 40% w / w, even more preferably in the range of 10% w / w to 45% w / w, and most preferably in the range of 10% w / w to 40% w / w.

[0054] The total amount of the one or more ester solvents (S2) is preferably in the range of 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w relative to the total weight of the emulsifiable concentrate (EC).

[0055] The one or more co-solvents (S3)

[0056] The final necessary component of the solvent system (S) is one or more co-solvents (S3).

[0057] The one or more co-solvents (S3) each have a water solubility greater than 1.50% w / w.

[0058] Preferably, at least one of the one or more cosolvents (S3), more preferably each of the one or more cosolvents (S3) has a water solubility greater than or equal to 2.00% w / w.

[0059] Further preferably, at least one of the one or more ester solvents (S2), and more preferably each of the one or more cosolvents (S3), has a water solubility greater than or equal to 3.00% w / w.

[0060] Preferably, at least one of the one or more co-solvents (S3), more preferably each of the one or more co-solvents (S3) has a melting temperature in the range of -100°C to 0°C, more preferably in the range of -90°C to -5°C, and most preferably in the range of -80°C to -10°C.

[0061] Preferably, at least one of the one or more cosolvents (S3), more preferably each of the one or more cosolvents (S3) has a pour point in the range of -100°C to 0°C, more preferably in the range of -90°C to -5°C, and most preferably in the range of -80°C to -10°C, as determined according to DIN ISO 3016.

[0062] Preferably, the combined one or more co-solvents (S3) have a pour point in the range of -100°C to 0°C, more preferably in the range of -90°C to -5°C, and most preferably in the range of -80°C to -10°C, as determined according to DIN ISO 3016.

[0063] Preferably, at least one of the one or more cosolvents (S3), more preferably each of the one or more cosolvents (S3) has 2 to 25 carbon atoms.

[0064] Preferably, at least one of the one or more cosolvents (S3), more preferably each of the one or more cosolvents (S3) has a flash point of at least 40°C, more preferably at least 50°C, and most preferably at least 60°C as determined according to ISO 2719.

[0065] In a particularly preferred embodiment, the one or more co-solvents (S3) are selected from the group consisting of: propylene carbonate, butyl carbonate, glyceryl carbonate, hexyl glycol, hexanediol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, triethylene glycol, butyl ethylene glycol, butyl diethylene glycol, butoxypropyl-2-ol, dipropylene glycol monobutyl ether, 2,2,4-trimethyl-1,3-pentanediol, di(ethylene glycol) monomethyl ether, di(ethylene glycol) ethyl ether, di(ethylene glycol) monopropyl ether, 3-methoxy-3-methyl-1-butanol, methoxypropanol, N,N-dimethyllactic acid, ethyl lactate, propyl lactate, butyl lactate, cyclohexanone, benzyl alcohol, and triethyl citrate. γ-Butyrolactone, γ-caprolactone, methyl acetopropionate, ethyl acetopropionate, 1,2-isopropyltriglyceride (acetone glycerol), glyceryl formal, n-methylpyrrolidone, n-ethylpyrrolidone, n-butylpyrrolidone, methyl 5-(dimethylamino)-2-methyl-5-oxovalerate, dimethylacetoacetamide, diethylacetoacetamide, dimethyl isosorbide, dihydrol-L-glucanone, methyl acetoacetate, ethyl acetoacetate, dimethyl 3-methylglutarate, and combinations thereof.

[0066] In a particularly preferred embodiment, the one or more co-solvents (S3) are selected from the group consisting of: propylene carbonate, hexyl ethylene glycol, propylene glycol, dipropylene glycol monomethyl ether, N,N-dimethyl lactamide, ethyl lactate, cyclohexanone, benzyl alcohol, triethyl citrate, γ-caprolactone, ethyl acetal propionate, 1,2-isopropyltriglyceride (acetone glycerol), hexanediol, and combinations thereof.

[0067] The total amount of the one or more co-solvents (S3) is preferably in the range of 1% w / w to 80% w / w relative to the total weight of the solvent system (S), more preferably in the range of 10% w / w to 60% w / w, even more preferably in the range of 15% w / w to 60% w / w, further preferably in the range of 15% w / w to 50% w / w, even more preferably in the range of 20% w / w to 50% w / w, even more preferably in the range of 23% w / w to 60% w / w, and most preferably in the range of 23% w / w to 50% w / w.

[0068] The total amount of the one or more co-solvents (S3) is preferably in the range of 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w relative to the total weight of the emulsifiable concentrate (EC).

[0069] One or more biocides

[0070] Another essential component of emulsifiable concentrate (EC) is one or more pest control agents.

[0071] There are no limitations on the one or more biocides of the present invention.

[0072] Pesticides are generally chemical or biological agents (such as pest-killing active ingredients, compounds, compositions, viruses, bacteria, antimicrobial agents, or disinfectants) that prevent, disable, kill, or otherwise thwart pests through their effects. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms that damage property, cause disturbances, spread diseases, or act as vectors for diseases. The term "pesticide" also includes plant growth regulators that alter the expected growth, flowering, or reproductive rate of plants; defoliants that cause leaves or other foliage to fall off the plant, generally promoting harvest; desiccants that promote the drying of living tissues, such as unwanted above-ground parts of plants; plant activators that activate plant physiological functions to defend against certain pests; safeners that reduce the unwanted herbicidal effects of pesticides on crop plants; and plant growth promoters that affect plant physiological functions, such as enhancing plant growth, biomass, yield, or any other quality parameter of the harvestable product of the crop plant.

