An emulsifiable concentrate having a benzaldehyde-based solvent system

Abstract

An emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers, one or more co-solvents and certain benzaldehyde-derived solvents, an emulsion-in-water (EW) formulation formed from said emulsifiable concentrate (EC), and the use of the certain benzaldehyde-derived solvents as a solvent in an agrochemical emulsifiable concentrate.

Description

[0001] An emulsifiable concentrate having a benzaldehyde-based solvent system

[0002] Field of the Invention

[0003] The present invention is directed to an emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers, one or more co-solvents and certain benzaldehyde-derived solvents, to an emulsion-in-water (EW) formulation formed from said emulsifiable concentrate (EC), and to the use of the combination of certain benzaldehydederived solvents with co-solvents as a solvent in an agrochemical emulsifiable concentrate.

[0004] Background to the Invention

[0005] When preparing agrochemical formulations, it is usually required to dissolve the agrochemically active ingredient, e.g. one or more pesticides in a solvent, which is then diluted in a larger volume of water in order for it to be applied in the form of a fine spray. Alternatively, it may be necessary to dilute the agrochemically active ingredient in a solution and load it onto a seed or solid carrier. Whilst some agrochemically active ingredients are salts and thus highly water-soluble, allowing for simply dissolution, many other non-ionic agrochemically active ingredients are hydrophobic and not at all water-soluble.

[0006] In the case of active ingredients that are not water-soluble, it is normally necessary to dissolve the formulation in a water-immiscible solvent and add one or more surfactants, so that the solution will form an oil-in-water emulsion, when added to water. Such a formulation is called an Emulsifiable Concentrate (EC) formulation. Alternatively, the water- immiscible solution comprising active ingredient can be pre-emulsified in water in a concentrated form. Such a formulation is called an Emulsion-in-water (EW) formulation.

[0007] Water-immiscible solvents commonly used for EC and EW formulations include, but are not limited to, aromatic hydrocarbons such as the SOLVESSO® series, paraffinic hydrocarbons such as the EXXSOL ® range, ester solvents such as the EXXATE® range, all of which are manufactured by EXXONMOBIL, and ester solvents such as methyloleate. Further, solvents which are water-immiscible at high concentration include cyclic hydrocarbons, such as cyclohexanone and isophorone. In more recent times, solvents which exhibit improved toxicity and reduced flammability profiles have been used. These include the dibasic ester solvents of long chain di-acids having from 8-16 carbon units, which are usually methyl ester derivatives, and fatty acid amide solvents, examples of which are the dimethylamide and morpholineamide derivatives of C6-C16fatty acids. Mono-alkylene carbonates such as ethylene, propylene and butylene carbonates, also find use as co-solvents.

[0008] Combinations of water-immiscible solvents with highly polar water-miscible co-solvents such as N-methyl pyrrolidinone (NMP), dimethylsulphoxide, dimethylisosorbide, monoethylene glycol, monopropylene glycol and various glycol ethers have been used in the past to achieve physical stability of the EC formulation, particularly if crystallisation of the active ingredient occurs at below ambient temperature. However, the use of such solvent combinations often leads to the problem of crystallisation in the diluted formulation. There exists in the pesticide industry a great desire to find alternatives to currently used solvents such as fatty acid esters, fatty acid amides, isophorone, methyl butyl ketone (MBK), NMP, etc. which may be expensive, difficult to source and / or are environmentally unattractive due to their inherent phytotoxicity, toxicity (e.g. teratogenicity) or regulatory status.

[0009] Solvents that avoid these phytotoxic / environmentally harmful properties are known, for example benzyl acetate; however, these solvents typically are only able to achieve moderate solubility across the broad range of commercially important pesticides. In particular, azoxystrobin and prothioconazole, both common fungicides, are known to be sparingly soluble in many of the solvents conventionally used.

[0010] As such, there remains a need for solvents suitable for use in emulsifiable concentrate formulations and emulsion-in-water formulations, which combine low phytotoxicity and generally benign (e.g. non-irritant) properties with high solubility for a range of commonly employed agrochemical active ingredients.

[0011] Furthermore, although this need has been recently addressed in PCT / EP2023 / 054565 by the use of benzaldehyde-derived solvents in emulsifiable concentrates, it has also been found that under certain circumstances with certain pesticides, only a limited choice of emulsifiers may be used if the resultant emulsion-in-water is to be stable. It is thus an object of the present invention to provide solvents / solvent mixtures that combine the advantageous properties of the benzaldehyde-derived solvent systems with the ability to use a broad range of emulsifiers, such as castor oil ethoxylates.

[0012] Summary of the Invention

[0013] The finding of the present invention is that the use of a co-solvent in addition to the benzaldehyde-derived solvent(s) combine low phytotoxicity and generally benign (e.g. nonirritant) properties with high solubility for a range of commonly employed agrochemical active ingredients, whilst also accommodating a wide range of emulsifiers that were not all successfully employed when the benzaldehyde-derived solvent is used as the sole solvent.

[0014] In a first aspect, the present invention is directed to an emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers, one or more co-solvents having a structure free from benzaldehyde moieties and one or more solvents having a structure according to formula (I): wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1 is selected from the group consisting of hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring, wherein the total amount, expressed as % w / w, of the one or more solvents having a structure according to formula (I) is greater than the total amount, expressed as % w / w, of the one or more co-solvents having a structure free from benzaldehyde moieties.

[0015] In a further aspect, the present invention is directed to an emulsion-in-water (EW) formulation, comprising an aqueous phase and a non-aqueous phase, wherein the nonaqueous phase is the emulsifiable concentrate (EC) of the first aspect.

[0016] In another aspect, the present invention is directed to a use of a co-solvent having a structure free from benzaldehyde moieties and a compound having a structure according to formula (I) wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring, as a solvent system in an agrochemical emulsifiable concentrate, preferably the emulsifiable concentrate (EC) according to the first aspect.

[0017] In a final aspect, the present invention is directed to a use of the emulsion-in-water (EW) formulation according to the further aspect described above for treating plants, thereby maintaining plant health, without causing plant damage.

[0018] Definitions

[0019] Emulsifiable concentrates are typically optically transparent oily liquid formulations that are prepared by dissolving a certain amount of pesticide in organic solvents (such as benzene, toluene, xylene, and solvent oil), which may also contain surfactants (i.e. emulsifiers) and other additives. These concentrates are suitable for dispersion within an aqueous phase to form an emulsion-in-water formulation. Emulsifiable concentrates must be monophasic, i.e. the pesticide and any emulsifiers must be completely soluble in the organic solvent at the concentrations used.

[0020] An emulsion is a mixture of two or more liquids that are normally immiscible, wherein one liquid forms a dispersed phase, suspended as tiny droplets within the other liquid, which is known as the continuous phase. Emulsions are typically referred to as oil-in-water (i.e. the water is the continuous phase) or water-in-oil (i.e. the oil is the continuous phase). In the context of agrochemical formulations, oil-in-water emulsions, known as emulsion-in-water formulations are often used to disperse hydrophobic pesticides across fields of crop plants. The U.S Environmental Protection Agency (EPA) defines a pesticide as "any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest". A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the context of agrochemical formulations, pesticides are used to actively target pests, typically fungi, insects, and / or weed plants, without unduly harming the crop plant.

