FORMULATION

Abstract

This invention relates to an emulsion comprising (i) an aqueous phase comprising an agrochemical A; and (ii) an oily phase comprising an agrochemical B; wherein either phase (i) is dispersed in phase (ii); or phase (ii) is dispersed in phase (i); agrochemical A is selected from mepiquat salts and chlormequat salts and mixtures of such salts; agrochemical B is trinexapac-ethyl; provided that the emulsion is not a microemulsion. It also relates to such an emulsion being a prepared mixture emulsion; to the use of such an emulsion for regulating plant growth; and to the use of such an emulsion for preventing and / or reducing lodging in crops.

Description

FORMULATION Field of Invention This invention relates to an emulsion comprising (i) an aqueous phase comprising an agrochemical product A; and (ii) an oily phase comprising an agrochemical product B; where either of the two phases (i) is dispersed in phase (ii); or phase (ii) is dispersed in phase (i); agrochemical A is selected from mepiquat salts and chlormequat salts and mixtures of such salts; agrochemical B is trinexapac-ethyl; provided that the emulsion is not a microemulsion. It also refers to such an emulsion being a prepared mixture emulsion; to the use of such an emulsion for regulating plant growth; and to the use of such an emulsion for preventing and / or reducing lodging of crop plants. Background of the Invention Document WO2015 / 075646A1 describes a prepared mixture microemulsion comprising trinexapac-ethyl and chlormequat chloride. However, it has been found that in such microemulsions, trinexapac-ethyl exhibits poor chemical stability and can decompose significantly during storage tests; the expert faces CQtoRnn / ίZΠZ / Β / YΙΛΙ Ref. 319903 with the problem of providing alternative formulations with improved chemical stability. Surprisingly, it has now been discovered that certain emulsions (that are not microemulsions) exhibit dramatically improved chemical stability of trinexapac-ethyl. Detailed Description of the Invention Therefore, the present invention provides an emulsion comprising (i) an aqueous phase comprising an agrochemical A; and (ii) an oil phase comprising an agrochemical B; where phase (i) is dispersed in phase (ii); or phase (ii) is dispersed in phase (i); agrochemical product A is selected from mepiquat salts and chlormequat salts and mixtures of such salts; Agrochemical product B is trinexapac-ethyl; provided that the emulsion is not a microemulsion. The emulsion can be stabilized by a soluble emulsifier; by solid particles; or by a combination of soluble emulsifier and solid particles. When phase (i) is dispersed in phase (ii) the emulsion is a water-in-oil emulsion (EO); when phase (ii) is dispersed in phase (i) the emulsion is an oil-in-water emulsion (EW). CQhGnn / 17Π7 / E / YILI Appropriately, phase (ii) is dispersed in phase (i); the emulsion is an oil-in-water (EW) emulsion. Preferably, an agrochemical product A of mepiquat chloride and chlormequat chloride is selected; more preferably, it is mepiquat chloride. Agrochemical product B is trinexapac-ethyl. An emulsion is a dispersion of one liquid in a second, continuous liquid phase, where the two liquids involved are essentially immiscible or have limited mutual miscibility. To form an emulsion, the two immiscible phases are mixed while supplying enough energy to cause one phase to break down into droplets dispersed in the second phase. The energy input can take different forms, such as agitation, ultrasound, or repeated forced flow through narrow orifices. The basic factor in the stability or instability of an emulsion is the degree of interfacial tension (i.e., free energy) between the droplets of the dispersed liquid and the other continuous liquid phase. In comparison, a microemulsion is a thermodynamically stable isotropic liquid mixture of an immiscible organic solution in water, water and surfactant, where the microemulsion is formed spontaneously by simply mixing the components (document WO2015 / 075646A1). Due to less favorable interfacial tension, oil-in-water (EW) and water-in-oil (EO) emulsions are thermodynamically unstable and will coalesce over time, resulting in phase separation. To retard emulsion droplet coalescence, the droplets can be stabilized