[0073] The following list of biocides applicable to the emulsifiable concentrates of this invention is intended to illustrate possible combinations but is not limiting: A) Respiratory depressants - Complex III inhibitors at the Qo site: azoxystrobin, fenoxystrobin, eugenol, fenoxystrobin, fenoxystrobin, flufenoxystrobin, flupyraclostrobin, fenoxystrobin, mandestrobin, fenoxystrobin, fenoxystrobin, fenoxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, fenoxy ... - Complex III inhibitors at the Qi site: cyazofamid, indoxofen, fenpicoxamid, pyridabenamide, pyridabenamide; - Complex II inhibitors: [List of inhibitors follows - not translated] - Other respiratory inhibitors: diflumetorim; nitrophenyl derivatives: fenvalerate, fenvalerate, fenvalerate, fluazinam, nitrofenoxam; ferimzone; organometallic compounds: triphenyltin salts, such as triphenyltin acetate, triphenyltin chloride, or triphenyltin hydroxide; silthiamethoxam; - The binding type of the quinone-extraquinone inhibitor stigmatellin is ametoctradin. B) Sterol biosynthesis inhibitors (SBI fungicides) - C14 demethylase inhibitors: Triazoles: azaconazole, bifenthrin, furazolidone, cyclohexidine, difenoconazole, tebuconazole, R-tebuconazole, flutriafol, cyproconazole, fluquinazole, flusilazole, fenbendazole, hexaconazole, imidacloprid, tebuconazole, cyproconazole, oximazole, paclobutrazol, tebuconazole, propiconazole, prothioconazole, silfluconazole, tebuconazole, flufenoxuron, triadimefon, triadimefon, tebuconazole, tebuconazole, fluopyram, ipfentrifluconazole, chlorfluazuron; Imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; Pyrimidines, pyridines, piperazines: chlorfenapyr, pyridaben, pyrazosulfanilamide; - δ14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, butylmorph, isotridecylmorph, benzyl benzoate, piperazine, spirocycline; - 3-Ketoreductase inhibitors: Cyclopyralid, Amifenoxam; - Other sterol biosynthesis inhibitors: chlorfenapyrazole; C) Nucleic acid synthesis inhibitors - RNA polymerase I inhibitors: Benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, furazolidone, oxazyl; - Other nucleic acid synthesis inhibitors: oxamyl, octathione, oxaquinoline, ethirimol sulfonate, 5-fluorocytosine, isopropylquinoline, fluopyram; D) Inhibitors of cell division and cytoskeleton - Microtubule polymerization inhibitors: benomyl, carbendazim, thiabendazole, methyl thiophanate, pyridachlometyl. - Other cell division inhibitors: ethoxysulfuron, thiamethoxam, pendimethalin, fluopyram, benomyl, benzoyl sulfide, pyraclostrobin, cyazofamid, fluopyram; E) Inhibitors of amino acid and protein synthesis - Methionine synthesis inhibitors: mepanipyrim, pyrimethanil; - Protein synthesis inhibitors: kasugamycin, kasugamycin hydrochloride hydrate, midomycin, streptomycin, oxytetracycline; F) Signal transduction inhibitors - MAP / histidine kinase inhibitors: fluoxetine, iprodione, procymidone, vinclozolin, fludioxonil; - Mechanism unknown: fluorophenoxyquinoline, propoxyiodoquinoline; G) Inhibitors of lipid and membrane synthesis - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyraclostrobin, isoprothiolane. - Lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole. - Compounds and fatty acids that affect cell membrane permeability: propamocarb; - Inhibitors of oxidized sterol-binding proteins: fluoxapiprolin and fluoxapiprolin. H) Inhibitors with multi-site action - Inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; - Thio- and dithiocarbamates: ferbam, mancozeb, mancozeb, metam, metiram, propineb, thiram, zineb, ziram. - Organochlorine compounds: dichlorophenoxyacetic acid, chlorothalonil, captan, chlorpyrifos, chlorfenapyr, dichlorophenol, hexachlorobenzene, pentachlorophenol and its salts, phthalide, para-methyl thiophanate; - Guanidine and others: Guanidine, dextrin, dextrin free base, biguanide salt, biguanide acetate, biguanide octylamine, biguanide octylamine triacetate, biguanide trioctylbenzene sulfonate, dithionin, fluoxetine, sulfadiazine, miticide; I) Inhibitors of cell wall synthesis - Dextran synthesis inhibitors: buspirone, polyoxin B; - Melanin synthesis inhibitors: quinolones, tricyclazole, propiconazole, dicyclomet, isoprothiolane, trifluoperoxynil; - Cellulose synthase inhibitors: dimethomorph, flumethomorph, dimethomorph, buprofen, benzimidazole, valamid, valamid; J) Plant defense inducers - Araratine-S-methyl, allylbenzol, isothiazine, tiadinil, prohexadione-calcium; phosphonates: tris(ethylphosphonic acid), aluminum tris(ethylphosphonate), phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium bicarbonate or sodium bicarbonate, dichlorobenzothiazole. K) Unknown mode of action - Bronitrofurazone, Cyclosulfuron, Cymoxanil, Dazomet, Imazalil, Dichloroisocyanurate, Pyridaben, Wild Bean Blight, Wild Bean Blight Methyl Sulfate, Diphenylamine, Seed Coating Ester, Amifenopyram, Flumetover, Flumetylsulforim, Sulfomethonium, Fluthiazolinium, Hypersensitive Protein, Chlorpyrifos, Phthalosporin, Quinoline Copper, Seboctylamine, Isobutylethoxyquinoline, Leaf Blight, Imidazin, Pyridaben, Thiamethoxam, Bromhexanil, Aminopyrifen, Flufenoxadiazam; L) Biological pesticides L1) Microbial agents with antifungal, antibacterial, antiviral, and / or plant defense activator activities: Powdery mildew parasiticus, Aspergillus flavus, Bacillus buddingus, Bacillus hygroscopicus, Bacillus amyloliquefaciens, Bacillus amyloliquefaciens subsp. plantae (also known as Bacillus belye), Bacillus megaterium, Bacillus mohaiweiensis, Bacillus mycosis fungi, Bacillus pumilus, Bacillus simplex, Bacillus halophyte, Bacillus subtilis, Bacillus amyloliquefaciens var. subtilis, Bacillus belye, Candida oligosacchari, Candida saitoana, Clavibactermegia ichiganensis (bacteriophage), Shield mold, Cryptococcus parasiticus, Cryptococcus albus, Dilophosphora alopecuri, Fusarium oxysporum, Clonestachys rosea f. catenulate (also known as Gliocladium) (catenulatum), pink bromoxynil, antibiotic lysinophil, mycolytic bromoxynil, drupocytosaccharomyces, microdochium dimerum, microsporum, Muscodor albus, Bacillus vesicularis, epiphytic Bacillus, polymyxa, pantothecin, Penicillium barometz, *Pseudomonas* species, *Pseudomonas leucosus*, *Pseudomonas flocculosa*, *Pichia aberrant*, *Pythium oligandrum*, *Sphaerodes mycoparasitica*, *Streptomyces glaucum*, *Streptomyces lidiflorus*, *Streptomyces purpureus*, *Trichoderma asperelloides*, *Trichoderma spp.*, *Trichoderma purpureus*, *Trichoderma harmatum*, *Trichoderma harzianum*, *Trichoderma polysporum*, *Trichoderma streptococcus*. stromaticum), Trichoderma virens, Trichoderma viride, Typhula phacorrhiza, Odman's sclerotium, Verticillium dahliae, and small zucchini yellow mosaic virus (non-toxic strain). L2) Biochemical pest control agents with antifungal, antibacterial, antiviral and / or plant defense activator activities: hypersensitive protein, Polygonum cuspidatum extract; L3) Microbial biocides with insecticidal, acaricidal, snailicidal, and / or nematode-killing activities: *Agrobacterium radiata*, *Bacillus cereus*, *Bacillus stolonifer*, *Bacillus thuringiensis*, *Bacillus thuringiensis* subsp. *cathays*, *Bacillus thuringiensis* subsp. *israelina*, *Bacillus thuringiensis* subsp. *wax borer*, *Bacillus thuringiensis* subsp. *kulstaq*, *Bacillus thuringiensis* subsp. *tenacylbrevicornu*, *Beauveria bassiana*, *Beauveria bassiana* species, *Chromobacterium sub-tsugae*, *Cotinus codlingus* granulovirus, *Pseudomonas codlingus* granulovirus, *Flavobacterium* species, *Bollworm nucleopolyhedrovirus*, *Cornus noctuida* nucleopolyhedrovirus, *Cornus noctuida* monochroa nucleopolyhedrovirus, *Heterobacter hygrophila*, *Cyclophorus flavus*, *Lecanicillium* *L. longisporum*, *L. muscarium*, *Metarhizium anisopliae*, *Metarhizium anisopliae microsporum*, *Metarhizium anisopliae locust*, *Nomura