WO2022115930A1

WO2022115930A1 - Suspoemulsion, process for preparing a suspoemulsion, method for controlling undesired vegetation and/or pests and method for treating seeds

Info

Publication number: WO2022115930A1
Application number: PCT/BR2021/050536
Authority: WO
Inventors: Rodrigo ADAMY; Yves Luiz Bezerra COSTA; Thaynara BARBOSA
Original assignee: Sumitomo Chemical Brasil Indústria Química S.A.
Priority date: 2020-12-04
Filing date: 2021-12-03
Publication date: 2022-06-09
Also published as: CL2023001582A1; CO2023004496A2; BR102020024869A2; AR124249A1

Abstract

The present invention describes suspoemulsion compositions comprising nanoscale reverse micelles and at least two active ingredients, one of the active ingredients being immiscible in water and another insoluble in water. In addition, the present invention discloses suspoemulsion compositions that are stable, even in the absence of organic solvents. The invention is of particular use for controlling undesired pests and/or vegetation by combining different active ingredients with different physical and chemical properties.

Description

Invention Patent Descriptive Report

SUSPO-EMULSION, SUSPO-EMULSION PREPARATION PROCESS, METHOD OF CONTROL OF UNWANTED VEGETATION AND/OR PESTS AND METHOD FOR TREATMENT OF SEEDS

Field of Invention

[0001] The present invention is located in the fields of Chemistry and Agrochemistry. More specifically, the present invention describes novel suspo-emulsion compositions. Still the present invention presents the process of preparing these compositions and methods of controlling pests and unwanted plants comprising the application of said compositions.

Background of the Invention

[0002] Suspo-emulsions are compositions that combine technologies of concentrated suspension and concentrated aqueous emulsion and, in general, have at least three phases, being formed by the combination of a continuous phase, containing one or more active components, with a discontinuous phase. which may also contain one or more active components, and a solid phase dispersed in at least one of the phases mentioned above.

[0003] The use of suspo-emulsions allows the combination of actives of different physicochemical properties, unstable or chemically incompatible, creating significant difficulties for the formulator. These difficulties are usually overcome through the use of organic solvents and/or low concentrations of actives.

[0004] The use of organic solvents in suspo-emulsions generates residues that, without treatment, can affect the environment and human health. Therefore, they are unwanted and discourage large-scale production of suspo-emulsions by companies, such as agrochemical companies, especially when green chemistry practices and sustainable production policies are increasingly encouraged and valued. [0005] In the search for the state of the art in scientific and patent literature, the following documents were found that deal with the subject:

[0006] Document CA2605797A1 discloses compositions in the form of water-in-oil suspo-emulsions, comprising at least one active ingredient immiscible in the oil phase and at least one active ingredient dispersed in the aqueous phase, in addition to surfactants and other adjuvants and additives.

[0007] CN107593725 discloses herbicidal compositions comprising metolachlor and, optionally, flumioxazin, in one embodiment, these compositions would be oil-in-water suspo-emulsions and/or water-in-oil emulsions.

[0008] Document JP1994092801 discloses an aqueous suspo-emulsion (oil in water) comprising two water-insoluble actives, one that is liquid and the other solid at room temperature.

[0009] WO 1999/045780 discloses concentrated herbicidal compositions comprising an aqueous phase, an oil phase and active ingredients dispersed in the aqueous phase. In one embodiment, the compositions are aqueous suspo-emulsions.

[0010] Thus, from what can be seen from the researched literature, no documents were found anticipating or suggesting the teachings of the present invention, so that the solution proposed here has novelty and inventive step compared to the state of the art.

Summary of the Invention

[0011] The present invention solves the problems of the state of the art from the development of new suspo-emulsion compositions, with reverse micelles of diameter on the nanometer scale, which remain stable even in the absence of solvents. Even so, the suspo-emulsions of the present invention maintain their stability and bioefficacy characteristics even with high concentrations of active ingredients in their composition.

