Agrochemical Compounds

Abstract

The present invention relates to emulsion concentrate (EC) formulations of succinate dehydrogenase inhibitor fungicides, the preparation of such formulations and their use in diluted form for the control of fungal pathogens, particularly in crops of useful plants. More specifically, the present invention relates to an emulsion concentrate of -difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide, comprising a blend of at least three surfactants and an aromatic ester solvent.

Description

[Technical Field]

[0001] The present invention relates to emulsifiable concentrate (EC) formulations of succinate dehydrogenase inhibitor fungicides, the preparation of such formulations and their use in diluted form for the control of fungal pathogens, especially in crops of useful plants. More specifically, the present invention relates to an emulsion concentrate of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide (pydiflumetofen) comprising a blend of at least three surfactants. [Background technology]

[0002] Two common types of formulations used in the agrochemical industry are suspension concentrates (SCs) and emulsifiable concentrates (ECs). Both have their advantages and disadvantages. One important advantage of EC formulations relates to the ultimate delivery of the active ingredient to its target. In suspensions (i.e., diluted SCs), solid agrochemical particles are delivered to the surface of leaves, fungi, insects, or nematodes, whereas in emulsions derived from ECs, the agrochemical active ingredient is dissolved in a solvent that allows penetration into the target tissue, such as plant tissue, fungi, insects, or nematodes. This more targeted application can result in greater bioavailability and therefore allow lower concentrations of the active ingredient to be used in the field. This is beneficial for many reasons and is particularly useful when the active ingredient is poorly soluble in commonly used solvents.

[0003] An emulsion is a colloidal mixture of two or more mutually immiscible liquids. There are two main types of emulsions: (i) oil-in-water (O / W), where the continuous phase is an aqueous solution and the dispersed phase is a water-immiscible organic liquid, typically oil, and (ii) water-in-oil (W / O), where the continuous phase is a water-immiscible organic liquid and the dispersed phase is aqueous. More complex emulsions, such as O / W / O (i.e., oil droplets contained within aqueous droplets dispersed in a continuous oil phase), are also possible.

[0004] Emulsions are thermodynamically unstable, and liquid / liquid systems have a natural tendency to separate and reduce their interfacial area and therefore their interfacial energy. The free energy of emulsion formation is given by Equation 1 below: ΔG 形態 =ΔAγ 12 -TΔS Equation 1 where ΔA is the change in interfacial area (where A=A2-A1), and γ 12 is the interfacial tension, ΔS is the change in entropy, and T is the temperature of the system.

[0005] As more droplets are generated during the formation of the emulsion, the interfacial area of ​​the system increases, and therefore the surface energy term, ΔAγ in Eq. 12 is positive. The entropy term, TΔS, is also positive because the generation of a large number of droplets is accompanied by an increase in configurational entropy. In most cases, ΔAγ 12 >>TΔS, so ΔG 形態 is positive, and emulsion formation is a non-spontaneous process: energy must be provided to the system for emulsification to occur, such as energy from mixing. (One exception to this is microemulsions, which can form spontaneously and are generally considered to be thermodynamically stable systems.)

[0006] Even after formation, the system remains thermodynamically unstable and the emulsion will break down over time by several processes. The following forms of instability are mechanisms by which the liquid size distribution and homogeneity of the system can change: creaming and sedimentation, coalescence, flocculation, and Ostwald ripening or disproportionation.

[0007] Creaming derives its name from the most commonly known example of the demulsification process - the separation of milk into cream and skim milk components. Creaming describes this separation of the dispersed and continuous phases due to differences in density. When external forces, such as gravity, are greater than the random movement of emulsion droplets (Brownian motion), a concentration gradient is formed within the system. This can cause emulsion droplets to move to the top (if their density is lower than that of the continuous phase) or to the bottom (if their density is greater than that of the continuous phase).

[0008] Coalescence occurs when two or more droplets fuse into one larger droplet. It can result from the close proximity of the droplets due to van der Waals attractive forces between them. It occurs when the thin liquid film between the droplets ruptures, possibly due to vibrational waves in the film.

[0009] Soft flocculation can generally be defined as "the aggregation of droplets to give 3D clusters where no coalescence occurs. Importantly, all droplets maintain their own integrity and remain as completely separate entities." This is due to the van der Waals attractive forces between droplets when the electrostatic repulsion between them is sufficiently reduced.