leishmania*, *Paecilomyces rosenbergii*, *Paecilomyces lilacinus*, *Bacillus japonicus*, *Bacillus pastoris* species, *Paecilomyces szawa*, *Paecilomyces punctata*, *P. ramosa*, *P. thornea*, *P. usgae*, *Pseudomonas fluorescens*, *Grey-winged noctuid moth nucleopolyhedrovirus*, *Skirmiceia skeletalina*, *Skirmiceia skeletalina*, *Skirmiceia skeletalina*, *Streptomyces flavus*, *Streptomyces flavus*. L4) Biochemical pest control agents with insecticidal, acaricidal, snail-killing, pheromone-based, and / or nematicidal activities: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-decadienoic acid ethyl ester (pear ester), (Z,Z,E)-7,11,13-hexadecanetrienal, heptyl butyrate, isopropyl myristate, lavender ester, cis-jasmone, 2-methyl-1-butanol, methyl eugenol, methyl jasmone, (E,Z)-2,13-octadecadien-1-ol, acetic acid (E,Z) -2,13-octadecadien-1-ol ester, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, termite pheromone, (E,Z,Z)3,8,11-tetradecadienyl acetate, (Z,E)9,12-tetradecadien-1-yl acetate, (Z)7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, Chenopodium ambrosiodes extract, neem oil, Quilay extract; L5) Microbial pest control agents with plant stress reduction, plant growth regulator, plant growth promotion and / or yield enhancement activities: Azotobacter agalactiae, Azotobacter brasiliensis, Azotobacter lipophila, Azotobacter iridozoensis, Azotobacter high-salt, Slow-growing rhizobia species, Slow-growing rhizobia ehrlich, Slow-growing rhizobia soybean, Slow-growing rhizobia lizardii, Slow-growing lupin rhizobia, Delfordia acidophila, Arbuscular mycorrhizal fungi, Mesophytic rhizobia species, Rhizobia pea biotype, Rhizobia pea clover biotype, Rhizobia pea broad bean biotype, Rhizobia tropicalis and Rhizobia spp. alfalfa; O) Insecticides from categories O.1 to O.29 0.1 Acetylcholinesterase (AChE) inhibitors: Aldicarb, fenvalerate, carbofuran, thiamethoxam, carbofuran, methyl ethyl sulfonate, carbaryl, carbamate, carbofuran, ethyl thiocarb, methyl ethyl sulfonate, chlorpyrifos, furazolidone, isoprocarb, methomyl, methomyl, chlorpyrifos, fenpyroxen, propoxur, thiamethoxam, thiophanate-methyl, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, phosmet, phosmet, dimethoate, dichlorvos, acephate, methyl chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos-S-methyl, diazinon, dichlorvos / DDVP, phosmet, dimethoate, methyl chlorpyrifos, acephate, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos-S-methyl, diazinon, dichlorvos / DDVP, chlorpyrifos, dimethoate, methyl chlorpyrifos, chlorpyrifos, chlorpyrifos-S-methyl, diazinon, dichlorvos / DDVP, dimethoate, dimethoate, chlorpyrifos, chlorpyrifos-S-methyl, dimethoate ... Phosphate, EPN, Ethiophos, Promethazine, Valdex, Benzophos, Fenitrothion, Fenthion, Thiazolium Phosphate, Heptenphos, Cyazolidinium Phosphate, Isopropylamine Phosphate, O-(Methoxyaminothio-phosphoryl)salicylic acid isopropyl ester, Isoxazolium Phosphate, Malathion, Phosphamidon, Methamidophos, Phosphamidon, Phosphamidon, Dibromophos, Omethoate, Sulfonate, Parathion, Methyl Parathion, Indomethacin, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Phosphamidon, Pyrazophos, Pyrazophos, Pyrazophos, Pyrazophos, Pyrazophos, Pyrazophos, Pyrazidazine ... O.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; acetamiprid, fipronil, butenpyram, pyrafluprole, pyriprole. O.3 Sodium channel modulators: Flufenoxuron, Allethrin, D-cis-trans Allethrin, D-trans Allethrin, Bifenthrin, κ-Bifenthrin, Bioallethrin, Bioallethrin S-cyclopentenyl, Biobenzylfuran, Cypermethrin, Cypermethrin, β-Cypermethrin, Trifluralin, λ-Cypermethrin, γ-Cypermethrin, Cypermethrin, α-Cypermethrin, β-Cypermethrin, θ-Cypermethrin, ζ-Cypermethrin, Phenoxycyanide, Delanolyl, Alkenyl Cypermethrin, fenvalerate, fenvalerate, cypermethrin, fenvalerate, flufenoxuron, flufenoxuron, cyhalothrin, deltamethrin, bromoflufenoxuron, heptamethrin, imidacloprid, chlorfluphenoxylate, methoxyfenozide, ε-methoxyfenozide, permethrin, fenvalerate, fenvalerate, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid, pyrethroid; DDT, methoxydichlorophenoxyacetic acid (DDT); 0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, thiamethoxam, cyclopyridamole, dinotefuran, imidacloprid, acetamiprid, thiamethoxam; nicotine; flupyradifurone, flupyrflufenoxam, trifluralin, dithiazolinium, flupyradifurone; 0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, ethyl spinosad; 0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, rapamycin, mibamectin; O.7 Juvenile hormone mimics: acetamiprid, acetamiprid, acetamiprid; phenoxycarb, fenvalerate; O.8 Various non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; trichloronitromethane, sulfonyl fluoride, borax, tartaric acid; O.9 Regulators of TRPV channels in string organs: Biprofen, Pymetrozine, Flufenoxuron; O.10 Mite growth inhibitors: Tetramethrin, Thiamethoxam, Flumethrin; Etoxazole; O.11 Microbial disruptors of the intestinal membrane in insects: Bacillus thuringiensis, Bacillus sphaericus, and their insecticidal proteins: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis; Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1; O.12 Mitochondrial ATP synthase inhibitors: bufenozide; triazole tin, tricyclic tin, fenbutatin, chlorfenapyr, trichlorfon; O.13 Oxidative phosphorylation decoupling agents via proton gradient interference: chlorfenapyr, DNOC, fipronil; O.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: chlorpyrifos, fenitrothion, chlorpyrifos, dichlorvos; O.15 Chitosan biosynthesis inhibitors type 0: bis(triflufenoxuron), flufenoxuron, diflufenoxuron, flucyclourea, flufenoxuron, flufenoxuron, lufenuron, flufenoxuron, polyfluorourea, flubendiamide, chlorfenapyr; O.16 Chitosan biosynthesis inhibitor type 1: thiamethoxam; O.17 Ecdyskin disruptor: cyromazine; O.18 Ecdysone receptor agonists: methoxyfenozide, fenbufenozide, chlorfenapyr, furazolidone, cyclotebufenozide; O.19 Octopus amine receptor agonist: Dimethicone; O.20 Inhibitors of electron transport in mitochondrial complex III: flufenoxuron, cypermethrin, pyrimethanil, bifenazate; O.21 Inhibitors of electron transport in mitochondrial complex I: quinclorac, azoxystrobin, pyrimethanil, pyridaben, pymetrozine, fenvalerate; rotenone; 0.22 Voltage-dependent sodium channel blockers: indoxacarb, cyfluthrin; 0.23 Acetyl-CoA carboxylase inhibitors: Spirodiclofen, Spirodiclofen, Spirodiclofen, Ethyl methoxypiperidine, Spirodiclofen diester, Spiroxamat. O.24 Inhibitors of electron transport in mitochondrial complex IV: aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide; 0.25 Inhibitors of electron transport in mitochondrial complex II: pyridaben, fenflurfen, etoxazole, pyrazolyl aniline; 0.28 Rianotinamide receptor modulators: chlorantraniliprole, broflanilide, cyclobrombutamide, flubendiamide, fluchlorfenapyr; tetrachlorantraniliprole; tetrazolium acetonide; thiofenoxam; chlorfenapyr; O.29 String organ modulator: flupyradifurone; 0.30 GABA-gated chloride channel allosteric modulators: brofenoxam, chlorfenapyr, isoxazolidinamide; O.33 Calcium-activated potassium channel regulator: Flufenoxuron (acynonapyr); O.34 Flumetoquin, an inhibitor of electron transport in mitochondrial complex III at the Qi site. O.UN Insecticidal compounds with unknown or uncertain modes of action: Afurazone, Azadirachtin, Sulfamethrin, Benzoate, Bromopropylate, Acaricide, Cryolite, Cyprodinil, Dichlorophenoxyacetic acid, Trichlorfon, Pyrimethanil, Floctoquin, Flumetoquin, Flufenoxuron, Flupyradifurone, Flurranazine, Methaldehyde, Oxadiazon, Piperazine, Trifluthrin, Thiophanate, Trifluthrin, Umifoxolaner, and Bacillus subtilis. The active ingredient of firmus (Votivo); trifluimidinamide; chlorpyrifos; saloran, loteranan; benzpyrimoxan; tigolaner; oxazolidinamide; cyclobutrifluram; indox; flufenoxuron; trifluimidinamide.