[0021] Phytotoxicity describes any adverse effects on plant growth, physiology or metabolism caused by a chemical or biological substance. In the context of agrochemical formulations, it is desired to avoid phytotoxic properties in order that the health of the crop plant is not impacted.

[0022] In the context of the present invention, alkyl refers to linear and branched chains alkyl chains, whilst aryl refers to any aromatic carbocyclic ring system, being either a single ring, for example phenyl group or a fused ring system, for example a naphthyl group or an anthracenyl group.

[0023] Detailed Description

[0024] In a first aspect, the present invention is directed to an emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers, one or more co-solvents having a structure free from benzaldehyde moieties and one or more solvents having a structure according to formula (I): wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring, wherein the total amount, expressed as % w / w, of the one or more solvents having a structure according to formula (I) is greater than the total amount, expressed as % w / w, of the one or more co-solvents having a structure free from benzaldehyde moieties.

[0025] The one or more solvents

[0026] One essential component of the emulsifiable concentrate (EC) is one or more solvents.

[0027] The one or more solvents according to the present invention each has a structure according to formula (I): wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring.

[0028] R represents 0 to 5 substitutions, i.e. 0, 1, 2, 3, 4, or 5 substitutions; however, it is preferred that R represents 0, 1, or 2 substitutions, more preferably 1 or 2 substitutions, alternatively 0 or 1 substitutions, most preferably 1 substitution.

[0029] Each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring.

[0030] The 5-membered or 6-membered ring formed from two instances of R may be a carbocyclic ring or a heterocyclic ring. Preferred examples of a carbocyclic ring include R = -(CH2)4- and R = -(CH2)3-, whilst preferred examples of a heterocyclic ring include R = -O(CH2)3-, R = - O(CH2)2O-, R = -O(CH2)2-, and R = -OCH2O-. The carbocyclic or heterocyclic rings may also be aromatic, for example R = -(CH)4-, R = -N(CH)3-, R = -(CH)N(CH)2-, R = -(NR'XCH),-, and R = -(CH)(NR1)(CH)-.

[0031] Preferably, each instance of R is selected from the group consisting of Cj to C10alkyl, aryl and OR1, more preferably the group consisting of Cj to C10alkyl and OR1wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl.

[0032] Each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, preferably from the group consisting of hydrogen and Cj to C4alkyl, more preferably from hydrogen, methyl and ethyl, most preferably R1is methyl.

[0033] In one embodiment, it is preferred that each instance of R is selected from the group consisting of alkyl and OR1, wherein R1is selected from the group consisting of hydrogen and Cl to C4 alkyl. In said embodiment, it is preferred that R represents 0, 1 or 2 substitutions, more preferably 0 or 1 substitutions, most preferably R represents 1 substitution.

[0034] In another embodiment, it is preferred that each instance of R is selected from the group consisting of hydroxy, ethoxy, methoxy, ethyl, and methyl. In said embodiment it is preferred that that R represents 0, 1 or 2 substitutions, more preferably 0 or 1 substitutions, most preferably 1 substitution. It is further preferred that each instance of R is OR1, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, more preferably from the group consisting of hydrogen and Cj to C4alkyl, yet more preferably from hydrogen, methyl and ethyl, most preferably R1is methyl.

[0035] It is particularly preferred that R represents one substitution and that this substitution is methoxy.

[0036] As such, it is preferred that at least one, preferably all, of the one or more solvents having a structure according to formula (I) is selected from the group consisting of 2-anisaldehyde, 3-anisaldehyde and 4-anisaldehyde, most preferably at least one of the one or more solvents having a structure according to formula (I) is 4-anisaldehyde, most preferably 4- anisaldehyde is the only solvent having a structure according to formula (I).

[0037] Alternatively, it may be preferred that R represents one substitution and that this substitution is hydroxy.

[0038] As such, it is preferred that at least one, preferably all, of the one or more solvents having a structure according to formula (I) is selected from the group consisting of 2- hydroxybenzaldehyde (i.e. salicylaldehyde), 3-hydroxybenzaldehyde and 4- hydroxybenzaldehyde, most preferably at least one of the one or more solvents having a structure according to formula (I) is salicylaldehyde (i.e. 2-hydroxybenzaldehyde), most preferably salicylaldehyde (i.e. 2-hydroxybenzaldehyde) is the only solvent having a structure according to formula (I).

[0039] Alternatively it may be preferred that R represents one substitution and that this substitution is methyl.

[0040] As such, it is preferred that at least one, preferably all, of the one or more solvents having a structure according to formula (I) is selected from the group consisting of 2- methylbenzaldehyde, 3-methylbenzaldehyde and 4-methylbenzaldehyde, most preferably at least one of the one or more solvents having a structure according to formula (I) is 4- methylbenzaldehyde, more preferably 4-methylbenzaldehyde is the only solvent having a structure according to formula (I).

[0041] Particularly preferred solvents according to formula (I) include benzaldehyde, 2- tolualdehyde, 3-tolualdehyde, 4-tolualdehyde, salicylaldehyde (i.e. 2-hydroxybenzaldehyde), 3-hydroxy benzaldehyde, 4-hydroxybenzaldehyde, 2-anisaldehyde (i.e. 2- methoxybenzaldehyde), 3-anisaldehyde, 4-anisaldehyde, 2-ethylbenzaldehyde, 3- ethylbenzaldehyde, 4-ethylbenzaldehyde, and 4-tertbutylbenzalydehyde.

[0042] In one embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is benzaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) is 2-tolualdeyhde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 3-tolualdeyhde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 4-tolualdeyhde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 2- hydroxybenzaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 3- hydroxybenzaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 4- hydroxybenzaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 2-anisaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 3-anisaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 4-anisaldehyde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 2- ethylbenzaldeyhde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 3-ethylbenzaldeyhde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 4-ethylbenzaldeyhde. In another embodiment, at least one of the one or more solvents having a structure according to formula (I) according to formula (I) is 4-tertbutylbenzaldeyhde.

[0043] Solvents having a structure according to formula (I) have a further advantage of having a pleasant smell. For example, 4-anisaldehyde has a sweet aniseed odor, 2-anisaldehyde has a licorice odor, vanillin (3-methoxy-4-hydroxybenzaldehade) has a vanilla odor, 4- tolualdehyde has a cherry-like odor, and benzaldehyde itself has an almond odor. These odors mean that the resulting emulsifiable concentrates (EC) and emulsions made therefrom are more pleasant to be used than many commercial amide-containing emulsifiable concentrate solvents, which typically have unpleasant fishy smells.

[0044] It is preferred that the solvent(s) according to formula (I) have / has a low water solubility, ensuring that an emulsion is formed, rather than a solution.

[0045] As such, it is preferred that at least one, preferably all, of the one or more solvents according to formula (I) has a water solubility of less than 1.00% w / w, more preferably of less than 0.50% w / w, most preferably of less than 0.30% w / w.

[0046] It is also preferred that at least one, preferably all, of the one or more solvents according to formula (I) has low phytotoxicity. This means that the presence of the solvent(s) in the emulsifiable concentrate (EC), and in any emulsion-in-water (EW) formulations formed therefrom, does not cause plant damage, more specifically does not cause plant damage to soya plants.