[0012] In a first aspect, the present invention presents a emulsion comprising: a) from 50% to 95% by mass of a continuous, water-immiscible phase, comprising: i) at least one water-immiscible active ingredient, and ii) at least one water-in-oil emulsifier with HLB in the range of 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

[0013] In a second aspect, the present invention presents a process for preparing a suspo-emulsion comprising the steps: a) Preparing a water-in-oil emulsion comprising: i) Mixing 50% to 95% by mass of at least one ingredient water-immiscible active with 5% to 40% by mass of at least one water-in-oil emulsifier with HLB in the range of 3 to 9; ii) Add in a high shear mixer 50% to 70% by mass of the mixture obtained in i) and from 35% to 50% by mass of water, and mix until obtaining a water-in-oil emulsion in which 90% of said micelles reverse is in the range between 0.1 pm to 40 pm; b) Preparing an aqueous suspension comprising 50% to 80% by mass of dispersed solid particles of a water-insoluble active ingredient; c) Mix 50% to 95% by mass of the emulsion obtained in a) with 5% to 50% by mass of the suspension obtained in b).

[0014] In a third aspect, the present invention presents a method of controlling unwanted vegetation and/or pests comprising the application of a suspo-emulsion comprising: a) from 50% to 95% by mass of a continuous, water-immiscible phase, comprising: i) at least one water-immiscible active ingredient, and ii) at least one water-in-oil emulsifier with HLB in the range 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

[0015] In a fourth aspect, the present invention features a method for treating seeds comprising applying a suspo-emulsion composition comprising: a) from 50% to 95% by mass of a continuous, water-immiscible phase, comprising : i) at least one water-immiscible active ingredient, and ii) at least one water-in-oil emulsifier with HLB in the range of 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

[0016] These and other objects of the invention will be immediately appreciated by those skilled in the art and will be described in detail below. Detailed Description of the Invention

[0017] Faced with formulations such as solution concentrates, emulsions, suspensions, foams, powders and water-dispersible granules, suspo-emulsions have several advantages, mainly, suspo-emulsions allow the combination of actives with different physicochemical properties, such as actives with different solubilities in water. This advantage is of great interest for the control of plants or weeds.

[0018] Plants or weeds are undesirable vegetations that arise in an agricultural space, competing for nutrients and space with the vegetation of interest, for example, soybean, rice, cotton, etc. The control of these weeds can be accomplished by the use of herbicidal compositions, however, the continuous use of herbicidal compositions can lead to the emergence of resistant plants, being a problem for the agriculture area.

[0019] Thus, compositions containing various herbicides, such as suspo-emulsions, are useful in weed control, as they allow the combination of actives with complementary modes of action. The combinations offer the benefit of broadening the spectrum of weed control and managing herbicide resistance that can develop in certain weeds through prolonged use.

[0020] Despite the advantage of combining different actives, suspo-emulsions are still not widely used as herbicide compositions. This is mainly due to the use of organic solvents to stabilize suspo-emulsions, and the low stability of water-in-oil suspo-emulsions without the presence of these organic solvents. Furthermore, poorly soluble and/or immiscible compounds in water have low concentrations in currently known aqueous suspo-emulsions.

[0021] The present invention solves this and other problems of the prior art from stable suspo-emulsion compositions, stable even with the elimination of waste (organic solvents), and with high concentrations of actives, including water-immiscible and water-insoluble actives.

[0022] In a first object, the present invention presents a suspo-emulsion composition comprising: a) from 50% to 95% by mass of a continuous phase, immiscible in water, comprising: i) at least one active ingredient immiscible in water, and ii) at least one water-in-oil emulsifier with HLB in the range of 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

[0023] In one embodiment, the suspo-emulsion comprises from 70% to 95% by mass of the water-immiscible continuous phase. In one embodiment, the suspo-emulsion comprises from 80% to 95% of the water-immiscible continuous phase. The continuous water-immiscible phase uses water-in-oil emulsifiers with HLB from 3 to 9, preferably from 3 to 7, mixed with a water-immiscible active ingredient, that is, a liquid active ingredient at room temperature.

[0024] In one embodiment, the continuous phase additionally comprises at least one emulsifier with HLB in the range of 12 to 18.