[0074] P) Herbicides from categories P1 to P15

[0075] P1) Inhibitors of lipid biosynthesis: - ACC-Hydroxyfen, quizalofop-p-ethyl, butanil, clethodim, clodinafop-propargyl, clodinafop-propargyl, thiamethoxam, cyhalofop-propargyl, cyhalofop-propargyl, quizal ... - Non-ACC herbicides: benfuresate, butylate, cycloate, cogon grass blight, piperazine, EPTC, pendimethalin, ethoxyfuran, tetrafluoropropionic acid, molinate, orbencarb, pebulate, bensulfanilamide, TCA, quizalofop-p-ethyl, gentamicin, and vernolate. P2) ALS inhibitors: - Sulfonylureas: Acrylsulfuron-methyl, Tetraazolidone, Benzosulfuron-methyl acid, Benzosulfuron-methyl, Chlorpyrisulfuron-methyl acid, Chlorpyrisulfuron, Greensulfuron, Ethersulfuron, Ciprosulfuron-methyl, Aminosulfuron-methyl acid, Aminosulfuron-methyl, Ethoxysulfuron-methyl, Pyrimisulfuron, Flupyrsulfuron-methyl, Flupyrsulfuron-methyl acid, Flupyrsulfuron-methyl sodium, Formamidesulfuron, Chlorpyrsulfuron-methyl acid, Chlorpyrsulfuron-methyl, Azoxypyrsulfuron-methyl, Methyliosulfuron-methyl acid, Methyliosulfuron-methyl sodium, Iosulfuron, Iosulfuron-methyl sodium, Disulfuron-methyl acid, Metazosulfuron, mesosulfuron acid, mesosulfuron, nicosulfuron, pyrimethanil, epoxypyrimethanil, flupyrimethanil, flupyrimethanil, promethazine, flusulfuron, pyrimethanil, pyrimethanil, sulfonylsulfuron, mesosulfuron acid, mesosulfuron, sulfonylsulfuron, thifensulfuron acid, thifensulfuron, etherbensulfuron, benzylsulfuron acid, benzylsulfuron, trifluridinesulfuron, flumethanil, flumethanil, and triflumethanil; - Imidazolinones: imidacloprid, imidacloprid methyl methoxyfenozide, methyl imidacloprid, imidacloprid, imidacloprid nicotinic acid, imidacloprid quinolinic acid, and imidacloprid; - Triazolopyrimidine herbicides, and sulfonyl aniline herbicides: chlorpyrifos, chlorpyrifos, chlorpyrifos, pyrimisulfan, pyrimisulfan, pyrimisulfan, penoxsulam, pyrimisulfan, and pyrimisulfan; - Pyrimidinyl benzoate esters: bispyribac-sodium, bispyribac-sodium, pyrimidinoxime, cyclopyrimidin, pyrimidin acid, pyrimidin, pyrimidin thiosulfate, pyrimidin thiosulfate-sodium; - Sulfonylaminocarbonyl-triazolone herbicides: fluoxetine, fluoxetine-sodium, propanil, propanil-sodium, thiazosulfuron acid, and thiazosulfuron; - and fluroxypyr; P3) Photosynthesis inhibitors: Ampicillin, a photosystem II inhibitor, is a triazine herbicide, including chlortriazine, triazinones, triazindiones, methylthiotriazines, and pyridazinones such as atrazine, atrazine, chlormequat, cypermethrin, diquat, isoamyl acetate, cyclomethazine, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn, and trietazin. Arylurea such as chlorobromopropylate, chlormequat, chloroxuron, oxazol, diquat, fenflur, isoproturon, and isopropargyl are also mentioned. Oxalon, linuron, fenproxil, methylbenzylthiazoline, pyranolol, methoxyfenozide, chlorpyrifos, cyclohexane, butyrazosulfuron, and thiadiazuron; phenyl carbamates such as desmedipham, karbutilat, phenmedipham, and ethyl betaine; nitrile herbicides such as bromofenoxim, bromobenzonitrile and its salts and esters, iodobenzonitrile and its salts and esters; uracils such as chlorpyrifos, cyclohexane, and terbuprofen; as well as bentazon and bentazon-sodium, pyridate, pyridafol, methyl chlorpyrifos, and propargite; and photosystem I inhibitors such as diquat, diquat dibromide, paraquat, paraquat dichloride, and paraquat dimethyl sulfate; P4) Protoporphyrinogen-IX oxidase inhibitor: Trifluralin, trifluralin sodium, pyrazosulfuron, benzalkonium chloride, pyrazosulfuron, methoxyfenozide, flupropargyl, pyrazosulfuron, pyrazosulfuron, methoxyfenozide, chlorimide, indole-methyl, cyprodinil, isopyram, flupyridazine, flupyridazine ethyl ester, flupyrazosulfuron, flupyrazosulfuron, propyzoxystrobin, ethoxysulfuron, cyprodinil, propyzoxystrobin, flupyrazosulfuron, cyprodinil, flupyrazosulfuron, cyprodinil, flupyrazosulfuron, cyprodinil, flupyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, mesosulfuron, thiamethoxam, flupyrazosulfuron, trifluralin, flupyrazosulfuron; P5) Bleaching agents and herbicides: - PDS inhibitors: flubutyrazole, pyrifluquinazon, fluroxypyr, flurochloridone, furazolidone, dapoxetine, flupyroxypyr, pyrimisulfuron; - HPPD inhibitors: benzobicyclon, benzofenap, flupyrazole, isoxaflutole, fenquinoline, isoxaflutole, mesotrione, oxotrione, pyrazolynate, pyrazoxyfen, sulfadiazine, tefuryltrione, pyrazosulfuron, benzopyrrolizumab, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxaflutole; - Bleaching agents, unknown targets: aclonifen, chlorpyrifos, flumeturon, bixlozone. P6) EPSP synthase inhibitors: Glyphosate, glyphosate-isopropylammonium, glyphosate-potassium and glyphosate-trimethyl sulfide (thiophos); P7) Glutamine synthase inhibitors: Bisammoniazoline (bisammoniazoline), bisammoniazoline-sodium, glufosinate, glufosinate-ammonia, and glufosinate-ammonia; P8) DHP synthase inhibitor: asulam; P9) Mitosis inhibitors: - Group K1: Dinitroaniline herbicides: fluroxypyr, sec-butylpyr, dichlorophenoxypyr, etalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, and trifluralin; Phosphoramides: acephate, acephate-methyl, and butamiphos; Benzoic acid herbicides: chlorthal, methyl chlorphthalate; Pyridines: fluthion and thiamethoxam; Benzamides: propyzamide and tebutam. - K2 group: carbetamide, chlorfenapyr, dicofol, dicofol-isopropyl methyl ester, dicofol-methyl ester, dicofol-isopropyl ester, dicofol-methyl ester, and chlorfenapyr. P10) VLCFA inhibitors: - Chloracetamides: acetochlor, alachlor, acetaminophen, butachlor, dimethachlor, dimethenamid, dimethenamid, pyrazochlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propisochlor, and thenylchlor. - Oxyacetanilides: Fluthiamethoxam and Benthiamethoxam; - Acetanilides: diphenamid, naphthylpropane, dichlorvos, and dichlorvos; - Tetrazolinones: fentrazamide; - Other herbicides: ailofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperazine, pyroxasulfone, sulfamethoxam, and isoxazoline; P11) Cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flumetsulam, indazon-flumetsulam, isoxaben, triazine-flumetsulam; P12) Decoupled herbicides: dinoterb, DNOC and their salts; P13) Plant growth regulator herbicides: 2,4-D and its salts and esters, such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts, such as aminopyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benzolin, chloramben and its salts and esters, clonprop, clopyralid and its salts and esters, dicamba and its salts and esters, dicamba and its salts and esters, 2,4-D propionic acid (dic... 2,4-D propionic acid and its salts and esters, flopyrauxifen, fluroxypyr, clopyroxyisopropyl butyroxyl clopyr, isooctyl clopyr, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl ester, MCPB and its salts and esters, mecoprop and its salts and esters, clopyr, florpyrauxifen, florpyrauxifen and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridinecarboxylic acid; P14) Plant auxin transport inhibitors: diflufenzopyr, diflufenzopyr sodium, naptalam, and naptalam sodium; P15) Other herbicides: bromobutyroxyfen, chlorfluazuron, chlorfenapyr, cyclohexane, bensulfuron, cyclopyrimorate and its salts and esters, malathion, dazomet, fenthion methyl sulfate, thiamethoxam, DSMA, chlorfluazuron, chlorfluazuron and its salts, ethoxybenzamide, chlorfluazuron, chlorfluazuron butyl ester, furazolidone, phosmet, phosmetammonium, indicarb, maleic hydrazine, flusulfuron, methyl thiophanate, methyl azide, methyl bromide, methyl chlorfluazuron, methyl iodide, MSMA, oleic acid, oxadiazon, nonanoic acid, barnyardgrass, cyhalothrin, tetraflufenoxam, cyhalothrin.

[0076] Q) Safety agent

[0077] (quinoline-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oxime-phenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamide, 1,8-naphthalenedicarboxylic anhydride, 2-halo-4-(haloalkyl)-5-thiazolic acid, thiophosphates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives, such as amides, esters and thioesters, provided that they have an acid group.

[0078] Each of the one or more pest control agents can be any substance used to control pests, whether chemical or biological, such as insecticides, herbicides, fungicides, acaricides, rodenticides, nematicides, and miticides.

[0079] Suitable insecticides can preferably be selected from the group consisting of neonicotinoids, diamides, benzoylureas and carbamates.

[0080] Preferably, each insecticide is selected from phenoxycarb, deltamethrin, piperonyl butyl ether, imidacloprid, thiamethoxam, acetamiprid, aldicarb, aldicarb sulfoxide, aldicarb sulfone, pirimicarb, chlorantraniliprole, terbufos, quinalphos, terbufos, phosmet, carbaryl, etoxazole, thiamethoxam, flonicamid, permethrin, phorate, profenofos, parathion, methyl parathion, acephate, phorate, fenthion, cypermethrin, fipronil, propoxur, methomyl, cyhalofop-p-ethyl, pymetrozine, nematicide, and deltamethrin. Cypermethrin, flucypermethrin, bifenthrin, pyrethrin, propargyl ester (mixture of isomers), permethrin (mixture of isomers), benzylflumethrin (mixture of isomers), pyrethrin (mixture of isomers), spinosad (J), abamectin (mixture of isomers), BPMC, chlorpyrifos, MIPC, spirotetramat, spinosad, trichlorfon, benzyl sulfoxide, benzyl sulfone, 3-hydroxycarbafuran, aldrin, DDE (p-p'), DDD (op), DDD (p-p'), DDE (op), DDT (o-p'), dieldrin, isodrin, isodrin aldehyde, isodrin ketone, decachlorophenone, or methamidophos (dodecyl chloride octahydro-1H-1,3,4-(epimethanetriyl)cyclobutadiene[cd]pentadiene).

[0081] Suitable herbicides can preferably be selected from the group consisting of: triazine and other photosystem 2 inhibitors, 2,6-dinitroaniline, ACCase inhibitors, PPO inhibitors, synthetic plant growth regulators, sulfonylureas, bipyrillium herbicides, chloroacetanilides, triazolopyrimidines, pyrazoles, and herbicide safeners.

[0082] Particularly preferred are those herbicides selected from paclobutrazol, diuron, linuron, isoproturon, metolachlor, pendimethalin, chlorfenapyr, 2,4,5-telopropionic acid, bentazon, metolachlor, chlorpyrifos, chlorpyrifos, 2,4-DB, oxazolidinyl acetamiprid, fenfluridine, clodinafop-propargyl, quizalofop-p-ethyl, cypermethrin, simazine, atrazine, deethyl atrazine, or cypermethrin.

[0083] Suitable fungicides may preferably be selected from the group consisting of: pyrimidines, aniline pyrimidines, triazoles and other sterol demethylation inhibitors, triazolopyrimidines, MAP kinase inhibitors, methoxyacrylates, adenosine deaminase inhibitors, pyrazoles and formamides.

[0084] Particularly preferred are those fungicides selected from the following: bifenthrin, boscalid, furazolidone, cyclophosphamide, benzyltriazole, tebuconazole, flutriafol, eticonazole, cyproconazole, fluquinazole, flusilazole, fenbendazole, hexaconazole, cyproconazole, tebuconazole, propiconazole, prothioconazole, tebuconazole, tetraflufenicol, triadimefon, triadimefon, tebuconazole, 2-aminobutane, 8-hydroxyquinoline sulfate, 2-phenylphenol (OPP), allethrin, chlorpromazine, pyraclostrobin, azoxystrobin, benomyl, fenpropathrin, benomyl, chlorpyrifos, bifenthrin, cyproconazole, ethirimol sulfonate, thiophanate-methyl, calcium polysulfide, captan, carbendazim, carbendazim, cyproconazole, quinalazine. , ... Amines, flufenacetin, captan, aluminum tris(ethyl phosphonate), tetrachlorophthalide, wheat-sparing agent, furazolidone, seed dressing amine, biguanide salts, hexachlorobenzene, imazalil, biguanide octylamine, isoprothiolane (IBP), iprodione, valerate, isoprothiolane, kasugamycin, copper preparations (such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, quinoline copper and Bordeaux mixture), mancozeb, mancozeb, mancozeb, mancozeb, pyraclostrobin, azoxystrobin, cymoxanil, metalaxyl, sulfadiazine, furazolidone, mancozeb, fenoxystrobin, benomyl, thiamethoxam, cyazofamid, nickel dimethyl dithiocarbamate, phthalimide, chlorpyrifos, furazolidone, oxadixyl, oxamocarb Carb, oxychlorpyrifos, isoprothiolane, pendimethalin, chlorpyrifos, azoxystrobin, natamycin, piperam, polyoxin, allylbenzylthiazide, prochloraz, iprodione, cymoxanil, propineb, pyraclostrobin, pyraclostrobin, pyridaben, pyrimethanil, pyrimethanil, flufenoxuron, pentachloronitrobenzene (PCNB), silthiamethoxam, spirocycline, sulfur and sulfur preparations, chlorothalonil, tetrachloronitrobenzene, thiamethoxam, thiabendazole, thiamethoxam, thiophanate-methyl, thiram, methyl thiophanate, parathion, imazalil, salicylamide, tricyclazole, isothiazinon, azoxystrobin, fluopyram, fenamidizin, tebuconazole, vinclozolinone, zineb, thiram, or benzoyl benzoate.