[0047] In particular, it is preferred that at least one, preferably all, of the one or more solvents according to formula (I) has low phytotoxicity, wherein low phytotoxicity is defined as being when an emulsion containing 99.0% w / w, relative to the total weight of the emulsion, of water and 1.0% w / w, relative to the total weight of the emulsion, of a non-aqueous phase containing 90% w / w of the solvent, 7.5% w / w castor oil ethoxylate and 2.5% w / w of calcium dodecylbenzenesulfonate, each relative to the total weight of the non-aqueous phase, causes at no greater plant damage than an aqueous solution of 0.075% w / w castor oil ethoxylate and 0.025% w / w of calcium dodecylbenzenesulfonate, each relative to the total weight of the aqueous solution, when measured 14 days after application to soya plants at an application rate of 200 L per hectare.

[0048] This is especially important for agrochemical emulsifiable concentrates, since it improves the specificity of the resultant emulsion-in-water, when applied to crop plants. The pesticides can actively target the relevant pest (e.g. insects, fungus or weed plants), whilst the crop plant is not adversely affected.

[0049] The total content of solvents with a structure according to formula (I) is preferably in the range from 10 to 80% w / w, more preferably from 15 to 70% w / w, most preferably from 25 to 60% w / w, relative to the total weight of the emulsifiable concentrate (EC).

[0050] The one or more co-solvents

[0051] Another essential component of the emulsifiable concentrate (EC) is one or more cosolvents.

[0052] The one or more co-solvents each have a structure that is free from benzaldehyde moieties.

[0053] The finding of the present invention is that a wide-range of co-solvents can be used in addition to the one or more solvents according to formula (I), allowing for a broader range of emulsifiers to be employed with certain pesticides that would not otherwise allow for the use of such emulsifiers.

[0054] In the broadest sense, the one or more co-solvents can be any solvent suitable for use in emulsifiable concentrates.

[0055] It is particularly preferred that the one or more co-solvents are selected from the group consisting of lactate esters, alkyl esters, aromatic esters, fatty acid esters, fatty acid amides and aromatic naphtha-based solvents. More preferably the one or more co-solvents are selected from the group consisting of lactate esters, fatty acid methyl esters, fatty acid dimethyl amides and aromatic naphtha-based solvents.

[0056] Suitable fatty acid esters include 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 icosanoate, methyl isononoate, 1-ethylhexyl palimatate, Caprylic / Capric Triglyceride, Propylene Glycol Dicaprylate / Dicaprate, Propane-1, 2, 3-triyl 2-ethylhexanoate, 2,2- bis [(octa noyloxy) methyl] butyl decanoate, Trimethylolpropane trioleate, and 2-ethylhexyl cocoate, and unsaturated variants thereof, such as methyl soyate ester, methyl canolate ester and methyl oleate, as well as fatty acid methyl ester mixtures, such as C8-C10 fatty acid methyl ester and C12-C18 fatty acid methyl ester, in addition to mixtures of any of the above.

[0057] Suitable fatty acid dimethylamides include dimethyl hexanamide, dimethyl heptanamide, dimethyl octanamide, dimethyl nonanamide, dimethyl decanamide, dimethyl undecanamide, dimethyl dodecanamide, dimethyl tridecanamide, dimethyl tetradecanamide, dimethyl pentadecanamide, dimethyl hexadecanamide, dimethyl heptadecanamide, dimethyl octadecanamide, dimethyl nonadecanamide, dimethyl icosanamide and unsaturated variants thereof, such as dimethyl soyate amide, dimethyl canolate amide and dimethyl oleanamide, as well as fatty acid dimethylamide mixtures, such as C8-C10 fatty acid dimethylamide and C12-C18 fatty acid dimethylamide, in addition to mixtures of any of the above.

[0058] Various aromatic naphtha-based solvents are commercially available and known to the person skilled in the art.

[0059] Suitable lactate esters include 2-ethyl hexyl lactate, butyl lactate, hexyl lactate, and octyl lactate.

[0060] Suitable alkyl esters include butyl acetate, hexyl acetate, 2-ethyl hexyl acetate, butyl propionate, hexyl propionate, dibutyl adipate, diisopropyl adipate, triethyl citrate, and 1,2- Cyclohexane dicarboxylic acid diisononyl ester.

[0061] Suitable aromatic esters include benzyl acetate, benzyl propionate, benzyl butonate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dibutyl terephthalate, Methyl salicylate, ethyl salicylate, propyl salicylate, and butyl salicylate.

[0062] It is preferred at least one, preferably all, of the co-solvents having a structure free from benzaldehyde moieties has a water solubility of less than 1.00% w / w, more preferably of less than 0.50% w / w, most preferably of less than 0.30% w / w.

[0063] In one particularly preferred embodiment, it is preferred that each of the one or more solvents according to formula (I) and each of the one or more co-solvents having a structure free from benzaldehyde moieties has a water solubility of less than 1.00% w / w, more preferably of less than 0.50% w / w, most preferably of less than 0.30% w / w.

[0064] The total content of co-solvents having a structure free from benzaldehyde moieties is preferably in the range from 5 to 70% w / w, more preferably from 10 to 50% w / w, most preferably from 15 to 40% w / w, relative to the total weight of the emulsifiable concentrate (EC). The one or more pesticides

[0065] Another essential component of the emulsifiable concentrate (EC) is one or more pesticides.

[0066] The one or more pesticides of the present invention are not limited.

[0067] A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term “pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.

[0068] A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term “pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.

[0069] The following lists of pesticides that are suitable for use in the emulsifiable concentrate of the invention is intended to illustrate the possible combinations but does not limit them:

[0070] A) Respiration inhibitors

[0071] - inhibitors of complex III at Qo site: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastro-bin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyribencarb, trie I opy rica rb / c h I orod i n ca r b, famoxadone, fenamidone, pyriminostrobin, bifujunzhi, metyltetraprole; - inhibitors of complex III at Qi site: cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid;

[0072] - inhibitors of complex II: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, pydiflumetofen, pyraziflumid, sedaxane, tecloftalam, thifluzamide, inpyrfluxam, pyrapropoyne, fluindapyr, isoflucypram, cyclobutrifluram;

[0073] - other respiration inhibitors: diflumetorim; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, meptyldinocap; ferimzone; organometal compounds: fentin salts, e.g. fentin-acetate, fentin chloride or fentin hydroxide; silthiofam;

[0074] - quinone outside inhibitor stigmatellin binding type: ametoctradin;

[0075] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0076] - C14 demethylase inhibitors: triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines, piperazines: fenarimol, pyrifenox, triforine;

[0077] - Deltal4-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;

[0078] - Inhibitors of 3-keto reductase: fenhexamid, fenpyrazamine;

[0079] - other Sterol biosynthesis inhibitors: chlorphenomizole;

[0080] C) Nucleic acid synthesis inhibitors

[0081] - RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixyl;

[0082] - other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, ipflufenoquin, quinofumelin;

[0083] D) Inhibitors of cell division and cytoskeleton

[0084] - tubulin polymerization inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, th io ph a nate- methyl, pyridachlometyl;

[0085] - other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, phenamacril, fluopimomide;

[0086] E) Inhibitors of amino acid and protein synthesis

[0087] - methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;

[0088] - protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloridehydrate, mildiomycin, streptomycin, oxytetracyclin;

[0089] F) Signal transduction inhibitors

[0090] - MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil; - mechanism unknown: quinoxyfen, proquinazid;