[0010] Ostwald ripening occurs when small droplets decrease in size until they disappear, and large droplets grow larger. The fundamental reason for this is the existence of a pressure difference (Δp) across a curved liquid / liquid interface (radius of curvature r and interfacial tension γ), as given by the equation shown in Equation 2.

number

[0011] This means that Δp is larger for smaller droplets than for larger ones. The chemical potential of the molecules that make up the droplets is also larger in smaller droplets. This difference in chemical potential drives the movement of molecules from the smaller droplets to the larger droplets across the aqueous continuous phase, thus reducing the total free energy of the system.

[0012] The kinetic stability of emulsions can most commonly be achieved by the addition of surfactants or surface active agents. Surfactants are amphiphilic (both oil and water loving) molecules composed of a hydrophilic "head" and a hydrophobic "tail." Surfactants "reside" at interfaces due to their dual nature. The free energy of surfactant molecules located at an interface is lower than the free energy of the molecules in the bulk. Therefore, absorption of surfactant molecules at an interface is a spontaneous process and results in a decrease in interfacial tension. From Equation 1, the interfacial tension γ 12 By lowering the interfacial area, a larger change in interfacial area ΔA and therefore a smaller size of emulsion droplets is obtained through the enthalpy term ΔAγ 12 It can be shown that the addition of surfactant molecules to a system often leads to the formation of smaller and more stable emulsion droplets compared to a system that does not contain any emulsifier.

[0013] The tail group of a surfactant molecule is usually a single or double, linear or branched hydrocarbon chain. The head group can be charged or neutral. Based on the type of head group, surfactants can be classified into four groups: nonionic, anionic, cationic, or amphoteric. Nonionic surfactants have a neutral head group, such as poly(ethylene oxide). Anionic and cationic surfactants have negatively and positively charged head groups, respectively. Common examples of these include ether sulfates and quaternized amines. Amphoteric surfactants, also known as zwitterions, combine both positive and negative groups.

[0014] In emulsions, at low concentrations (below the critical micelle concentration), surfactants are absorbed to the droplet surface by their hydrophobic moieties, while the hydrophilic moieties provide charge stabilization in the case of anionic and cationic surfactants and steric stabilization in the case of nonionic surfactants. Anionic and cationic surfactants impart electrostatic charges to the droplets, thereby repelling them from each other and preventing them from approaching closely, thereby preventing droplet coalescence. Nonionic surfactants create a physical barrier to droplet coalescence. Close approach of emulsion droplets will result in a loss of configurational entropy of the surfactant chains. Thus, entropy acts as a repulsive force between the droplets.

[0015] The hydrophilic-lipophilic balance (HLB) is a measure of the ratio of hydrophilic and lipophilic (hydrophobic) portions of a surfactant molecule. An HLB range of 8-18 typically provides a good oil-in-water emulsion. With sufficient energy, emulsion droplets can form both O / W and W / O emulsions, with the type that survives being determined primarily by the surfactant used. The critical packing parameter, p, is given by Equation 3:

number

[0016] Emulsion droplet size is also one physical property that can affect emulsion stability. Smaller droplets generally result in more stable emulsions. This is because very small droplet sizes cause a significant reduction in gravitational force, and thus Brownian motion may be sufficient to overcome gravity. This can be shown by Stokes' equation (Equation 4), which estimates the creaming or settling velocity of a system:

number

[0017] The temperature stability of emulsions in diluted or concentrated form is also important. The solubility of any solid is generally temperature-dependent, with solids tending to leave solution / crystallize at lower temperatures. Crystallization occurs when the concentration of a solute in a solvent exceeds its equilibrium solubility. Ideally, therefore, the agrochemical active ingredient in an EC formulation has high solubility in the solvent, which is dispersed throughout the continuous phase. Therefore, for oil-in-water emulsions / emulsifiable concentrates, it is desirable for the agrochemical active ingredient to have high solubility in a water-immiscible solvent, while for water-in-oil emulsions / emulsifiable concentrates, it is desirable for the agrochemical active ingredient to have high solubility in a water-miscible solvent.