[0085] Suitable acaricides can preferably be selected from pyridaben, aldicarb, methyl phosmet, trisulfite, dimethoate, chlorpyrifos, triazophos, malathion, phosmet, chlorpyrifos, thiamethoxam, propargite, spirodiclofen, methamidophos, phorate, pyrimethanil, methyl pyrimidin, epn, dichlorvos, ethion, fenitrothion, diazinon, chlorpyrifos, sulfadiazine, pyridaben, cypermethrin, bifenazate, spirodiclofen, azoxystrobin (a mixture of isomers), cypermethrin, or carbafuran.

[0086] A suitable rodenticide is phosmet.

[0087] A suitable nematicide is chlorpyrifos.

[0088] A suitable acaricide is tetradifon.

[0089] In the context of emulsifiable concentrates of agricultural chemicals, the one or more pest control agents are preferably selected from the group consisting of insecticides, herbicides, fungicides, and combinations thereof, wherein examples of each class of pest control agents may be as defined above and below.

[0090] Particularly preferred is that at least one of the one or more biocides is selected from the group consisting of: azoxystrobin, prothioconazole, pyraclostrobin, ethoxyflufenoxam, difenoconazole, oxadiazon, propiconazole, cyclohexane, flufenoxuron, flufenoxuron, flufenoxuron, cyhalofop-p-ethyl, tebuconazole, cyfluthrin, clodinafop-propargyl, deltamethrin, and pendimethalin.

[0091] Preferably, the total biocidal content in the emulsifiable concentrate (EC) is in the range of 1% w / w to 50% w / w relative to the total weight of the emulsifiable concentrate (EC), more preferably in the range of 5% w / w to 40% w / w, and most preferably in the range of 10% w / w to 35% w / w.

[0092] In the context of emulsifiable concentrates of agrochemicals, it is also well known that more than one pest control agent can be used to obtain so-called combination formulations. Such combination formulations can have improved effects because these individual pest control agents act synergistically, or alternatively, multiple pest control agents can have activity against different pests; for example, one pest control agent can be a herbicide and another can be an insecticide.

[0093] In one embodiment, the emulsifiable concentrate (EC) contains two or more biocides.

[0094] Many such combinations are commercially available and well-known in the art. Therefore, there are no particular limitations on the selection of combinations of pest control agents.

[0095] In a preferred embodiment, at least one of the two or more biocides, more preferably at least two, is selected from the group consisting of: azoxystrobin, prothioconazole, pyraclostrobin, ethoxyflufenoxam, difenoconazole, oxadiazon, propiconazole, cyclohexane, flufenoxuron, flufenoxuron, flufenoxuron, tebuconazole, cyfluthrin, clodinafop-propargyl, deltamethrin, and pendimethalin.

[0096] One or more emulsifiers

[0097] Another essential component of emulsifiable concentrate (EC) is one or more emulsifiers.

[0098] The one or more emulsifiers of this invention are not particularly limited. In their broadest form, the one or more emulsifiers can be selected from any conventional emulsifiers typically used in the field of agricultural chemical compositions and formulations.

[0099] For example, the one or more emulsifiers may be selected from: - 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide are added to the straight-chain C14. 8-22 fatty alcohols, C 12-22 Products on fatty acids and alkylphenols containing 8 to 15 carbon atoms; - C1 of the addition products of 1 to 30 mol ethylene oxide on glycerol 12-18 Fatty acid monoesters and diesters; - Glyceryl monoesters and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms, as well as sorbitol monoesters and diesters and their ethylene oxide addition products. - 15 to 60 mol of ethylene oxide added to castor oil and / or hydrogenated castor oil; - Polyol esters, and especially polyglycerol esters, such as polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimer isostearate; - 2 to 15 mol of ethylene oxide added to castor oil and / or hydrogenated castor oil; - Based on straight chain, branched chain, unsaturated or saturated C 6-22 Esters of fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g., sorbitol), alkyl glucosides (e.g., methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g., cellulose); - Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts; - Lanolin; - Polysiloxane / polyalkyl polyether copolymers and their derivatives; - A mixture of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or C 6-22 Fatty acids, methyl glucose, and polyols are preferably mixed esters of glycerol or polyglycerol, and - Polyalkylene glycols.

[0100] The one or more emulsifiers are preferably selected from the group consisting of nonionic emulsifiers, anionic emulsifiers, and combinations thereof.

[0101] Particularly preferred is that at least one of the one or more emulsifiers is a nonionic emulsifier.

[0102] It is also preferred that at least one of the one or more emulsifiers is an anionic emulsifier.

[0103] In a particularly preferred embodiment, the one or more emulsifiers comprise nonionic emulsifiers and anionic emulsifiers, more preferably consisting of nonionic emulsifiers and anionic emulsifiers.

[0104] In another particularly preferred embodiment, the one or more emulsifiers comprise two nonionic emulsifiers, more preferably two nonionic emulsifiers.

[0105] Suitable nonionic emulsifiers can be selected from the group consisting of: copolymers containing ethylene oxide and propylene oxide monomers, alcohol alkoxylates, alkyl polyglucosides, amino polyols, polyalkylene glycols, alkoxylated animal or vegetable fats and oils such as corn oil ethoxylates, soybean oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, glycerides such as glyceryl monostearate, fatty alcohol alkoxylates and oxo alcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylates, alkylphenol alkoxylates such as isononylphenol ethoxylates, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar surfactants such as sorbitan fatty acid esters (e.g., sorbitan monooleate and sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglucosides, N-alkyl glucamides, alkyl methyl sulfoxides, alkyl dimethylphosphine oxides such as tetradecyl dimethylphosphine oxide, or combinations thereof.

[0106] Preferably, at least one of the one or more emulsifiers is castor oil ethoxylate. Alternatively, preferably, at least one of the one or more emulsifiers is a copolymer containing ethylene oxide and propylene oxide monomers.

[0107] In one specific embodiment, at least one of the one or more emulsifiers is castor oil ethoxylate, and at least one of the one or more emulsifiers is a copolymer containing ethylene oxide and propylene oxide monomers.

[0108] Suitable anionic emulsifiers include salts, wherein the anions can be selected from the group consisting of: fatty acids, fatty alcohol ether sulfates, fatty alcohol sulfates, alkylbenzene sulfonates, ether phosphates, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates or isoalkyl sulfonates, alkylnaphthalene sulfonates, alkyl methyl ester sulfonates, acylglutamates, alkyl sulfosuccinates, sarcosines, taurines, and combinations thereof, while the cations can be selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and combinations thereof.

[0109] Preferably, at least one of the one or more emulsifiers is an alkylbenzene sulfonate, more preferably a linear alkylbenzene sulfonate.

[0110] In a particularly preferred embodiment, the one or more emulsifiers comprise castor oil ethoxylate and alkylbenzene sulfonate, more preferably castor oil ethoxylate and alkylbenzene sulfonate. In this particularly preferred embodiment, the alkylbenzene sulfonate is more preferably a linear alkylbenzene sulfonate.

[0111] The total content of the one or more emulsifiers in the emulsifiable concentrate (EC) is preferably in the range of 1% w / w to 30% w / w, more preferably in the range of 5% w / w to 25% w / w, and most preferably in the range of 10% w / w to 20% w / w relative to the total weight of the emulsifiable concentrate (EC).

[0112] Emulsifiable concentrate (EC)

[0113] As detailed above, the emulsifiable concentrate (EC) according to the present invention comprises one or more biocides, one or more emulsifiers, and solvents as described above.

[0114] Particularly preferred combinations of one or more amide solvents (S1), one or more ester solvents (S2), one or more co-solvents (S3), and one or more emulsifiers are given in Table B:

[0115] Where S1a is dimethyldodecanoamide, S1b is dimethyldecanoamide, and S2a is C 12-18 Fatty acid methyl esters, S2b is C 6-10 Fatty acid methyl esters, S2c is methyl octanoate, S2d is 2-ethylhexyl acetate, S2e is dibutyl adipate, S3a is propylene carbonate, S3b is γ-caprolactone, S3c is dimethyl lactamide, S3d is ethyl lactate, S3e is acetone glycerol, S3f is cyclohexanone, S3g is benzyl alcohol, S3h is ethyl levulinate, S3i is hexyl ethylene glycol, S3j is triethyl citrate, S3k is hexanediol, E1 is any emulsifier, E2 is a block copolymer containing ethylene oxide and propylene oxide monomers, E3 is a sulfonate, and E4 is ethoxylated castor oil.