[0091] G) Lipid and membrane synthesis inhibitors

[0092] - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;

[0093] - lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;

[0094] - compounds affecting cell membrane permeability and fatty acides: propamocarb;

[0095] - inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin;

[0096] H) Inhibitors with Multi Site Action

[0097] - inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

[0098] - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;

[0099] -organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid;

[0100] - guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, fluoroimide, methasulfocarb, chinomethionat;

[0101] I) Cell wall synthesis inhibitors

[0102] - inhibitors of glucan synthesis: validamycin, polyoxin B;

[0103] - melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb;

[0104] - cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate;

[0105] J) Plant defence inducers

[0106] - acibenzolar-S-methyl, probenazol, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium or sodium bicarbonate, dichlobentiazox;

[0107] K) Unknown mode of action

[0108] - bronopol, cyflufenamid, cymoxanil, dazomet, debacarb, diclocymet, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenitropan, fenpyrazamine, flumetover, flumetylsulforim, flusulfamide, flutianil, harpin, nitrapyrin, nitrothal-isopropyl, oxin-copper, seboctylamine, tebufloquin, tecloftalam, triazoxide, pyrisoxazole, , benziothiazolinone, bromothalonil, aminopyrifen, flufenoxadiazam;

[0109] L) Biopesticides

[0110] LI) Microbial pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pu I lu Ians, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleo-phila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructi-cola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paeni-bacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudo-zyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Tricho-derma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);

[0111] L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;

[0112] L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and / or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tene-brionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium sub-tsugae, Cydia pomonella granulovirus, Cryptophlebia leucotreta granulovirus, Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus, Helicoverpa zea nucleopolyhedrovirus, Helicoverpa zea single capsid nucleopolyhedrovirus, Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus, Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus;

[0113] L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and / or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-l-yl acetate, ethyl formate, (E,Z) -2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,ll,13-hexadecatrienal, heptyl buty-rate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-l-ol, (E,Z)-2,13-octadecadien-l-ol acetate, (E,Z)-3,13-octadecadien-l-ol, (R)-l-octen-3-ol, pentatermanone, (E,Z,Z) 3,8,11- tetradecatrienyl acetate, (Z,E) 9,12-tetradecadien-l-yl acetate, (Z) 7 tetradecen-2-one, (Z)- 9-tetradecen-l-yl acetate, (Z)-ll-tetradecenal, (Z)-ll-tetra-decen-l-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;

[0114] L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and / or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;

[0115] 0) Insecticides from classes 0.1 to 0.29 0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, pro-thiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;

[0116] 0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole;

[0117] 0.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon- momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor;

[0118] 0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;

[0119] 0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;

[0120] 0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;

[0121] 0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;

[0122] 0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;

[0123] 0.9 Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon;

[0124] 0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;

[0125] 0.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Abl; 0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;

[0126] 0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid;

[0127] 0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;

[0128] 0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;

[0129] 0.16 Inhibitors of the chitin biosynthesis type 1: buprofezin;

[0130] 0.17 Moulting disruptors: cyromazine;

[0131] 0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;

[0132] 0.19 Octopamin receptor agonists: amitraz;

[0133] 0.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;

[0134] 0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;

[0135] 0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone;

[0136] 0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat;

[0137] 0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;

[0138] 0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide;

[0139] 0.28 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cycl a n i I i pro I e, flubendiamide, fluchlodiniliprole; tetrac h I ora ntra n i I i p rol e; tetraniliprole; tiorantraniliprole; cyhalodiamide;

[0140] 0.29 Chordotonal organ modulators: flonicamid;

[0141] 0.30 GABA-gated chloride channel allosteric modulators: broflanilide, fluxametamide, isocycloseram;

[0142] 0.33 Calcium-activated potassium channel modulators: acynonapyr;

[0143] 0.34 Mitochondrial complex III electron transport inhibitors at Qi site: flometoquin;

[0144] O.UN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropylate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, flu-ensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl but-oxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindolizine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflanilide, n icof I u pro I e; indazapyroxamet; flupentiofenox; cyclobutrifluram.

[0145] P) Herbicides from the classes Pl to P15

[0146] Pl) lipid biosynthesis inhibitors:

[0147] - ACC-herbicides: alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fl uazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P- methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim;

[0148] - non ACC herbicides: benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;

[0149] P2) ALS inhibitors:

[0150] - sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron- sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron- methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trif loxysu Ifu ron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;

[0151] - imidazolinones: imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;

[0152] - triazolopyrimidine herbicides and sulfonanilides: cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam;

[0153] - pyrimidinylbenzoates: bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium;

[0154] - sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl;

[0155] - and triafamone;

[0156] P3) photosynthesis inhibitors: amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat- dichloride and paraquat-dimetilsulfate;

[0157] P4) protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon- ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, f lumiclorac, f I u miclorac-penty I , f lumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, epyrifenacil;

[0158] P5) bleacher herbicides:

[0159] - PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;

[0160] - HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tol pyralate, topramezone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione;

[0161] - bleacher, unknown target: aclonifen, amitrole flumeturon, bixlozone;

[0162] P6) EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate- trimesium (sulfosate);

[0163] P7) glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;

[0164] P8) DHP synthase inhibitors: asulam;

[0165] P9) mitosis inhibitors:

[0166] - group KI: dinitroanilines: benfluralin, butralin, dinitramine, ethalf I u ra I i n, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin; phosphoramidates: amiprophos, amiprophos-methyl, and butamiphos; benzoic acid herbicides: chlorthal, chlorthal-dimethyl; pyridines: dithiopyr and thiazopyr; benzamides: propyzamide and tebutam;

[0167] - group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham;

[0168] PIO) VLCFA inhibitors:

[0169] - chloroacetamides: acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor,

[0170] - oxyacetanilides: flufenacet and mefenacet;

[0171] - acetanilides: diphenamid, naproanilide, napropamide and napropamide-M;

[0172] - tetrazolinones: fentrazamide;

[0173] - other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isoxazoline;

[0174] PH) cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam;

[0175] P12) decoupler herbicides: dinoseb, dinoterb and DNOC and its salts;

[0176] P13) auxinic herbicides:

[0177] 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, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr- butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, florpyrauxifen-benzyl and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6- yl)picolinic acid;

[0178] P14) auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;

[0179] P15) other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tetflupyrolimet, tridiphane.

[0180] Q) Safeners (quinolin-8-oxy)acetic acids, 1- pheny I -5-haloa I ky I - 1 H - 1,2,4-triazol -3-car boxyl ic acids, 1- p h eny I -4,5 -d i hyd ro-5-a I ky I - 1 H - py razo I -3,5 -d ica r boxy I ic acids, 4,5 -di hydro-5,5 -diary 1-3- isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4- (aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1,8- naphthal ic anhydride, 2-halo-4- (haloal kyl) -5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.

[0181] In the context of agrochemical emulsifiable concentrates, the one or more pesticides are preferably selected from the group consisting of insecticides, herbicides, fungicides and combinations thereof, wherein the examples of each class of pesticide may be as defined above and below.

[0182] It is particularly preferred that least one of the one or more pesticides is selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenacet, epoxiconazole, fluxapyroxad, fenbuconazole and tebuconazole.