[0025] In one embodiment, the suspo-emulsion comprises from 5% to 30% by mass of the aqueous discontinuous phase. In one embodiment, the suspo-emulsion comprises from 5% to 20% of the water-immiscible continuous phase. The aqueous discontinuous phase presents reverse micelles with reduced diameters being surprisingly stable even with the use of a high amount of active ingredients.

[0026] In one embodiment, the water-in-oil emulsion used in the preparation of the suspo-emulsion comprises from 50% to 70% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 69.5% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 69% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 68.5% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 68% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 67.5% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 67% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 66.5% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 66% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 65.5% by weight of the oil phase. In one embodiment, the water-in-oil emulsion comprises from 50% to 65% by weight of the oil phase.

[0027] In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 pm and 45 pm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 40 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 35 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.1 µm and 30 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 25 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 20 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have diameter at range between 0.1 um and 18 um. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.1 µm and 15 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.1 µm and 13 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.1 µm and 12.5 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 12 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 11 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.1 µm and 10 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 µm and 8 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.5 µm and 8 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 0.8 µm and 8 µm. In one embodiment, at least 90% of the discontinuous phase reverse micelles have a diameter in the range between 1 pm and 8 pm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 1 pm and 6 pm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.5 µm and 6 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 0.8 µm and 6 µm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 1 pm and 5 pm. In one embodiment, at least 90% of the discontinuous phase reversed micelles have a diameter in the range between 1 µm and 2.5 µm.

[0028] In one embodiment, at least 50% of the discontinuous phase reverse micelles have a diameter in the range between 0.1 pm and 10 pm. In one embodiment, at least 50% of the discontinuous phase reverse micelles have diameter in the range between 0.1 pm and 8 pm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 0.5 µm and 8 µm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 0.8 µm and 8 µm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 1 pm and 8 pm. In one embodiment, at least 50% of the discontinuous phase reverse micelles have a diameter in the range between 1 pm and 6 pm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 0.5 µm and 6 µm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 0.8 µm and 6 µm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 1 pm and 5 pm. In one embodiment, at least 50% of the discontinuous phase reversed micelles have a diameter in the range between 1 µm and 2.5 µm.

[0029] In one embodiment, the active ingredient is an agrochemical selected from the group of pesticide, insecticide, fungicide, herbicide, acaricide, molluscicide, nematicide and/or plant growth modifying agent. In one embodiment, the composition additionally comprises a water-soluble active ingredient.

[0030] In one embodiment, the continuous phase comprises from 0.5 g/L to 800 g/L of water-immiscible active ingredient. In one embodiment, the continuous phase comprises from 300 g/L to 800 g/L of water-immiscible active ingredient.

[0031] In one embodiment, the water-immiscible active ingredient is a protein synthase inhibitor and/or very long-chain fatty acid inhibitor herbicide, suppressing cell growth and preventing protein synthesis, comprising acetamides, chloroacetamides , oxyacetamides, tetrazolinones, among others. In one embodiment, the water-immiscible active ingredient is a herbicide comprising acetochlor, alachlor, butachlor, butenachlor, delachlor, diethyl, dimethachlor, dimethenamid, dimethenamid-P, mephenacet, metazochlor, metolachlor, napropamide, pretilachlor, pronamide, propachlor, propisochlor, prinachloryl, terbuchlor, tenylchlor, indaphane, cafenstrol, fentrazamide, pyroxasulfone, phenoxasulfone, napropamide, anilophos, flufenacet and their salts, esters, isomers, stereoisomers and combinations thereof. In one embodiment, the water-immiscible active ingredient is S-metolachlor.

[0032] In one embodiment, the aqueous discontinuous phase comprises from 10 g/L to 400 g/L of dispersed solid particles of a water-insoluble active ingredient. In one embodiment, the aqueous discontinuous phase comprises from 30 g/L to 200 g/L of dispersed solid particles of a water-insoluble active ingredient.

[0033] In one embodiment the water-insoluble active ingredient is a herbicide from the group of phenylphthalimides, comprising cinidon-ethyl, flumezin, flumiclorac, flumioxazin and flumipropyn. In one embodiment, the water-insoluble active ingredient is flumioxazin.