[0018] Key requirements for an agrochemical EC formulation relate to (i) the solubility of the agrochemical active ingredient in a water-immiscible solvent that results in a good quality emulsion upon dilution, (ii) the stability of the emulsion formed upon dilution over a range of temperatures, and (iii) the stability of the concentrate during cold storage. From the above discussion of the basic technology, it can be seen that optimizing these parameters for any given active ingredient is a nontrivial task and is highly dependent on the particular active ingredient incorporated into the formulation.

[0019] The compound 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide (common name pydiflumetofen) is a potent fungicidal agrochemical described in WO 2010 / 063700, which also discusses general formulation options for such N-alkoxy-(phenyl-ethyl)-pyrazole carboxamides. Both WO 2015 / 124542 and WO 2015 / 12543 describe basic formulations of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide, but with low concentrations of the active ingredient and fully water-miscible solvents. Summary of the Invention [Means for solving the problem]

[0020] The present invention therefore provides an alternative formulation type of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and addresses the need for an optimal emulsifiable concentrate, particularly with regard to providing an optimal surfactant component for such formulations.

[0021] Thus, in a first aspect, there is provided a fungicidal emulsifiable concentrate comprising: (a) the fungicide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide; (b) at least one solvent selected from the group consisting of aromatic ester solvents, acetophenone, dimethyl lactamide, and gamma butyrolactone; (c) a surfactant blend of at least three surfactants, at least two of the surfactants being nonionic surfactants, and at least one of the surfactants being calcium dodecylbenzene sulfonate, an anionic surfactant; A fungicidal emulsifiable concentrate comprising:

[0022] In a further aspect, there is provided a fungicidal emulsion comprising a fungicidal emulsifiable concentrate as described herein and an agrochemically acceptable diluent. Obviously, such emulsions are of the oil-in-water type. DETAILED DESCRIPTION OF THE INVENTION

[0023] The choice of solvent for an agrochemical EC formulation is important and depends on the particular active ingredient (solute). Additionally, the choice of solvent for an emulsifiable concentrate formulation can affect the physical stability, application characteristics, and biological performance of the agrochemical formulation. In this case, the active ingredient is the fungicide pydiflumetofen, or its IUPAC name, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide (the name "pydiflumetofen" is used interchangeably herein with its IUPAC name, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide). Pydiflumetofen is difficult to solubilize in many commonly used agrochemical formulation solvents, as discussed above and shown in Table 1 below.

[0024] [Table 1]

[0025] The above solvents (and others) were tested for their ability to maintain pydiflumetofen in solution in the dispersed phase of an emulsion formed in a continuous aqueous phase (i.e., their ability to act as solvents for the dispersed phase of an oil-in-water emulsion). Tests were conducted using pydiflumetofen dissolved in EC formulations at concentrations of 12.5%, 10.0%, 7.5%, 6.25%, and 5% (w / v). These studies revealed that both methyl benzoate and a solvent blend of dipropylene glycol dibenzoate with dimethyl lactamide were superior solvents for use in the EC formulations of pydiflumetofen described herein. Not only are they able to dissolve a larger amount of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide, but furthermore, formulations of pydiflumetofen in these solvents also showed good low-temperature storage capacity and / or very good emulsion stability upon dilution.

[0026] When a blend of dipropylene glycol dibenzoate and dimethyl lactamide is used, ratios of dipropylene glycol dibenzoate to dimethyl lactamide of 1:1.36, 1.1:1, 1.3:1, and 3:2, inclusive, provide best results. A preferred ratio range is 1.1:1 to 3:2 dipropylene glycol dibenzoate to dimethyl lactamide, inclusive.

[0027] The present invention is based on the discovery that not only is pydiflumetofen difficult to solubilize, but emulsions of pydiflumetofen require a blend of different surfactants for optimal emulsification and stability.

[0028] As mentioned above, emulsions are inherently thermodynamically unstable, and one way to optimize stability is to incorporate a surface-active agent or surfactant that acts as an emulsifier. Fourteen nonionic surfactants with different chemical properties and HLB values ​​ranging from 6 to 17 were initially screened for suitability as emulsifiers for pydiflumetofen EC formulations. None of these, when used alone as the only surfactant in the test formulation, produced stable pydiflumetofen EC formulations with the desired emulsifying properties. However, five surfactants listed in Table 2 provided interesting enough results to select them for further evaluation, including nonionic surfactant B. ni and C ni is the most promising from the single surfactant screening.