[0183] In one especially preferred embodiment, the one or more pesticides comprise azoxystrobin and optionally further pesticides as described above. In one particularly preferred embodiment, azoxystrobin is the only pesticide present.

[0184] It is a finding of the present invention that the solubility of each of these commercially important pesticides is generally improved in the solvent combination according to the present invention, when compared with typical solvent systems used for agrochemical emulsifiable concentrates, such as benzyl acetate, fatty acid dimethylamides and aromatic naphtha-based solvents used without the solvent having a structure according to formula (I).

[0185] It is thus preferred that the total pesticide content in the emulsifiable concentrate (EC) is in the range from 5 to 60% w / w, more preferably in the range from 7 to 50% w / w, most preferably in the range from 10 to 40% w / w, relative to the total weight of the emulsifiable concentrate (EC).

[0186] In the context of agrochemical emulsifiable concentrates, it is also well known that more than one pesticide may be used, resulting in a so-called combination formulation. Such combination formulations may have improved effects since the individual pesticides act in a synergistic manner or alternatively, the multiple pesticides may be active against different pests, for example, one pesticide may be a herbicide and another may be an insecticide.

[0187] In one embodiment, the emulsifiable concentrate (EC) comprises two or more pesticides.

[0188] Many such combination formulations are commercially available and are well known in the field. As such, the choice of which combination of pesticides is selected is not particularly limited.

[0189] In a preferred embodiment, at least one, more preferably at least two, of the two or more pesticides is / are selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenacet, epoxiconazole, fluxapyroxad, fenbuconazole and tebuconazole.

[0190] It is particularly preferred that at least one of the one or more pesticides is azoxystrobin.

[0191] Particularly preferred combinations include azoxystrobin and cyproconazole, azoxystrobin and prothioconazole, cyproconazole and fenbuconazole, and azoxystrobin and tebuconazole.

[0192] The one or more emulsifiers

[0193] Another essential component of the emulsifiable concentrate (EC) is one or more emulsifiers.

[0194] The one or more emulsifiers of the present invention are not particularly limited. In its broadest form, the one or more emulsifiers may be selected from any conventional emulsifiers typically used in the field of agrochemical compositions and formulations.

[0195] For example, the one or more emulsifiers may be selected from:

[0196] - products of the addition of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear C8-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group;

[0197] - C12-18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol; - glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof

[0198] - addition products of 15 to 60 mol ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0199] - polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate;

[0200] - addition products of 2 to 15 mol ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0201] - partial esters based on linear, branched, unsaturated or saturated C6-22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, - dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose);

[0202] - mono-, di and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and salts thereof;

[0203] - wool wax alcohols;

[0204] - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;

[0205] - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol, and

[0206] - polyalkylene glycols

[0207] The one or more emulsifiers are preferably selected from the group consisting of non-ionic emulsifiers, anionic emulsifiers and combinations thereof.

[0208] It is particularly preferred that at least one of the one or more emulsifiers is a non-ionic emulsifier.

[0209] It is also preferred that at least one of the one or more emulsifiers is an anionic emulsifier.

[0210] In one particularly preferred embodiment, the one or more emulsifiers comprises, more preferably consists of, a non-ionic emulsifier and an anionic emulsifier.

[0211] Suitable non-ionic emulsifiers may be selected from the group consisting of copolymers containing ethylene oxide and propylene oxide monomers, alcohol alkoxylates, alkyl polyglucosides, aminopolyols, polyalkylene glycols, alkoxylated animal or vegetable fats and oils such as corn oil ethoxylates, soybean oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates, glycerol esters such as glycerol monostearate, fatty alcohol alkoxylates and oxoalcohol 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 polyglycosides, N- alkylgluconamides, alkylmethyl sulfoxides, alkyldimethylphosphine oxides such as tetradecyldimethylphosphine oxide, or combinations thereof. It is preferred that at least one of the one or more emulsifiers is a fatty acid ester ethoxylate, more preferably is a castor oil ethoxylate.

[0212] Suitable anionic emulsifiers include salts wherein the anion may be selected from the group consisting of fatty acids, fatty alcohol ethersulfates, fatty alcohol sulfates, alkylbenzene sulfonates, ether phosphates, alkyl sulfates, alkyl ether sulfates, alkylsulfonates or isoalkylsulfonates, alkylnaphthalenesulfonates, alkyl methyl ester sulfonates, acyl glutamates, alkylsulfosuccinates, sarcosinates, taurates and combinations thereof, whilst the cation may be selected from the group selected from alkali metal ions, alkaline earth metal ions, ammonium ions and combinations thereof..

[0213] It is preferred that at least one of the one or more emulsifiers is an alkyl benzene sulfonate, more preferably a linear alkylbenzene sulfonate.

[0214] In one especially preferred embodiment, the one or more emulsifiers comprises, more preferably consists of, a fatty acid ethoxylate and an alkylbenzene sulfonate. In this especially preferred embodiment, the fatty acid ester ethoxylate is more preferably a castor oil ethoxylate. The alkyl benzene sulfonate is likewise more preferably a linear alkylbenzene sulfonate.

[0215] The total content of the one or more emulsifiers in the emulsifiable concentrate (EC) is preferably in the range from 1 to 30% w / w, more preferably in the range from 5 to 20% w / w, most preferably in the range from 10 to 15% w / w, relative to the total weight of the emulsifiable concentrate (EC).

[0216] The emulsifiable concentrate (EC)

[0217] As detailed above, the emulsifiable concentrate (EC) according to the present invention comprises one or more pesticides, one or more emulsifiers, one or more solvents having a structure according to formula (I), and one or more co-solvents having a structure free from benzaldehyde moieties, as described above.

[0218] Particularly preferred combinations of one or more co-solvents with ionic and non-ionic emulsifiers are given in Table A:

[0219] wherein Cl is dimethyl nonanamide, C2 is C8-C10fatty acid dimethylamide, C3 is dimethyl decanamide, C4 is dimethyl dodecanamide, C5 is methyl hexanoate, C6 is methyl octanoate, C7 is methyl decanoate, C8 is methyl dodecanoate, C9 is methyl hexadecanoate, CIO is methyl octadecanoate, CH is methyl soyate ester, C12 is methyl canolate ester, C13 is methyl oleate, C14 is C8-C10fatty acid methyl ester, C15 is C12-C18fatty acid methyl ester, C16 is 2-ethyl hexyl lactate, C17 is 2-ethyl hexyl acetate, C18 is dibutyl adipate, C19 is diisopropyl adipate, C20 is 1,2-cyclohexane dicarboxylic acid diisononyl ester, C21 is benzyl acetate, C22 is methyl benzoate, C23 is dibutyl terephthalate, C24 is aromatic naphtha (C9- C10), C25 is aromatic naphtha (C10) and C26 is aromatic naphtha (C10-C13), Al is an al kyl benzene sulfonate and A2 is sodium dioctyl sulfosuccinate, whilst N1 is castor oil ethoxylate (20 to 40 EC), N2 is ethoxylated sorbitol hexaoleate, N3 is ethoxylated sorbitol monolaurate, N4 is a copolymer containing ethylene oxide and propylene oxide monomers, N5 is ethoxylated C10-C12alcohols, N6 is ethoxylated linear C16-C18alcohols, N7 is ethoxylated C16- C18and C18unsaturated alcohols, N8 is ethoxylated 2-propyl heptyl, N9 is ethoxylated and propoxylated 2- propyl heptyl , N 10 is ethoxylated branched C10-rich C9-Cnalcohols, Nil is ethoxylated isotridecanol , N12 is ethoxylated branched and linear C13-C15alcohols, N 13 is ethoxylated and propoxylated C12-C14alcohols, N14 is ethoxylated and propoxylated C13-C15alcohols, N 15 is ethoxylated and propoxylated C16-C18alcohols, N 16 is ethoxylated and butoxylated C13-C15alcohols and N17 is ethoxylated and propoxylated butanol.