[0034] In one embodiment, the water-insoluble active ingredient is a herbicide that inhibits protoporphyrinogen oxidase, comprising fomesafen, lactofen and oxyfluorfen, flumioxazin, oxadiazon, carfentrazone, flumiclorac-pentyl, indaziflam, tebuthiuron, sulfentrazone, diuron, linuron , sulfometuron, chlorsulfuron, metsulfuron, chlorimuron, atrazine, simazine, quizalofop, butroxydim, nicosulfuron, primsulfuron, bensulfuron, ametryn, pendimethalin, isoproturon, chlortoluron, diflufenicanafop, mesotrione, aclonifen, fluorochloriduronmethyl, oxyfenorfol, oxyfenfluorfol.

[0035] In one embodiment, the ratio of water-immiscible active ingredient to water-insoluble active ingredient is from 12:1 to 1:1. In one embodiment, the ratio is 12:1, 10:1, 8:1, 5:1, 2:1, or 1:1.

[0036] In one embodiment, the emulsifier is non-ionic polymeric or phosphate ester emulsifier. In one embodiment the emulsifier is selected from the group consisting of polyethylene glycol block copolymer and 12-hydroxystearic acid, polyalkylene glycol ether, ethoxylated propoxylated polyarylphenol and combinations thereof.

[0037] By way of example, and not exhaustively, said emulsifiers defined above may be selected among Dispersogen™ LFH, Dispersogen™ LFS, Emulsogen® 3475, Emulsogen® 3510, Emulsogen® ED 236, Emulsogen® EL 200, Emulsogen® EL 300 LM, Emulsogen® EL 360, Emulsogen® EL 400, Emulsogen® EL 540, Emulsogen® ELO 200, Emulsogen® EP 4901 , Emulsogen® M, Emulsogen® TS 100, Emulsogen® TS 160, Emulsogen® TS 200, Emulsogen® TS 290, Emulsogen® TS 540, Emulsogen® TS 600, Emulsogen® V 1816, Genagen™ OS 070, Genapol® C 050, Genapol® C 070, Genapol® C 100, Genapol® C 120, Genapol® C 200, Genapol® C ED 1616, Genapol® ID 060, Genapol® ID 100, Genapol® LA 030, Genapol® LA 070, Genapol® LA 080, Genapol® O 100, Genapol® O 109, Genapol® O 150, Genapol® O 200, Genapol® PF 10, Genapol® PF 20, Genapol® PF 40, Genapol® PF 80, Genapol® PN 30, Genapol® T 150, Genapol® UD 050, Genapol® UD 079, Genapol® UD 080, Genapol® X 050, Genapol® X 060, Atlox™ CS100A, Atlox 4916, Zephrym™ PD2206, Atlox™ 4 914, Etocas™ 5, Span™ 40, Span™ 60, Span™ 65, Span™ 80, Span™ 85, Synperonic™ A2, Synperonic™ PE/L 101 , Synperonic™ PE/L 61 and/or Atlox™ 4912.

[0038] In one embodiment, the suspo-emulsion comprises at least one defoamer. In one embodiment, at least one defoamer is selected from the group consisting of ACP-1920, AFE-1520 ANTIFOAM EMULSION, AFE-300 ANTIFOAM EMULSION, DOWSIL™ AFE-3101, SAG 1572, XIAMETER™ ACP-1400, XIAMETER™ AFE-0050 , XIAMETER™ AFE-1430, XIAMETER™ AFE-1520, Silcolapse RG 21, SILFOAM S.R.E and SAG1571 [0039] In one embodiment, the suspo-emulsion comprises at least one antifreeze. In one embodiment, the antifreeze is selected from the group consisting of propylene glycol, diethylene glycol, monoethylene glycol and glycerin.

[0040] In one embodiment, the suspo-emulsion comprises at least one thickener. In one embodiment, the thickener concentration is from 0.1 g/L to 2 g/L. In one embodiment, the thickener concentration is from 0.6 g/L to 1.2 g/L. Non-exhaustive examples of thickeners that can be used in the present application include Kelzam AP, Kelzam S Plus and Rhodopol 23.

[0041] Additionally, the suspo-emulsions are optionally obtained by a procedure free of organic residues and which generally comprises three steps.