by adding emulsifiers. These emulsifiers can be surfactants, polymers, or solid particles that adsorb onto the liquid / liquid interface. Emulsifiers reduce the interfacial tension between the phases, facilitating emulsion droplet formation. They also form a physical barrier that prevents the emulsion droplets from coalescing. Colloidal solids can stabilize dispersed emulsion droplets by adsorbing onto the liquid-liquid interface (i.e., in the present invention, they may further comprise solid particles at the interface between phase (i) and phase (ii)). Such emulsions are Pickering emulsions. The colloidal solids must be small enough to coat the surface of the emulsion droplets. The colloidal solids must have sufficient affinity for the liquids that form both the dispersed and continuous phases so that they are able to adsorb onto the liquid-liquid interface and thereby stabilize the emulsion. A wide variety of solid materials can be used as colloidal stabilizers for the Pickering emulsions of the present invention, including carbon black, oxides of CQhAnn / ίZРZ / B / YILI metals, metal hydroxides, metal carbonates, metal sulfates, polymers that are insoluble in any of the components present in the formulation, silica, and clays. Clay particles may be crosslinked. Specific examples of colloidal solids include zinc oxide, iron oxide, copper oxide, titanium oxide, aluminum oxide, calcium carbonate, precipitated silica and combustion silica, natural and synthetic clays such as attapulqite, kaolinite, and Laponite®, as well as mixtures thereof. Colloidal solids may be modified on the surface; for example, combustion or precipitated silica may be modified by the presence of dimethyldichlorosilane, hexadecylsilane, or aluminum oxide, or by alkane decoration. Pickering emulsions may also include a deflocculant (such as Sokalan® PA 30CL). Crosslinked Pickering emulsions may also include retention aids (such as Pluronic® 6400). The polymers suitable for use as stabilizers in the present invention include polymeric fibers, which have been modified to impart surfactant properties to the fibers. Surfactants are compounds that reduce the surface tension of water. Examples of surfactants include ionic surfactants (anionic, cationic, or amphoteric) and nonionic surfactants. Surfactants can also be used as emulsifiers. Emulsions according to the invention typically comprise at least one surfactant (one, two, three, or more surfactants). Suitable ionic surfactants are alkali, alkaline earth and ammonium salts of aromatic sulfonic acids, for example of lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, dibutylnaphthalenesulfonic acid or fatty acids, alkyl or alkylaryl sulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa, hepta and octadecanols, and of fatty alcohol glycol ethers, sulfonated naphthalene condensates and its derivatives with formaldehyde, naphthalene condensates or of naphthalenesulfonic acids with phenol and formaldehyde, polycarboxylates or phosphate esters of alkoxylated alcohols. Suitable nonionic surfactants are polyoxyethylene octyl phenol ethers, alkoxylated alcohols such as isooctyl, octyl or nonylphenol ethoxylate, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol acetate polyglycol ether, sorbitol esters, residual aqueous lignin-sulfite solution, and also proteins, denatured proteins, polysaccharides (by CQbRnn / Lznz / E / YiAi (e.g., methylcellulose), hydrophobically modified starches, polyvinyl alcohols (e.g., Mowiol®), polyalkoxylates, polyvinylamines, polyethyleneimines, polyvinylpyrrolidones and their copolymers or block polymers. The preferred nonionic surfactants are polyvinyl alcohols. Polyvinyl alcohols prepared by saponification of polyvinyl acetate are particularly preferred, with a degree of saponification of at least 60%, but preferably 80–95%. Suitable products of this type are those marketed under the registered trademark Mowiol®. A particularly preferred polyvinyl alcohol is Mowiol® 4-88, with a molecular weight of approximately 31,000 daltons and a degree of saponification of 86.7–88.7 mol%. The oil phase comprises a liquid that does not substantially dissolve in or become miscible with water. Examples of oils suitable for use as the oil phase include, but are not limited to, methylated