[0116] In addition to these essential components, emulsifiable concentrates (ECs) may further contain adjuvants commonly used in agrochemical formulations. The choice of these adjuvants depends on the specific application, type of formulation, or active ingredient. Examples of suitable adjuvants include surfactants (such as solubilizers, protective colloids, wetting agents, and thickeners), retainers, wetting agents, spreading agents, absorption enhancers, penetrants, spray drift control agents, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, optionally colorants and binders (e.g., for seed treatment) or conventional adjuvants used in bait formulations (e.g., attractants, feeding agents, bittering substances).

[0117] The emulsifiable concentrate (EC) according to the present invention preferably comprises, more preferably, the following: a) The one or more biocides relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 50% w / w, more preferably 5% w / w to 40% w / w, and most preferably 10% w / w to 35% w / w; b) The one or more emulsifiers comprising 1% w / w to 30% w / w, more preferably 5% w / w to 25% w / w, and most preferably 10% w / w to 20% w / w of the total weight of the emulsifiable concentrate (EC); c) The solvent system (S) comprising 1% w / w to 90% w / w, more preferably 10% w / w to 85% w / w, and most preferably 25% w / w to 80% w / w of the total weight of the emulsifiable concentrate (EC); and d) Optionally, one or more adjuvants may be used relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 30% w / w, more preferably 2% w / w to 20% w / w, and most preferably 3% w / w to 15% w / w. The total amount of components a), b), c), and d) does not exceed 100%.

[0118] Alternatively or concurrently, the emulsifiable concentrate (EC) according to the present invention preferably comprises, more preferably, the following: a) The one or more biocides relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 50% w / w, more preferably 5% w / w to 40% w / w, and most preferably 10% w / w to 35% w / w; b) The one or more emulsifiers comprising 1% w / w to 30% w / w, more preferably 5% w / w to 25% w / w, and most preferably 10% w / w to 20% w / w of the total weight of the emulsifiable concentrate (EC); c) The one or more amide solvents (S1) are present in an amount of 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w relative to the total weight of the emulsifiable concentrate (EC). d) The one or more ester solvents (S2) at 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w relative to the total weight of the emulsifiable concentrate (EC); e) the one or more co-solvents (S3) comprising 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w of the total weight of the emulsifiable concentrate (EC); and f) Optionally, one or more adjuvants comprising 1% w / w to 30% w / w, more preferably 2% w / w to 20% w / w, and most preferably 3% w / w to 15% w / w relative to the total weight of the emulsifiable concentrate (EC). The total amount of components a), b), c), d), e), and f) does not exceed 100%.

[0119] The emulsifiable concentrate (EC) is preferably stable in liquid form at 21°C for at least 2 weeks.

[0120] The emulsifiable concentrate (EC) is preferably stable in liquid form at -5°C for at least 24 hours.

[0121] Preferably, the emulsifiable concentrate (EC) has a flash point of at least 40°C, more preferably at least 50°C, and most preferably at least 60°C, as determined according to ISO 2719.

[0122] As mentioned above, the present invention finds that many typical commercially important biocides exhibit improved solubility in the solvent system (S) according to the invention, compared to typical solvent systems used for emulsifiable concentrates of agrochemicals.

[0123] In addition to this discovery, it was further found that the emulsifiable concentrate (EC) of the present invention forms a highly stable emulsion when mixed with water to form an emulsion, a so-called emulsion-in-water (EW) formulation.

[0124] The stability of water-in-emulsion formulations can be assessed by determining how much sediment or cream forms after homogenization (i.e., emulsification). Both cream and sedimentation represent deviations from ideal emulsion behavior, where dispersed particles either rise to the surface (creaming) or sink to the bottom (sedimentation) depending on their density. When determining the degree of creaming or sedimentation, whether the emulsion droplets remain as is or aggregate to form a new continuous phase is not critical – both are sufficient to indicate that the emulsion has decomposed.

[0125] The stability of a given emulsion depends on many factors, including the nature of the two immiscible phases, the relative amounts of each phase, and the emulsifier used to stabilize the emulsion. In the context of this invention, for the purpose of quantifying emulsion stability, a stable emulsion is considered to be an emulsion that forms a cream and / or settles in amounts less than or equal to a given quantity 24 hours after homogenization.

[0126] The discovery of this invention is that the emulsifiable concentrate (EC) of this invention is suitable for use in forming a wide range of emulsion-in-water (EW) formulations when mixed with and homogenized with water, demonstrating unexpectedly beneficial emulsion stability.

[0127] To quantify this beneficial characteristic of emulsifiable concentrate (EC), a model emulsion system containing 5.0 mL of emulsifiable concentrate (EC) and 95.0 mL of water can be used. In this case, a stable emulsion is defined as an emulsion that produces less than or equal to 1.5 mL of cream or sediment 24 hours after the formation of the emulsion.

[0128] Therefore, preferably, the emulsifiable concentrate (EC) forms a stable emulsion when 5.0 mL of the emulsifiable concentrate (EC) is combined with 95.0 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 1.5 mL of cream or sediment 24 hours after the formation of the emulsion.

[0129] More preferably, within 24 hours of the formation of the emulsion, the emulsion forms a cream or sediment of less than or equal to 1.0 mL. Most preferably, within 24 hours of the formation of the emulsion, the emulsion forms a cream or sediment of less than or equal to 0.5 mL.

[0130] If the emulsion does produce measurable levels of sediment or cream, it is further preferred that the emulsion be rehomogenized, i.e., reemulsified, to reform a stable emulsion, wherein the stable emulsion is as defined above, wherein less than or equal to 1.5 mL of cream or sediment is formed 30 minutes after rehomogenization, more preferably wherein less than or equal to 1.0 mL of cream or sediment is formed 30 minutes after rehomogenization, and most preferably wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after rehomogenization.

[0131] The methods used for initial homogenization and rehomogenization are well known in the art, and the exact method used in such tests is not critical.

[0132] In other words, it is preferable that homogenization is performed by gently inverting the emulsion 10 times, and re-homogenization is also performed by gently inverting the emulsion 10 times.

[0133] As those skilled in the art will understand, the threshold at which the amount of cream or sediment will indicate that an emulsion is unstable depends on the amount of each phase present in the emulsion. Therefore, alternative tests can be envisioned, for example.

[0134] A model emulsion system comprising 0.5 mL of emulsifiable concentrate (EC) and 99.5 mL of water can be used to evaluate low-temperature stability. In this case, a stable emulsion is defined as an emulsion that produces less than or equal to 1.0 mL of cream or sediment after 24 hours at 5°C. Therefore, it is further preferred that the emulsifiable concentrate (EC) forms a stable emulsion when 0.5 mL of the emulsifiable concentrate (EC) and 99.5 mL of water are combined and homogenized at 5°C, wherein a stable emulsion is defined as an emulsion having less than or equal to 0.5 mL of cream or sediment after 24 hours of emulsion formation (which has been maintained at 5°C).

[0135] More preferably, 24 hours after the formation of the emulsion, the emulsion forms a cream or sediment of less than or equal to 0.2 mL.

[0136] If the emulsion does produce measurable levels of sediment or cream, it is further preferred that the emulsion be rehomogenized, i.e., reemulsified, to reform a stable emulsion, wherein the stable emulsion is as defined above, wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after rehomogenization, preferably wherein less than or equal to 0.2 mL of cream or sediment is formed 30 minutes after rehomogenization.

[0137] Emulsion-in-water (EW) formulations

[0138] As described above, the emulsifiable concentrate (EC) of the present invention is best suited for forming highly stable emulsion-in-water (EW) formulations.

[0139] In another aspect, the present invention relates to an emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is an emulsifiable concentrate (EC) of the first aspect.

[0140] The precise amounts of emulsifiable concentrate (EC) and water present in the emulsion-in-water (EW) formulation are not critical; however, it is preferred that the emulsion-in-water (EW) formulation comprises, more preferably, the following: an amount of emulsifiable concentrate (EC) according to the first aspect in the range of 0.01% w / w to 80.0% w / w and an amount of water in the range of 20.0% w / w to 99.99% w / w, both of which are expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0141] Further preferably, the emulsion-in-water (EW) formulation comprises, more preferably, an amount of emulsifiable concentrate (EC) according to the first aspect in the range of 0.1% w / w to 50.0% w / w and an amount of water in the range of 50.0% w / w to 99.9% w / w, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0142] Particularly preferred is that the emulsion-in-water (EW) formulation comprises, more preferably, an amount of emulsifiable concentrate (EC) according to the first aspect in the range of 0.5% w / w to 5.0% w / w and an amount of water in the range of 95.0% w / w to 99.5% w / w, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0143] In addition to the emulsifiable concentrate (EC) and water as described in the first aspect, emulsion-in-water (EW) formulations may further contain adjuvants (so-called tank adjuvants) commonly used in agrochemical formulations. The choice of these adjuvants depends on the specific application, the type of formulation, or the active ingredient. Examples of suitable adjuvants include surfactants (such as solubilizers, protective colloids, wetting agents, and thickeners), retainers, wetting agents, spreading agents, absorption enhancers, penetrants, spray drift control agents, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, optionally colorants and binders (e.g., for seed treatment) or conventional adjuvants used in bait formulations (e.g., attractants, feeding agents, bittering substances).