[0042] The first step consists of preparing a phase composed of water-in-oil emulsifiers and one or more water-immiscible active ingredients, this step being the main responsible for the absence of process residues, since it does not require the use of organic solvents. for mixing the active compound with the emulsifiers.

[0043] The second stage of the developed process is the formation of a water-in-oil emulsion, comprising the mixture of the solution of the first stage with water. In addition, the step consists of the use of a high shear mixing equipment, one of those responsible for reducing the diameters of the reverse micelles formed and, consequently, increasing the stability of the emulsion.

[0044] Finally, the third step consists of preparing a concentrated aqueous suspension with one or more insoluble solid active ingredients. The suspo-emulsion is finished by mixing the emulsion from the second stage with the aqueous suspension.

[0045] In a second object, the present invention presents a process for preparing a suspo-emulsion comprising the steps: a) Preparing a water-in-oil emulsion comprising: i) Mixing 50% to 95% by mass of at least one ingredient water-immiscible active with 5% to 40% by mass of at least one water-in-oil emulsifier with HLB in the range of 3 to 9; ii) Add in a high shear mixer 50% until 70% by mass of the mixture obtained in i) and from 35% to 50% by mass of water, and mix until obtaining a water-in-oil emulsion in which 90% of said reverse micelles are in the range between 0.1 gm to 40 gm ; b) Preparing an aqueous suspension comprising 50% to 80% by mass of dispersed solid particles of a water-insoluble active ingredient; c) Mix 50% to 95% by mass of the emulsion obtained in a) with 5% to 50% by mass of the suspension obtained in b).

[0046] In one embodiment, in step a) i) 60% to 95% by mass of at least one water-immiscible active ingredient is mixed. In one embodiment, 80% to 95% by weight of at least one water-immiscible active ingredient is mixed.

[0047] In one embodiment, in step a) i) 5% to 20% by mass of at least one water-in-oil emulsifier is mixed with HLB in the range of 3 to 9.

[0048] In one embodiment, in step a) ii) 50 to 70% by mass of the mixture obtained in i) is added to the high shear mixer. In one embodiment, 50 to 69.5% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 69% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 68.5% by weight of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 68% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 67.5% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 67% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 66.5% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 66% by mass of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 65.5% by weight of the mixture obtained in i) is added to the mixer. In one embodiment, 50 to 65% by mass of the mixture is added to the mixer. obtained in i).

[0049] In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion (mixture obtained in "i") have a diameter in the range between 0.1 pm and 35 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 30 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 25 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 20 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 18 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 15 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 13 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 12.5 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 12 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 11 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 10 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 8 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.5 pm and 8 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.8 pm and 8 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 1 pm and 8 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have diameter in the range between 1 µm and 6 µm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.5 pm and 6 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.8 pm and 6 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 1 pm and 5 pm. In one embodiment, at least 90% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 1 pm and 2.5 pm.

[0050] In one embodiment, at least 50% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 8 pm. In one embodiment, at least 50% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 6 pm. In one embodiment, at least 50% of the reverse micelles in the water-in-oil emulsion have a diameter in the range between 0.1 pm and 5 pm. In one embodiment, at least 50% of the reverse micelles in the water-in-oil emulsion have a diameter in the range of 0.1 µm to 2.5 µm.

[0051] In one embodiment, step a) ii) takes place for 5 to 30 minutes at a rotation of 5000 to 15000 rpm. In one embodiment, step a) ii) takes place for 5 to 15 minutes. In one embodiment, the addition of the oil phase to the aqueous phase is carried out at the rate of 5 to 20 ml per second (ml/sec). In one embodiment, the addition of the oil phase to the aqueous phase is carried out at the rate of 10 to 15 mL/sec.

[0052] In one embodiment, the aqueous suspension prepared in step b) comprises from 50% to 70% by mass of dispersed solid particles of a water-insoluble active ingredient.