vegetable oils, aromatic oils, and hydrocarbon solvents (for example, aromatics or aliphatic esters). The agrochemical product B may itself be an oil, or it may be soluble in a hydrophobic solvent to form an oil phase, or it may be dispersed in the oil phase, or it may be adsorbed to the oil-aqueous phase interface of the present invention. An emulsion of the present invention optionally contains an Ostwald ripening inhibitor. Ostwald ripening inhibitors suitable for use in the present invention are soluble or miscible in the dispersed phase, or may themselves serve as the dispersed phase containing at least one active ingredient, which is substantially insoluble in the continuous phase, or have the active ingredient adsorbed to the liquid-liquid interface between the continuous and dispersed phases as a colloidal solid. The Ostwald ripening inhibitors must have a greater affinity for the dispersed phase than for the continuous phase. Ostwald ripening inhibitors suitable for oil-in-water emulsions include solvents such as vegetable oils, methylated vegetable oils, mineral oils, liquid hydrocarbon solvents, and polymers or oligomers with a molecular weight of at least 200 daltons, preferably at least 400 daltons.Examples of suitable polymers are polymers and copolymers of styrene, alkyl styrenes, isoprenes, butenes, butadienes, acrylonitriles, alkyl acrylates, alkyl methacrylates, vinyl chlorides, vinylidene chlorides, and vinyl esters. Polymeric co-stabilizers can be used in combination with colloidal solids to stabilize emulsion droplets. The polymeric co-stabilizers useful in the present invention are water-soluble polymers of a molecular weight sufficient to be soluble in CQhAnn / Lznz / E / YiAi polymers exhibit reduced solubility under certain pH, temperature, or electrolyte concentration conditions, and this reduction is sufficient to cause flocculation of the solid colloidal particles. The polymer's solubility can be controlled by pH-sensitive groups, which may include, but are not limited to, polyethylene oxides, or by electrolyte-dependent groups, where the polymer becomes less soluble at high electrolyte strengths. These electrolyte-dependent groups may include, but are not limited to, polyacrylic acids and polyethylenes. Representative polymeric co-stabilizers include, but are not limited to, hydroxypropyl cellulose, hydroxymethylpropyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, acrylic graft polymers, and polyvinyl alcohols. Typically, agrochemical B will be present in the emulsion at 25g / l to 150g / l, suitably 33g / l to 100g / l. Typically, agrochemical product A will be present in the emulsion at 200g / l to 600g / l, or appropriately 225g / l to 500g / l. Appropriately, trinexapac-ethyl is present in the emulsion at 50g / l to 100g / l while mepiquat chloride is present in the emulsion at 225g / l to 450g / l. Appropriately, trinexapac-ethyl is present in the CQbAnn / ίZΖΠZ / Β / YΙΛΙ emulsion a of 33g / l to 50g / l while chlormequat chloride is present in emulsion a of 400 to 600g / l (preferably 500g / l). Generally, any agrochemically active ingredient (agrochemical A or agrochemical B) shall be present at a concentration of approximately 0.000001% to approximately 90% w / w; preferably from approximately 0.001% to approximately 90% w / w. The agrochemical compositions of the invention may be presented in the form of a ready-to-use formulation or in the form of a concentrate suitable for further dilution by the end user, and the concentration of the agrochemical and the combination of (i) plus (ii) shall be adjusted accordingly. In concentrated form, the compositions of the invention generally contain, independently, an agrochemical A and an agrochemical B, each at 1% to 90% w / w, more preferably 2% to 75% w / w, and even more preferably 3% to 50% w / w, of the total composition. The compositions of the present invention relate to concentrates designed to be added to a farmer's spray tank and can be applied directly without further dilution. The present invention also relates to compositions produced in a farmer's spray tank when the concentrate is mixed with water in the spray tank. CQhAnn / Lznz / E / YiAi The compositions of the present invention may include other ingredients such as a viscosity