[0029] [Table 2]

[0030] The five nonionic surfactants listed in Table 2 were then tested in various binary combinations with the anionic surfactants listed in Table 3.

[0031] [Table 3]

[0032] Surprisingly, B ni and C ni performed best as the sole nonionic surfactant, whereas the anionic surfactant B an When combined in a binary blend with nonionic surfactant A ni , B ni and D ni resulted in emulsions of better quality overall.

[0033] However, despite the vast number of binary surfactant combinations (varying ratios and components) tested, the quality of the emulsions formed was generally poor. Among the anionic surfactants tested, calcium dodecylbenzenesulfonate (B in Table 3) an , Ca-DDBS) were carried forward for further optimization.

[0034] Based on the results obtained with the single surfactants and binary blends of surfactants described herein, the ability of ternary emulsifier blend combinations to provide good quality emulsions upon dilution, combined with acceptable low temperature storage stability, was investigated using the tests described herein.

[0035] As an example, two nonionic surfactants (D in Table 2 above) at a combined level of 10% by weight ni and A ni ) and one anionic surfactant (B in Table 3 above) an Ternary combinations of 121 different ratios were tested for their ability to emulsify pydiflumetofen dissolved in methyl benzoate up to 7.5% (w / v). The droplet size and emulsion stability of each ratio were evaluated as described in "Materials and Methods" below. Table 4 provides details of the surfactant ratios and results for the five best EC samples analyzed (i.e., lowest AET values ​​and best initial emulsification).

[0036] [Table 4]

[0037] Emulsion stability testing of Samples 1 and 2 diluted in hard water Samples A and D (Table 5 below) showed that further improvements could be made with respect to emulsion stability after 2 hours at both 5°C and 30°C, and therefore two further approaches were taken: (i) including additional surfactant, and (ii) varying the total surfactant loading.

[0038] In the EC formulations described herein, pydiflumetofen can be dissolved in the solvents described above at a concentration of 5-10% (w / v) of the total formulation. Preferably, the EC formulations of the present invention contain pydiflumetofen at 6-8% (w / v) of the total formulation, more preferably 6-7% (w / v) of the total formulation. Thus, specific examples of pydiflumetofen concentrations in the emulsifiable concentrates of the present invention include 6.0, 6.05, 6.1, 6.15, 6.2, 6.25, 6.3, 6.35, 6.4, 6.45, 6.5, 6.55, 6.6, 6.65, 6.7, 6.75, 6.8, 6.85, 6.9, and 6.95 (w / v) of the total formulation. By varying the total amount of solvent in the composition, the composition can be adjusted to change the amount of active ingredient used. Therefore, the surfactant ratio remains the same as the total surfactant content. Similarly, when a solvent blend is used, the ratio of solvents within the blend remains the same even though the total solvent content is adjusted.

[0039] Additional formulation components may include silicone-based antifoam agents at a maximum concentration of up to 0.05% (w / v) of the total composition, but more typically at concentrations of 0.001%, 0.005%, 0.01%, 0.02%, 0.03% or 0.04% (w / v).

[0040] If desired, a microbicide / antibiotic component may also be included in the formulation to prevent microbial contamination of the emulsifiable concentrate during long-term storage under adverse conditions.

[0041] Additional fungicidal active ingredients can be incorporated into the emulsifiable concentrate of the present invention together with 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide.Preferred examples of additional fungicidal active ingredients for use in such combination include azole fungicides, particularly azoles selected from the group consisting of difenoconazole, prothioconazole, propiconazole and tebuconazole.Of these, prothioconazole is the preferred mixing partner. [Example]

[0042] Formulation Development Materials and Methods The methods and equipment used to identify and characterize the emulsifiable concentrates of the invention described herein are described below.

[0043] Droplet size analysis: As mentioned above, droplet size affects formulation stability, and generally, the smaller the droplet size, the more stable the formulation. The droplet size in the test EC formulations of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide was analyzed by various methods, including laser diffraction (using a laser diffraction particle size analyzer from Malvern Panalytical Ltd.), optical microscopy, and the use of an Agrochemical Emulsion Tester (AET) from Rank Brothers Ltd. The AET provides emulsion stability readings as a function of turbidity and droplet size. A higher value indicates a wider droplet size distribution and less stable emulsion, while a lower value indicates a more stable emulsion with a narrower distribution of smaller droplet sizes.