[0220] For each of the 884 embodiments of Table A, any solvent having a structure according to formula (I) may be used. It is preferred that, for each of the 884 embodiments of Table A, benzaldehyde is used. It is also preferred that, for each of the 884 embodiments of Table A, 4-tolualdehyde is used. Alternatively, for each of the 884 embodiments of Table A, salicylaldehyde (i.e. 2-hydroxybenzaldehyde) is used. Most preferably, for each of the 884 embodiments of Table A, 4-anisaldehyde is used.

[0221] In addition to these essential components, the emulsifiable concentrate (EC) may further comprise adjuvants conventionally used for agrochemical formulations, the choice of the adjuvants depending on the specific use form, the type of formulation or the active substance. Examples of suitable adjuvants are surface-active substances (such as solubilisers, protective colloids, wetters and tackifiers), retention agents, wetting agents, spreaders, uptake enhancers, penetration agents, spray drift controllers, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, optionally colorants and adhesives (for example for the treatment of seed) or conventional adjuvants for bait formulations (for example attractants, feedants, bittering substances).

[0222] The emulsifiable concentrate (EC) according to the present invention preferably comprises, more preferably consists of: a) from 5 to 60% w / w, more preferably from 7 to 50% w / w, most preferably from 10 to 40% w / w, relative to the total weight of the emulsifiable concentrate (EC), of one or more pesticides; b) from 1 to 30% w / w, more preferably from 5 to 20% w / w, most preferably from 10 to 15% w / w, relative to the total weight of the emulsifiable concentrate (EC), of one or more emulsifiers; c) from 5 to 70% w / w, more preferably from 10 to 50% w / w, most preferably from 15 to 40% w / w, relative to the total weight of the emulsifiable concentrate (EC), of the one or more co-solvents having a structure free from benzaldehyde moieties d) from 10 to 80% w / w, more preferably from 15 to 70% w / w, most preferably from 25 to 60% w / w, relative to the total weight of the emulsifiable concentrate (EC), of the one or more solvents with a structure according to formula (I); and e) optionally from 1 to 79% w / w, more preferably from 5 to 63% w / w, most preferably from 10 to 40% w / w, relative to the total weight of the emulsifiable concentrate (EC), of one or more adjuvants, wherein the total amount of components a), b), c), d), and e) do not exceed 100%.

[0223] The total amount, expressed as % w / w, of the one or more solvents having a structure according to formula (I) is greater than the total amount, expressed as % w / w, of the one or more co-solvents having a structure free from benzaldehyde moieties. More preferably, the total amount of the one or more co-solvents having a structure free from benzaldehyde moieties is in the range from 5 to 49% w / w, more preferably in the range from 15 to 45% w / w, most preferably in the range from 30 to 40% w / w, relative to the sum of the total amount of the one or more co-solvents having a structure free from benzaldehyde moieties and the total amount of the one or more solvents having a structure according to formula (I).

[0224] As mentioned above, it is a finding of the present invention that many typical commercially important pesticides have improved solubility in the solvent combination according to the present invention, when compared with typical solvent systems used for agrochemical emulsifiable concentrates.

[0225] In addition to this finding, it has been further found that the inventive emulsifiable concentrates (EC) form highly stable emulsions when mixed with water to form emulsions, so called emulsion-in-water (EW) formulations.

[0226] The stability of an emulsion-in-water formulation may be evaluated by determining how much sedimentation or cream is formed following homogenization (i.e. following emulsification). Both cream and sedimentation represent a departure from idealized emulsion behavior, where the disperse particles either rise to the surface (creaming) or sink to the bottom (sedimentation) depending on their density. When determining the extent of creaming or sedimentation, it is not critical whether the emulsified droplets remain as such or aggregate to form a new continuous phase - both are sufficient to determine that the emulsion has broken down. The stability of a given emulsion is dependent on a number of factors, including the nature of the two immiscible phases, the relative amounts of each phase, and the emulsifiers used to stabilize the emulsion. For the purposes of quantifying emulsion stability in the context of the present invention, a stable emulsion is viewed as an emulsion that forms less than or equal to a given amount of cream and / or sedimentation 24 hours after homogenization.

[0227] It is a finding of the present invention that the inventive emulsifiable concentrates (EC) are suitable for forming a wide range of emulsion-in-water (EW) formulations, when mixed with water and homogenized, which demonstrate unexpectedly beneficial emulsion stability.

[0228] In order to quantify this beneficial feature of the emulsifiable concentrates (EC), a model emulsion system comprising 5.0 mL of the emulsifiable concentrate (EC) and 95.0 mL of water may be used, in which case a stable emulsion is defined as an emulsion that produces less than or equal to 1.0 mL of cream or sediment, 24 hours after formation of said emulsion.

[0229] As such, it is preferred that the emulsifiable concentrate (EC) forms a stable emulsion when 5.0 mL of said 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 1.0 mL of cream or sediment, 24 hours after formation of said emulsion.

[0230] More preferably the emulsion forms less than or equal to 0.5 mL of cream or sediment, 24 hours after formation of said emulsion.

[0231] If the emulsion does produce a measurable level of sediment or cream, it is further preferred that the emulsion may be re-homogenized, i.e. re-emulsified, to reform a stable emulsion, wherein a stable emulsion is as defined as above, wherein less than or equal to 1.0 mL of cream or sediment is formed 30 minutes after re-homogenization, more preferably wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after rehomogenization.

[0232] Methods for the initial homogenization and re-homogenization are well known in the art, and the precise method used in such a test is not critical.

[0233] That said, it is preferred that the homogenization is carried out by gentle inversion of the emulsion 10 times and that the re-homogenization is likewise carried out by gentle inversion of the emulsion 10 times.

[0234] As would be understood by the person skilled in the art, the threshold of how much cream or sediment would indicate that an emulsion would not be stable is dependent on the amounts of each phase present in the emulsion. As such, alternative tests, such as may be envisaged.

[0235] A model emulsion system comprising 0.5 mL of the emulsifiable concentrate (EC) and 99.5 mL of water may be used to assess stability, in which case a stable emulsion is defined as an emulsion that produces less than or equal to 0.5 mL of cream or sediment, 24 hours after formation of said emulsion. It is thus further preferred that the emulsifiable concentrate (EC) forms a stable emulsion when 0.5 mL of said emulsifiable concentrate (EC) is combined with 99.5 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 0.5 mL of cream or sediment, 24 hours after formation of said emulsion.

[0236] More preferably the emulsion forms less than or equal to 0.2 mL of cream or sediment, 24 hours after formation of said emulsion.