modifier, an antifoaming agent, an antibacterial agent, a colorant or a perfume, etc. A composition of the present invention may be presented in the form of a premixed emulsion formulation, packaged within a single container and ready for use directly after dilution. The invention also contemplates capsule suspension formulations prepared by emulsion polymerization. The compositions of the present invention can be used in a method for regulating plant growth comprising applying an effective amount of the composition to one or more plants. The compositions of the present invention can be used in a method for preventing and / or reducing lodging of crop plants comprising applying an effective amount of the composition to one or more plants. The compositions of the present invention can be used in a method for improving the root system comprising applying an effective amount of the composition to one or more plants. The above methods may involve one or more plants that are rapeseed or monocotyledonous plants, preferably CQtoRnn / ίZРZ / В / YILI selected from cereals, rice, corn and sugar cane; more preferably the plants are cereal plants. The above methods may involve an effective amount of the composition applied at a rate of 0.5 to 5 l / ha, more appropriately 1 to 3 l / ha. The following examples demonstrate the improved chemical stability associated with emulsions according to the present invention. Unless otherwise stated, all concentrations and ratios are by weight. Example 1 This example provides emulsions, according to the present invention, comprising trinexapac-ethyl (at a concentration of 100 g / 1) and chlormequat chloride (at a concentration of 450 g / 1)). Emulsion A: A 100 ml container was filled with chlormequat chloride (36.7 g) and water (27.4 g). The mixture was stirred with a paddle stirrer until the chlormequat chloride was completely dissolved. Imerys® RLO 7645 clay (8.0 g) was added and mixed with a paddle stirrer. A 50% w / w solution of trinexapac-ethyl in Solvesso® 200ND (16.0 g) was mixed using a Silverson® high-shear mixer (5000 rpm) while maintaining the temperature below 25 °C. A homogeneous emulsion had formed within 10 minutes. Emulsion B: A 100 mL container was filled with chlormequat chloride (36.7 g) and water (27.4 g). The mixture was stirred with a paddle stirrer until the chlormequat chloride was completely dissolved. A 20% w / w solution of Mowiol® 4-88 in water (8.1 g) was added. The mixture was homogenized by stirring with a paddle stirrer. A 50% w / w solution of trinexapac-ethyl in Solvesso® 200ND (16.0 g) was mixed using a Silverson® high-shear mixer (5000 rpm) while maintaining the temperature below 25 °C. A homogeneous emulsion had formed within 10 minutes. Example 2 This example provides emulsions, according to the present invention, comprising trinexapac-ethyl (at a concentration of 100 g / 1) and mepiquat chloride (at a concentration of 450 g / 1) ). Emulsion C: A 380 ml container was filled with mepiquat chloride (114.2 g) and water (60.8 g). The mixture was stirred with a paddle stirrer until the mepiquat chloride was completely dissolved. Imerys® RLO 7645 clay (25.4 g) was mixed in using a paddle stirrer. The clay was dispersed for 5 minutes using a Silverson® high-shear mixer (5000 rpm) while maintaining the temperature below 25°C. A 50% w / w trinexapac-ethyl solution in Solvesso®200ND (49.9 g) was added while the high-shear mixing (5000 rpm) continued. After 5 minutes, A homogeneous emulsion had formed with CQfrRnn / Lznz / E / Yii. The concentration was adjusted by adding water (15.8 g). The formulation was homogenized by stirring with a paddle stirrer for 2 hours. Emulsion D: A 250 mL container was filled with mepiquat chloride (68.9 g) and water (46.0 g). The mixture was stirred with a paddle stirrer until the mepiquat chloride was completely dissolved. A 20% w / w solution of 4-88 Mowiol® in water (15.0 g) was added, and the mixture was stirred with a paddle stirrer for 10 minutes. A 50% w / w solution of trinexapac-ethyl in Solvesso® 200ND (30.1 g) was mixed using a Silverson® high-shear mixer (5000 rpm) while maintaining the temperature below 25 °C. After 10 minutes, a homogeneous emulsion had formed. Example 3 This is a comparative example. Microemulsion E: A microemulsion