[0044] Emulsion Stability Test: Test samples of the EC formulation of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide were diluted with standard water samples of known hardness (Table 5) in glass receivers, which were then incubated overnight at 5°C and 30°C.

[0045] [Table 5]

[0046] Initial emulsification was assessed in the morning using the 4-point scale set forth in Table 6 below.

[0047] [Table 6]

[0048] The emulsion quality was visually assessed after homogenizing the samples by inversion using a scale of 0 to 5 as shown in Table 7 below.

[0049] [Table 7]

[0050] Further visual evaluations were performed at 0.5, 2, and 24 hours after homogenization, and the amount of any cream or oil was also recorded. After 24 hours, the samples were re-homogenized, the number of inversions required to re-emulsify was recorded, and the samples were re-incubated for 5 or 30 minutes (as appropriate) before a final visual evaluation, including by microscopy, was performed.

[0051] Foam persistence test - small and medium scale Small-scale testing involves preparing 200 ml of emulsion at maximum application rate. First, 180 ml of standard water D is weighed into a 250 ml graduated cylinder. The required mass of formulation is then added and topped up to 200 ml with water. The cylinder is capped and inverted 30 times over a 60-second period (approximately 2 seconds per inversion). The foam level is recorded after 10 seconds, 1 minute, 3 minutes, and 12 minutes.

[0052] The medium-scale (10 liter) test utilizes high levels of mechanical agitation to induce foaming. The test is conducted in a clear glass tank, and measurements are taken of foam height at various times throughout the test.

[0053] EC compound storage stability Samples of the EC formulations were stored under the conditions listed in Table 8 below. Samples were visually evaluated for phase separation, crystallization, color change, turbidity, and viscosity. Stored samples were also tested for pH and stability of any resulting emulsions. Chemical stability of the active ingredients was assessed by HPLC analysis for any degradation products.

[0054] [Table 8]

[0055] Applicable Test Spray tests were conducted by spraying through a standard spray nozzle equipped with a nozzle filter. Test emulsions were made by large-scale dilution of emulsifiable concentrates in tap water in a 100 L commercial farm sprayer tank. After spraying, the spray tank, filter, and nozzle were checked for sediment.

[0056] Example formulation The EC formulations of the present invention were developed as described above. Three EC formulations containing 6-7% (w / v) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]amide are provided as illustrative examples of the present invention, as listed in Table 9 below. When solvent blends are utilized, the dipropylene glycol dibenzoate to dimethyl lactamide ratio is 3:2 for EC3 and 1.1:1 for EC2, falling within the optimal range of 1.1:1 and 3:2, inclusive. The total amount of emulsifier in the emulsifiable concentrate is 10% (w / v) for EC1, 15% (w / v) for EC2, and 15% (w / v) for EC3.

[0057] [Table 9]

[0058] Each of these emulsifiable concentrates, EC1, EC2 and EC3, demonstrated excellent stability in concentrate form and the ability to produce well-stable emulsions upon dilution.

[0059] EC1 and EC2 are directly comparable in that they contain 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]amide as the only active ingredient. Using the above-described tests during formulation development, it is found that 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]amide has greater solubility in EC1, resulting in a formulation that exhibits better refrigerated storage characteristics than EC2. However, the emulsion formed upon dilution of EC2 exhibited greater stability than the emulsion formed upon dilution of EC1.

[0060] EC3 indicates that a further active ingredient, in this case the azole fungicide prothioconazole, may also be incorporated into the EC formulation of the present invention.

Claims

1. 1. A fungicidal emulsifiable concentrate comprising: (a) the fungicide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide; (b) at least one solvent selected from the group consisting of aromatic ester solvents, acetophenone, dimethyl lactamide, and gamma butyrolactone; (c) a surfactant blend of at least three surfactants, at least two of the surfactants being nonionic surfactants, and at least one of the surfactants being calcium dodecylbenzenesulfonate, an anionic surfactant; A fungicidal emulsifiable concentrate comprising:

2. 2. The fungicidal emulsifiable concentrate of claim 1, wherein the aromatic ester solvent is selected from dipropylene glycol dibenzoate and methyl benzoate.