[0237] If the emulsion does produce a measurable level of sediment or cream, it is further preferred that the emulsion may be re-homogenized, i.e. re-emulsified, to reform a stable emulsion, wherein a stable emulsion is as defined as above, wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after re-homogenization, preferably wherein less than or equal to 0.2 mL of cream or sediment is formed 30 minutes after rehomogenization.

[0238] Emulsion-in-water (EW) formulation

[0239] As described above, the emulsifiable concentrates (EC) of the present invention are most suitable for forming highly stable emulsion-in-water (EW) formulations.

[0240] In a further aspect, the present invention is directed to an emulsion-in-water (EW) formulation, comprising an aqueous phase and a non-aqueous phase, wherein the nonaqueous phase is the emulsifiable concentrate (EC) of the first aspect.

[0241] The precise amounts of the 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 consists of, an amount in the range from 0.01 to 80.0% w / w of the emulsifiable concentrate (EC) according to the first aspect and an amount in the range of from 20.0 to 99.99% w / w of water, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0242] It is further preferred that that the emulsion-in-water (EW) formulation comprises, more preferably consists of, an amount in the range from 0.1 to 50.0% w / w of the emulsifiable concentrate (EC) according to the first aspect and an amount in the range of from 50.0 to 99.9% w / w of water, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation.

[0243] It is especially preferred that the emulsion-in-water (EW) formulation comprises, more preferably consists of, an amount in the range from 0.5 to 5.0% w / w of the emulsifiable concentrate (EC) according to the first aspect and an amount in the range of from 95.0 to 99.5% w / w of water, both amounts being expressed relative to the total weight of the emulsion-in-water (EW) formulation. In addition to the emulsifiable concentrate (EC) according to the first aspect and water, the emulsion-in-water (EW) formulation may further contain adjuvants conventionally used for agrochemical formulations (co-called tank adjuvants), the choice of the adjuvants depending on the specific use form, the type of formulation or the active substance. Examples of suitable adjuvants are surface-active substances (such as solubilisers, protective colloids, wetters and tackifiers), retention agents, wetting agents, spreaders, uptake enhancers, penetration agents, spray drift controllers, crystallization inhibitors, organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, optionally colorants and adhesives (for example for the treatment of seed) or conventional adjuvants for bait formulations (for example attractants, feedants, bittering substances).

[0244] All preferable embodiments and fallback positions relating to the emulsifiable concentrate (EC) of the first aspect are applicable mutatis mutandis to the emulsion-in-water (EW) formulation of the further aspect.

[0245] Use

[0246] In yet a further aspect, the present invention is directed to a use of a co-solvent having a structure free from benzaldehyde moieties and a compound having a structure according to formula (I) wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group selected from hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring, as a solvent system in an agrochemical emulsifiable concentrate, preferably the emulsifiable concentrate (EC) according to the first aspect.

[0247] All preferable embodiments and fallback positions relating to the emulsifiable concentrate (EC) of the first aspect are applicable mutatis mutandis to the use of a compound having a structure according to formula (I) of the present aspect.

[0248] Likewise, all preferable embodiments and fallback positions relating to the compound(s) having a structure according to formula (I) given for the first aspect are applicable mutatis mutandis to the compound having a structure according to formula (I) as used in the present aspect.

[0249] All preferable embodiments and fallback positions relating to the co-solvent(s) having a structure free from benzaldehyde moieties of the first aspect are applicable mutatis mutandis to the co-solvent(s) having a structure free from benzaldehyde moieties as used in the present aspect.

[0250] In a final aspect, the present invention is directed to a use of the emulsion-in-water (EW) formulation according to the further aspect described above for treating plants, thereby maintaining plant health, without causing plant damage.

[0251] Plant damage may be evaluated relative to the treatment of the plant with an aqueous solution containing the same emulsifiers, simply without the solvent and the pesticide. Avoiding plant damage is generally achieved by using one or more pesticides known to have low phytotoxicity in combination with a solvent having low phytotoxicity.

[0252] In particular, it is preferred that the solvent has low phytotoxicity, wherein low phytotoxicity is defined as being when an emulsion containing 99.0% w / w, relative to the total weight of the emulsion, of water and 1.0% w / w, relative to the total weight of the emulsion, of a nonaqueous phase containing 90% w / w of the solvent, 7.5% w / w castor oil ethoxylate and 2.5% w / w of calcium dodecylbenzenesulfonate, each relative to the total weight of the nonaqueous phase, causes at no greater plant damage than an aqueous solution of 0.075% w / w castor oil ethoxylate and 0.025% w / w of calcium dodecylbenzenesulfonate, each relative to the total weight of the aqueous solution, when measured 14 days after application to soya plants at an application rate of 200 L per hectare.

[0253] The phytotoxicity of various commonly-used pesticides is within the common general knowledge of the person skilled in the art.

[0254] All preferable embodiments and fallback positions relating to the emulsion-in-water (EW) formulation of the further aspect described above are applicable mutatis mutandis to the use of the emulsion-in-water (EW) formulation for treating plants of the final aspect.

[0255] Experimental Section

[0256] Materials used:

[0257] Solvents: Solvesso 200 ND was purchased from Exxon Mobil. Methyl hexanoate, methyl octanoate, methyl decanoate, dimethyl octanamide, dimethyl decanamide, and 4- anisaldehyde were sourced from BASF.

[0258] CIPAC D water: Made in the lab using a standard recipe published by CIPAC “MT 18.1.4”: Standard Waters .The water has a hardness of 342 ppm, with a 4:1 mixture of Ca:Mg ions at pH 6-7.

[0259] The pesticides: azoxystrobin was purchased from a commercial source

[0260] The co-solvents: The identity of the various co-solvents is given below:

[0261] Co-solvent 1 Methyl hexanoate

[0262] Co-solvent 2 Methyl octanoate

[0263] Co-solvent 3 Methyl decanoate

[0264] Co-solvent 4 Dimethyl octanamide

[0265] Co-solvent 5 Dimethyl decanamide

[0266] Co-solvent 6 Solvesso 200 ND (aromatic naphtha (C10-C13) with <1% naphthalene)

[0267] Co-solvent 7 Dibutyl adipate

[0268] Co-solvent 8 2-Ethylhexyl acetate

[0269] The emulsifiers: The emulsifiers used in the experiments are listed below.

[0270] Emulsifier 1 EO-PO-EO block copolymer, 40% EC, Molar Mass 4600 g / mol

[0271] Emulsifier 2 Castor Oil ethoxylate (30 EC units)

[0272] Emulsifier 3 Castor Oil ethoxylate (40 EO units)

[0273] Emulsifier 4 Calcium dodecylbenzene sulfonate 70% in isobutanol

[0274] Emulsifier 5 Calcium dodecylbenzene sulfonate 60% in 2-ethylhexanol

[0275] Emulsifier 6 Castor Oil ethoxylate (54 EO units)

[0276] Methods:

[0277] The emulsion was tested for its dispersibility by the effect known as blooming.