was prepared comprising trinexapac-ethyl (at a concentration of 2.14% w / w) and chlormequat chloride (at a concentration of 25% w / w) according to document WO2015 / 075646A1, page 18, table 1. Solution F: Trinexapac-ethyl was melted at 50 °C prior to use. A 150 ml glass bottle was filled with mepiquat chloride (28.7 g), water (6.9 g), ethanol (69.1 g), and trinexapac-ethyl (6.6 g). The bottle was left on a roller for 16 hours. During this time, a clear, homogeneous solution formed. CQtoRnn / ίZΠZ / Β / YΙΛΙ Solution G: Trinexapac-ethyl was melted at 50 °C prior to use. A 150 ml glass bottle was filled with mepiquat chloride (28.7 g), water (6.4 g), 1,2-propylene glycol (91.0 g), and trinexapac-ethyl (6.6 g). The bottle was left on a roller for 16 hours. During this time, a clear, homogeneous solution formed. Example 4 This example illustrates the stability of trinexapac-ethyl in the presence of chlormequat chloride. The comparative emulsions and microemulsions according to the previous examples were subjected to accelerated storage tests (2 weeks at 54°C) through which the chemical stability of trinexapac-ethyl was measured using standard analytical techniques; the concentration of The remaining trinexapac-ethyl CQhRnn / 17P7 / E / YILI compared to the reference sample stored at -18°C is provided, as a percentage, in Table 1 below, where the g / 1 concentrations of trinexapac-ethyl [TXP] plus chlormequat chloride [CCC] are provided: Table 1 Formulation Mixture Component TXP::CCC (g / i) Formulation Type TXP after 2 weeks at 54 °CE Chlormequat Chloride 20:235 Microemulsion 75% A Chlormequat Chloride 100::450 Pickering Emulsion 99% B Chlormequat Chloride 100::450 Emulsion 99% Trinexapac-ethyl was significantly more stable within the emulsion formulations according to the present invention than within a microemulsion. Example 5 This example illustrates the stability of trinexapac-ethyl in the presence of mepiquat chloride. The emulsions and comparator solutions according to the above examples were subjected to accelerated storage tests (2 weeks at 54 °C) through which the chemical stability of trinexapac-ethyl was measured using standard analytical techniques; the concentration of trinexapac-ethyl remaining compared to the reference sample stored at -18 °C is provided, as a percentage, in Table 2 below, where the g / 1 concentrations of trinexapac-ethyl [TXP] plus mepiquat chloride [MPQ] are provided: CQhAnn / Lznz / E / YiAi Table 2 Formulation Mixture Component TXP::MPQ (g / 1) Formulation Type TXP after 2 weeks at 54 °CF Mepiquat Chloride 50::225 Solution 74% G Mepiquat Chloride 50::225 Solution 77% C Mepiquat Chloride 100::450 Pickering Emulsion 99% D Mepiquat Chloride 100::450 Emulsion 98% Trinexapac-ethyl was significantly more stable within the emulsion formulations according to the present invention than within solutions. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

Having described the invention as above, the following claims are claimed as property:

1. An emulsion characterized in that it comprises (i) an aqueous phase comprising an agrochemical product A; and (ii) an oily phase comprising an agrochemical product B; wherein phase (i) is dispersed in phase (ii); or phase (ii) is dispersed in phase (i); the agrochemical product A is selected from mepiquat salts and chlormequat salts and mixtures of such salts; the agrochemical product B is trinexapac-ethyl; provided that the emulsion is not a microemulsion.

2. An emulsion according to claim 1, characterized in that phase (ii) is dispersed in phase (i).

3. An emulsion according to claim 1 or 2, characterized in that the agrochemical product A is mepiquat chloride or chlormequat chloride.

4. A composition according to claim 1, 2 or 3, characterized in that it further comprises an emulsifier.

5. A composition according to claim 1, 2, 3 or 4, characterized in that it further comprises solid CQhAnn / ίZΖΠZΖ / Β / YΙΛΙ particles at the interface between phase (i) and phase (ii).

6. A composition according to any of claims 1 to 5, characterized in that the concentration of an agrochemical product A is 200g / l to 600g / l.

7. A composition according to any of claims 1 to 6, characterized in that the concentration of an agrochemical product B is 25g / l to 150g / l.