[0144] All preferred embodiments and alternatives relating to the emulsifiable concentrate (EC) of the first aspect can be adapted to the emulsion-in-water (EW) formulations of the other aspect with the necessary modifications.

[0145] use

[0146] In a final aspect, the present invention relates to the use of one or more ester solvents (S2) having a water solubility of less than 1.50% w / w for improving the stability of water-in-oil emulsion formulations, wherein the non-aqueous phase comprises one or more amide solvents (S1) having a water solubility of less than 1.50% w / w and one or more cosolvents (S3) having a water solubility of greater than 1.50% w / w.

[0147] All preferred embodiments and alternatives relating to the one or more ester solvents (S2), the one or more amide solvents (S1), and the one or more cosolvents (S3) of the first aspect may be applied to the one or more ester solvents (S2), the one or more amide solvents (S1), and the one or more cosolvents (S3) of this aspect with necessary modifications.

[0148] Similarly, all preferred embodiments and alternatives relating to the water-in-oil emulsion formulations given for the second aspect can be applied to the water-in-oil emulsion formulations of this aspect with necessary modifications.

[0149] Experimental Section

[0150] Materials used: Solvents: All solvents listed in Table B are sourced from BASF or alternative commercial sources.

[0151] Table B: Solvents used in the formulations of the present invention and the comparative formulations:

[0152] NM - Not measured - Measurement upon opening the cup (see below for details) - Not given because S2a and S2b are mixtures of several individual solvents. As a guide, C6 fatty acid methyl esters have a Tm of -71°C and C... 10 Fatty acid methyl esters have a Tm of -18°C and a C 12 Fatty acid methyl esters have a Tm of 4°C and C 18 Fatty acid methyl esters have a Tm of 40°C.

[0153] Use the following method to obtain the data given in Table B: Melting temperature: The melting temperature of the solvent alone was determined by differential scanning calorimetry (DSC).

[0154] Pour point: The pour point of individual solvents and mixtures of solvents is determined according to DIN ISO 3016. For individual solvents, the pour point is typically 0°C to 5°C higher than the melting point.

[0155] Flash point: Flash points of individual solvents and mixtures of solvents are determined according to ISO 2719 (i.e., the Pensky-Martens closed-cup method). Values ​​marked with two asterisks (i.e., 130) are indicated. The value was measured using DIN ISO 2592 (i.e., the Cleveland open cup method), which typically gives values ​​that are approximately 5°C–10°C higher than those obtained using ISO 2719.

[0156] Water solubility: The water solubility of the solvent was determined according to a method based on CIPAC MT157.1 and OECD 105 by evaluating the amount of undissolved solvent in water after vigorous mixing and settling. In this study, different amounts of solvent and water were mixed in graduated cylinders or separatory funnels with glass stoppers under vigorous shaking, followed by settling for at least 30 minutes to allow for separation. For example, if undissolved solvent was observed after thoroughly mixing 0.1 g of solvent in 100 mL of water, the solvent had a water solubility equal to or less than 0.1% (≤ 1 g / L). This method can be repeated with different amounts of solvent and water to allow for the determination of the solvent's water solubility.

[0157] CIPAC D Water: Standard Water prepared in the laboratory using the standard formulation "MT 18.1.4" published by CIPAC. This water has a hardness of 342 ppm and a Ca:Mg ion mixture of 4:1 at pH 6-7.

[0158] Pesticides: ethoxyflufenican, tebuconazole, prothioconazole, azoxystrobin, fluthiamethoxam, and difenoconazole were purchased from various commercial sources.

[0159] Emulsifiers: The emulsifiers used in the experiment are listed below.

[0160]

[0161] The following methods were used to evaluate various combinations of solvents in the formulations of the present invention and comparative formulations: 1. Emulsion concentrate (EC) stability at room temperature (21°C) After stirring at room temperature (21°C), all components in the mixture readily dissolve in the solution to form a free-flowing emulsion concentrate (EC). If the resulting EC remains stable without any precipitation after being stored at room temperature for at least 2 weeks, it is called "stable". C = clear, S = stable, L = liquid, U1 = unstable due to separation, U2 = unstable due to solidification.

[0162] 2. At low temperature ( - Emulsion concentrate stability at 5°C

[0163] After stirring at room temperature (21°C), all components in the mixture readily dissolve in the solution to form a free-flowing emulsion concentrate (EC). An EC is considered "stable" if it remains liquid at -5°C and remains stable without precipitation after being stored at -5°C for at least 24 hours. C = clear, S = stable, L = liquid, U1 = unstable due to separation, U2 = unstable due to solidification.

[0164] 3. Emulsion stability at room temperature (21°C) at 5% concentration

[0165] The dispersibility of an emulsion is tested by an effect known as blooming.

[0166] The emulsion was evaluated based on its spontaneous emulsification (referred to in the art as "self-emulsification") upon addition of the concentrate to water, using a visual evaluation given on a scale of 1 to 5, where 1) Excellent, "emulsion cloud," does not sink to the bottom of the graduated cylinder; 2) Good, "emulsion cloud," but sinks to the bottom of the graduated cylinder; 3) Okay, "poor emulsion cloud," larger droplets; 4) Poor, "no emulsion cloud," small "particles" observed; 5) Very poor, no emulsion, oil and aqueous phases separate immediately.

[0167] In the following examples, emulsifiable concentrates were prepared, and the resulting 5% w / w emulsions were evaluated for various water hardnesses at 21°C after 24 hours. Emulsion stability was determined by measuring changes in cream or sediment over time.

[0168] To measure emulsion stability, 5.0 mL of the emulsifiable concentrate was diluted in 95.0 mL of CIPAC D water in a 100 mL measuring cylinder. The stability of the resulting oil-in-water emulsion was evaluated after 1, 2, 4, and 24 hours. A highly stable emulsion did not form a cream or sediment after 24 hours, or had less than 1.5 mL of cream or sediment, and could be easily reemulsified without forming a cream or sediment after standing for 24 hours, wherein such reemulsified emulsions were evaluated 30 minutes after reemulsification. Both initial emulsification and reemulsification were achieved by gently inverting the emulsion 10 times. In the table below, Y (i.e., yes) indicates that at most 1.5 mL of cream or sediment was observed after 24 hours, while N (i.e., no) indicates that more than 1.5 mL of cream or sediment was observed after 24 hours.

[0169] 4. Emulsion stability at low concentration (0.5%) and low temperature (5°C)

[0170] In the following examples, emulsifiable concentrates were prepared, and the resulting 0.5% w / w emulsions were evaluated at 21°C after 24 hours with various water hardnesses. Emulsion stability was determined as a function of time, with the amount of cream or sediment measured.

[0171] To measure emulsion stability, 0.5 mL of the emulsifiable concentrate was diluted in 99.5 mL of CIPAC D water in a 100 mL measuring cylinder. The stability of the resulting oil-in-water emulsion was assessed after 24 hours. A highly stable emulsion did not form a cream or sediment after 24 hours, or had less than 1.0 mL of cream or sediment. Emulsification was achieved by gently inverting the emulsion 10 times. In the table below, Y (i.e., yes) indicates that at most 1.0 mL of cream or sediment was observed after 24 hours, while N (i.e., no) indicates that more than 1.0 mL of cream or sediment was observed after 24 hours.

[0172] 5. Emulsion stability testing using low-temperature recirculation testing

[0173] Low-temperature emulsion recirculation tests were conducted to evaluate the stability of the emulsion under field application conditions. In this study, a 5 L temperature-controlled container isothermally maintained at 4°C was prepared, containing 3 L of a biocidal emulsion with a 0.5% w / w emulsifiable concentrate. The emulsion contained 3 L of CIPAC D water and 15 g of emulsifiable concentrate, resulting in an emulsion concentration of 0.5% w / w. The resulting emulsion was pumped at 1 L / min through a metal filter with a 140 µm pore size attached to the temperature-controlled container at 4°C for 6 hours, during which pressure was continuously monitored. The fully stable emulsion maintained a pressure < 1.0 bar throughout the 6-hour recirculation period, and after the 6-hour recirculation, the filter was removed and the emulsion was dried, with the total collected solids measured being < 100 mg.

[0174]

[0175] NM = Not measured (usually due to a failure of a test higher up in the table).

[0176] NE = No emulsion formed (usually due to the high water solubility of the solvent system). = Forms crystals, rather than cream / settling As can be seen from Tables 1a to 7b, amide solvents alone (e.g., S1a, see CEd) tend to have poor emulsifiable concentrate stability (typically solidifying or separating after storage at -5°C) and generally poor emulsion stability. Ester solvents alone (e.g., S2a, see CEe) have very poor active ingredient solubility, and separation (i.e., U1) is observed in all cases even at room temperature; therefore, emulsion stability testing is generally not possible, and even when such testing is performed, the emulsion stability is poor. Cosolvents alone (e.g., S3a, see CEf) have poor emulsifiable concentrate stability (especially at low temperatures) and do not form stable emulsions.