3. 3. A fungicidal emulsifiable concentrate according to claim 1 or 2, wherein one of the non-ionic surfactants is a castor oil ethoxylate.

4. A fungicidal emulsifiable concentrate according to any one of claims 1 to 3, wherein one of the non-ionic surfactants is a copolymer butanol PO / EO.

5. 5. A fungicidal emulsifiable concentrate according to any one of claims 1 to 4, comprising a second solvent different from the first solvent, the second solvent being selected from the group consisting of aromatic ester solvents, acetophenone, dimethyl lactamide and gamma butyrolactone.

6. 7. The fungicidal emulsifiable concentrate of claim 6, wherein the second solvent is dimethyl lactamide.

7. A fungicidal emulsifiable concentrate according to any one of claims 1 to 5, comprising a third non-ionic surfactant.

8. 8. A fungicidal emulsifiable concentrate according to claim 7, wherein said third nonionic surfactant is polyoxyethylene sorbitan monolaurate.

9. A fungicidal emulsifiable concentrate according to any one of claims 1 to 8, comprising a second fungicide selected from the azole group of fungicides.

10. 10. A fungicidal emulsifiable concentrate according to claim 9, wherein the second fungicide is selected from the group consisting of difenoconazole, propiconazole, prothioconazole and tebuconazole.

11. (a) the fungicide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide; (b)(i) methyl benzoate, (c)(i) condensation products of castor oil and ethylene oxide; (c)(ii) calcium dodecylbenzenesulfonate; (c)(iii) copolymer butanol PO / EO; (c)(iv) polyoxyethylene sorbitan monolaurate, and (d) Silicone antifoaming agent A fungicidal emulsifiable concentrate according to any one of claims 1 to 8, comprising:

12. 12. A fungicidal emulsifiable concentrate according to claim 11, wherein the weight ratio of c(i):c(ii):c(iii) is 2:2:

1.

13. 12. A fungicidal emulsifiable concentrate according to claim 11, wherein the weight ratio of c(i):c(ii):c(iii):c(iv) is 3:3:1:

3.

14. (a) the fungicide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide; (b)(i) dipropylene glycol dibenzoate; (b)(ii) dimethyl lactamide, (c)(i) condensation products of castor oil and ethylene oxide; (c)(ii) calcium dodecylbenzenesulfonate; (c)(iii) copolymer butanol PO / EO, and (d) Silicone antifoaming agent A fungicidal emulsifiable concentrate according to any one of claims 1 to 7, comprising:

15. (a)(i) the fungicide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide; (a)(ii) prothioconazole, (b)(i) dipropylene glycol dibenzoate; (b)(ii) dimethyl lactamide, (c)(i) condensation products of castor oil and ethylene oxide; (c)(ii) calcium dodecylbenzenesulfonate; (c)(iii) copolymer butanol PO / EO, and (d) Silicone antifoaming agent 11. A fungicidal emulsifiable concentrate according to claim 9 or 10, comprising:

16. 16. A fungicidal emulsifiable concentrate according to claim 14 or 15, wherein the weight ratio of c(i):c(ii):c(iii) is 2:2:

1.

17. A fungicidal emulsifiable concentrate according to any one of claims 14 to 16, wherein the weight ratio of (b)(i):(b)(ii) is from 1.1:1 to 3:2, inclusive.

18. A fungicidal emulsion comprising a fungicidal emulsifiable concentrate according to any one of claims 1 to 17 diluted with an agrochemically acceptable aqueous diluent.

19. Use of a fungicidal emulsifiable concentrate according to any one of claims 1 to 17 or a fungicidal emulsion according to claim 18 for controlling fungal pathogens in crops of useful plants.

20. 18. A method for making a fungicidal emulsion concentrate according to any one of claims 1 to 17, comprising combining 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide, at least one solvent selected from the group consisting of dipropylene glycol dibenzoate, methyl benzoate acetophenone, dimethyl lactamide and gamma butyrolactone, the anionic surfactant calcium dodecylbenzenesulfonate, and at least two nonionic surfactants.

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