[0278] The emulsions were assessed according to their spontaneous emulsification when the concentrate is added to water (known in the art as "blooming") with a visual assessment given on a scale of 1 to 5, whereby 1). Excellent, “cloud of emulsion”, does not sink to bottom of cylinder. 2). Good, “cloud of emulsion”, but sinks to bottom of cylinder 3). Okay, “poor emulsion cloud”, larger droplets 4). Poor, “no emulsion cloud”, small “particles” observed 5). Very poor, no emulsion, oil and water phases immediately separate" Initial emulsion quality is assessed following the addition of the emulsion concentrate to water and resulting inversion ten times to enable mixing. Herein, a visual assessment is made on the resulting emulsions on a scale of 1 to 5, whereby 1). Excellent, “white / blue colour”, fine droplets 2). Good, “milky white” 3). Okay, “less-milky”, small particles observed 4). Poor, “large droplets” 5). Very poor, phase separation

[0279] The water solubility of the solvent was determined according to a method based on CIPAC MT157.1 and OECD 105 via the visual assessment of undissolved solvent in water after vigorous mixing and standing. Herein, various amounts of solvent and water were mixed with vigorous shaking in a glass-stoppered graduated cylinder or separating funnel, followed by standing for at least 30 min to enable separation. For example, if undissolved solvent was observed after thorough mixing of 0.1 g solvent in 100 mL of water, the solvent had a water-solubility equal to or below 0.1% (< 1 g / L). This method can be repeated with various amounts of solvent and water to enable the determination of the water-solubility of the solvent.

[0280] Under these test conditions, 4-anisaldehyde has a water solubility of 0.20% w / w.

[0281] Example 1: Effect of co-solvent on emulsifiable concentrate stability with varied emulsifiers

[0282] Emulsifiable concentrates were prepared in the following examples and the resulting 5% w / w emulsions in various water hardness at 21 ° C after 24 hours were assessed. Emulsion stability was determined as a function of time, with the amount of either cream or sediment measured.

[0283] To measure emulsion stability, 5.0 mL of the emulsifiable concentrate was diluted in 95.0 mL CIPAC D water in a 100 mL measuring cylinder. The resulting oil-in-water emulsion stability was assessed after 1, 2, 4 and 24 hours. A highly stable emulsion does not form cream, or have less than 1.0 mL cream after 24 hours, and can be readily re-emulsified after 24 h of standing without the formation of cream, with such re-emulsified emulsions assessed 30 minutes after re-emulsification. Both the initial emulsification and the reemulsification were achieved by gently inverting the emulsion 10 times.

[0284] Table 1 Testing of azoxystrobin EC formulations with various co-solvent / emulsifier combinations

[0285] * Emulsion tests conducted in CIPAC D water (342 ppm hardness, 4:1 Ca:Mg, pH 6 - 7) at 21 ° C ** NM = not measured, due to instability of EC

[0286] Table lb Testing of EC formulations with various pesticides and pesticide mixtures

[0287] * Emulsion tests conducted in CIPAC D water (342 ppm hardness, 4:1 Ca:Mg, pH 6 - 7) at 21 ° C ** NM = not measured, due to instability of EC

[0288] As can be seen from RE1 to RE3, emulsifiable concentrates containing azoxystrobin, which is a notoriously difficult active ingredient to solubilise, experience unacceptably poor emulsion stability unless a specific combination of an EO-PO-EO block copolymer with an alkylbenzene sulfonate is employed (i.e. RE3). CE1 to CE4 further demonstrate that this trend holds even for emulsifiable concentrates with lower amounts of azoxystrobin. By comparing RE2 with RE1, CE2 with CE1 and CE4 with CE3, it can be seen that the use of the alkylbenzene sulfonate helps to improve the emulsion stability relative to the use of the fatty acid ethoxylate alone; however, it is only via the use of various co-solvents, such as esters (IE1, IE5 and IE6), fatty acid amides (IE2 and IE3) and aromatic naphtha-based solvents (IE4), that acceptable emulsion stability may be achieved. The use of co-solvents in combination with benzaldehyde-based solvents thus allows the person skilled in the art more flexibility when selecting appropriate emulsifiers for emulsifiable concentrates than would be the case when the benzaldehyde-based solvents are employed without a suitable co-solvent. IE7 to I E14 demonstrate the flexibility of this approach with a wide range of pesticides / pesticide combinations.

Claims

Claims:

1. An emulsifiable concentrate (EC) comprising one or more pesticides, one or more emulsifiers, one or more co-solvents having a structure free from benzaldehyde moieties and one or more solvents having a structure according to formula (I):wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, and optionally two instances of R can be joined to form a 5-membered or 6-membered ring, wherein the total amount, expressed as % w / w, of the one or more solvents having a structure according to formula (I) is greater than the total amount, expressed as % w / w, of the one or more co-solvents having a structure free from benzaldehyde moieties.

2. The emulsifiable concentrate (EC) according to claim 1, wherein each instance of R is OR1.

3. The emulsifiable concentrate (EC) according to claim 2, wherein at least one, preferably all, of the one or more solvents having a structure according to formula (I) is selected from the group consisting of 2-anisaldehyde, 3-anisaldehyde and 4-anisaldehyde, more preferably at least one of the one or more solvents having a structure according to formula (I) is 4-anisaldehyde, most preferably 4-anisaldehyde is the only solvent having a structure according to formula (I).

4. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein at least one of the one or more co-solvents, more preferably each of the one of more co-solvents, is selected from the group consisting of lactate esters, fatty acid esters, fatty acid amides and aromatic naphtha-based solvents.

5. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein the at least one, preferably all, of the one or more solvents having a structure according to formula (I) and the one or more co-solvents having a structure free from benzaldehyde moieties has a water solubility of less than 1.00% w / w, more preferably of less than 0.50% w / w, most preferably of less than 0.30% w / w.

6. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein at least one of the one or more pesticides is selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, difenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenacet, epoxiconazole, fluxapyroxad, fenbuconazole and tebuconazole.

7. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein the total pesticide content is in the range from 5 to 60% w / w, more preferably in the range from 7 to 50% w / w, most preferably in the range from 10 to 40% w / w, relative to the total weight of the emulsifiable concentrate (EC).

8. The emulsifiable concentrate (EC) according to any one of the preceding claims, comprising two or more pesticides.

9. The emulsifiable concentrate (EC) according to any one of the preceding claims, containing one or more non-ionic emulsifier(s) and one or more anionic emulsifier(s).

10. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein at least one of the one or more emulsifiers is a fatty acid ester ethoxylate.

11. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein at least one of the one or more emulsifiers is an alkyl benzene sulfonate.

12. The emulsifiable concentrate (EC) according to any one of the preceding claims, wherein the emulsifiable concentrate (EC) forms a stable emulsion when 5.0 mL of said 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 1.0 mL of cream or sediment, 24 hours after formation of said emulsion.

13. An emulsion-in-water (EW) formulation, comprising an aqueous phase and a nonaqueous phase, wherein the non-aqueous phase is the emulsifiable concentrate (EC) according to any one of claims 1 to 12.

14. A use of a co-solvent having a structure free from benzaldehyde moieties and a compound having a structure according to formula (I)wherein R represents 0 to 5 substitutions, wherein each instance of R is selected from the group consisting of deuterium, halogen, Cj to C10alkyl, aryl, OR1, and NR^, wherein each R1is selected from the group consisting of hydrogen and Cj to C10alkyl, and optional ly two instances of R can be joined to form a 5-membered or 6-membered ring, as a solvent system in an agrochemical emulsifiable concentrate, preferably the emulsifiable concentrate (EC) according to any one of claims 1 to 12.

15. A use of the emulsion-in-water (EW) formulation according to claim 13 for treating plants, thereby maintaining plant health, without causing plant damage.

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