[0177] The combination of S1 and S2 (see CEb) is superior to S1 and S2 alone, but still fails to overcome the problem of low-temperature stability of the emulsifiable concentrate (due to coagulation or separation), and the overall emulsion stability remains poor. The combination of S1 and S3 (see CEa) occasionally provides better emulsion stability at low temperatures; however, the overall emulsion stability remains poor, especially at low concentrations / low temperatures. The combination of S2 and S3 (see CEc) exhibits poor active ingredient solubility at low temperatures (and occasionally at room temperature), and its emulsion stability at room temperature is inconsistent.

[0178] Excellent emulsion concentrate stability at room and low temperatures, as well as excellent emulsion stability at high concentrations / room and low concentrations / low temperatures, can only be achieved by using a ternary combination of S1, S2, and S3. Furthermore, these effects can be achieved with a range of suitable amide solvents (S1), a range of suitable ester solvents (S2), and a range of (partially) suitable water-soluble cosolvents (S3) (as shown for the series of inventive examples IEa to IEo).

Claims

1. An emulsifiable concentrate (EC) comprising one or more biocides, one or more emulsifiers, and a solvent system (S), the solvent system (S) comprising, more preferably, the following: a) One or more amide solvents (S1) having a water solubility of less than 1.50% w / w; b) One or more ester solvents (S2) having a water solubility of less than 1.50% w / w; and c) One or more cosolvents having a water solubility greater than 1.50% w / w (S3).

2. The emulsifiable concentrate (EC) according to claim 1, wherein, The combined one or more amide solvents (S1) have a pour point in the range of -100°C to 20°C, more preferably in the range of -60°C to 15°C, and most preferably in the range of -40°C to 10°C, as determined according to DIN ISO 3016.

3. The emulsifiable concentrate (EC) according to claim 1 or claim 2, wherein, At least one of the one or more amide solvents (S1) has 7 to 20 carbon atoms.

4. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein, The one or more amide solvents (S1) are selected from the group consisting of: dimethylhexanoamide, dimethylheptanoamide, dimethyloctanoamide, dimethylnonanoamide, dimethyldecanoamide, dimethylundecanoamide, dimethyldodecanoamide, dimethyltridecanoamide, dimethyltetradecanoamide, dimethylpentadecananoamide, dimethylhexadecanoamide, dimethylhexadecanoamide, dimethylheptadecanoamide, dimethyloctadecanoamide, dimethylnonadecananoamide, dimethyleicosanoamide and their unsaturated variants, such as dimethylsoybean oleamide, dimethyl erucic acid rapeseed oleamide and dimethyl oleamide, and mixtures of fatty acid dimethylamides, such as C6-C 10 Fatty acid dimethylamide and C 12 -C 18 Fatty acid dimethylamide, and any combination thereof.

5. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein, The one or more ester solvents (S2) are selected from the group consisting of: methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl dodecanoate, methyl tridecanoate, methyl tetradecanoate, methyl pentadecanoate, methyl hexadecanoate, methyl heptadecanoate, methyl octadecanoate, methyl nonadecanoate, methyl eicosanoate, methyl isononanoate, 1-ethylhexyl palmitate, caprylic / decanoic acid triglyceride, propylene glycol dicaprylate / didecanoate, propane-1,2,3-triyl-2-ethylhexanoate, 2,2-bis[(octanoyloxy)methyl]butyl decanoate, trimethylolpropane trioleate, 2-ethylhexyl acetate, dibutyl adipate, and 2-ethylhexyl cocoate, and their unsaturated variants, such as methyl soybean oleate, methyl rapeseed oil with low erucic acid, and methyl oleate, and mixtures of fatty acid methyl esters, such as C6-C 10 Fatty acid methyl esters and C 12 -C 18 Fatty acid methyl esters, and combinations thereof.

6. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein, The one or more co-solvents (S3) are selected from the group consisting of: propylene carbonate, butyl carbonate, glyceryl carbonate, hexyl ethylene glycol, hexanediol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, triethylene glycol, butyl ethylene glycol, butyl diethylene glycol, butoxypropyl-2-ol, dipropylene glycol monobutyl ether, 2,2,4-trimethyl-1,3-pentanediol, di(ethylene glycol) monomethyl ether, di(ethylene glycol) ethyl ether, di(ethylene glycol) monopropyl ether, 3-methoxy-3-methyl-1-butanol, methoxypropanol, N,N-dimethyllactic acid, ethyl lactate, propyl lactate, butyl lactate, cyclohexanediol ... Hexanone, benzyl alcohol, triethyl citrate, γ-butyrolactone, γ-caprolactone, methyl levulinate, ethyl levulinate, 1,2-isopropyltriglyceride (acetone glycerol), glyceryl formal, n-ethylpyrrolidone, n-ethylpyrrolidone, n-butylpyrrolidone, methyl 5-(dimethylamino)-2-methyl-5-oxovalerate, dimethylacetoacetamide, diethylacetoacetamide, dimethyl isosorbide, dihydro-L-glucose ketone, methyl acetoacetate, ethyl acetoacetate, dimethyl 3-methylglutarate, and combinations thereof.

7. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein, The solvent system (S) consists of the following: a) The one or more amide solvents (S1) comprising 1% w / w to 80% w / w, more preferably 10% w / w to 60% w / w, and most preferably 20% w / w to 50% w / w of the total weight of the solvent system (S); b) the one or more ester solvents (S2) comprising 1% w / w to 80% w / w, more preferably 5% w / w to 60% w / w, and most preferably 10% w / w to 40% w / w of the total weight of the solvent system (S); and c) the one or more co-solvents (S3) comprising 1% w / w to 80% w / w, more preferably 10% w / w to 60% w / w, and most preferably 20% w / w to 50% w / w of the total weight of the solvent system (S). The total amount of components a), b) and c) does not exceed 100%.

8. The emulsifiable concentrate (EC) according to any one of the preceding claims, comprising, more preferably consisting of, the following: a) The one or more biocides relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 50% w / w, more preferably 5% w / w to 40% w / w, and most preferably 10% w / w to 35% w / w; b) The one or more emulsifiers comprising 1% w / w to 30% w / w, more preferably 5% w / w to 25% w / w, and most preferably 10% w / w to 20% w / w of the total weight of the emulsifiable concentrate (EC); c) The solvent system (S) comprising 1% w / w to 90% w / w, more preferably 10% w / w to 85% w / w, and most preferably 25% w / w to 80% w / w of the total weight of the emulsifiable concentrate (EC); and d) Optionally, one or more adjuvants may be used relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 30% w / w, more preferably 2% w / w to 20% w / w, and most preferably 3% w / w to 15% w / w. The total amount of components a), b), c), and d) does not exceed 100%.

9. The emulsifiable concentrate (EC) according to any one of the preceding claims, comprising, more preferably consisting of, the following: a) The one or more biocides relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 50% w / w, more preferably 5% w / w to 40% w / w, and most preferably 10% w / w to 35% w / w; b) The one or more emulsifiers comprising 1% w / w to 30% w / w, more preferably 5% w / w to 25% w / w, and most preferably 10% w / w to 20% w / w of the total weight of the emulsifiable concentrate (EC); c) One or more amide solvents (S1) at 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w relative to the total weight of the emulsifiable concentrate (EC); d) One or more ester solvents (S2) relative to the total weight of the emulsifiable concentrate (EC) of 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w; e) the one or more co-solvents (S3) comprising 1% w / w to 70% w / w, more preferably 3% w / w to 50% w / w, and most preferably 5% w / w to 40% w / w of the total weight of the emulsifiable concentrate (EC); and f) Optionally, one or more adjuvants may be used relative to the total weight of the emulsifiable concentrate (EC) at 1% w / w to 30% w / w, more preferably 2% w / w to 20% w / w, and most preferably 3% w / w to 15% w / w. The total amount of components a), b), c), d), e), and f) does not exceed 100%.

10. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein, At least one of the one or more biocides is selected from the group consisting of: azoxystrobin, prothioconazole, pyraclostrobin, ethoxyflufenoxam, difenoconazole, oxadiazon, propiconazole, fluthiamethoxam, flutriafol, and tebuconazole.

11. The emulsifiable concentrate (EC) according to any one of the preceding claims, comprising at least one first emulsifier being a fatty acid ester ethoxylate and at least one second emulsifier being a copolymer comprising ethylene oxide and propylene oxide monomers or at least one second emulsifier being a sulfonate.

12. The emulsifiable concentrate (EC) according to any one of the preceding claims, which is stable in liquid form at -5°C for at least 24 hours.

13. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein, The emulsifiable concentrate (EC) forms a stable emulsion when 0.5 mL of the emulsifiable concentrate (EC) is combined with 99.5 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having at most 1.0 mL of cream or sediment 24 hours after the formation of the emulsion.

14. An emulsion-in-water (EW) formulation comprising an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase is an emulsifiable concentrate (EC) according to any one of claims 1 to 13.

15. The use of one or more ester solvents (S2) having a water solubility of less than 1.50% w / w for improving the stability of water-in-emulsion formulations, wherein, The non-aqueous phase comprises one or more amide solvents (S1) having a water solubility of less than 1.50% w / w and one or more cosolvents (S3) having a water solubility of greater than 1.50% w / w.

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