[0053] In one embodiment, in step c) 70% to 95% by mass of the emulsion obtained in a) is mixed with 5% to 30% by mass of the suspension obtained in b). In one embodiment, in step c) 80% to 95% by mass of the emulsion obtained in a) is mixed with 5% to 20% by mass of the suspension obtained in b). [0054] In a third object the present invention presents a method of controlling unwanted vegetation and/or pests comprising the application of a suspo-emulsion comprising: a) from 50% to 95% by mass of a continuous phase, immiscible in water comprising: i) at least one water-immiscible active ingredient, and ii) at least one water-in-oil emulsifier having HLB in the range of 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

[0055] In one embodiment, the composition is diluted with water prior to the application step.

[0056] In one embodiment, the control method further comprises applying a diverse agrochemical composition before or after the application of said suspo-emulsion.

[0057] In one embodiment, pests are plants or weeds that arise in an agricultural space, competing for nutrients and space with the vegetation of interest, e.g. soybeans, rice, canola, cotton, etc. In one embodiment, the active ingredients are herbicides and are useful for weed control.

[0058] In one embodiment the unwanted vegetation is at least one selected from the group consisting of Amaranthus sp, Brassica sp, Digitaria sp, Elusine sp, Echinochloa sp and Chlorís sp. In one embodiment, the unwanted vegetation is at least one selected from the group consisting of Amaranthus hybridus, Amaranthus palmeri, Brassica rapa, Digitaria sanguinalis, Digitaria insularis, Elusine indica, Echinochloa colona and Ch loris sp. In one embodiment, the water-immiscible active ingredient is for pest control in corn, soybean, peanut, sugarcane, cotton and fallow crops.

[0059] In one embodiment, the step of applying the composition is performed pre-planting, pre-emergence or post-emergence.

[0060] In one embodiment, the application of the herbicidal composition is carried out by backpack sprayer, tractor or plane. In one embodiment, the application of the herbicidal composition is carried out at a dose of 40 to 100 L/ha. In one embodiment, the dose is from 50 L/ha to 80 L/ha.

[0061] In a fourth object, the present invention presents a method for treating seeds comprising the application of a suspo-emulsion comprising: a) from 50% to 95% by mass of a continuous phase, immiscible in water, comprising: i ) at least one water-immiscible active ingredient, and ii) at least one water-in-oil emulsifier with HLB in the range of 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

[0062] In the context of the present patent application, the present terms are defined:

[0063] Suspo-emulsion: As used herein, the term "suspo-emulsion" refers to a mixture composed of at least three phases, comprising a continuous phase, a discontinuous phase, and a dispersed solid phase. still, one suspo-emulsion may comprise water-insoluble active ingredients, wherein at least one of these active ingredients is in the form of a suspension (dispersed solid phase) and at least one other active is present in the form of an emulsion.

[0064] Reverse micelles: As used herein, the term "reverse micelles" refers to spontaneous and reversible formations of globular aggregates of amphiphilic molecules in apolar solution.

[0065] Water-in-oil emulsion: As used herein, the term "water-in-oil emulsion" refers to a mixture of two immiscible liquids, the internal phase being aqueous (discontinuous) and the external phase being oily (continuous).

[0066] Insoluble: As used herein, the term "insoluble" refers to the property of a solute, indicating that it is poorly soluble in a given solvent. In one embodiment, insoluble is understood to be a solute with a solubility lower than 1 g/mL, more preferably, with a solubility lower than 0.5 g/mL, at ambient temperature and pressure (25 °C and 1 atm).

[0067] Immiscible: As used herein, the term "Immiscible" refers to the inability of a mixture of liquids to spontaneously form a single, homogeneous phase. In one embodiment, a liquid with a solubility in a liquid (solvent) of less than 1 g/mL, more preferably, with a solubility of less than 0.5 g/mL, at ambient temperature and pressure is understood to be immiscible.

[0068] HLB: As used herein, the term "HLB" refers to hydrophile-lipophile balance. Reference values can be found in the literature, including, non-exhaustively, references such as MCCUTCHEON'S, Detergents. Emulsifiers. North American Edition, 2020. Also, HLB values of different molecules can be calculated, an example of how to calculate this value is defined by Griffin (Classification of surface-active agents by"HLB". J. Soc. Cosmet. Chem ., v. 1, pp. 311-326, 1949 and Calculation of HLB values of non-ionic surfactants. J. Soc. cosmetic Chem., v. 5, p. 249-256, 1954.), yet other examples of calculating HLB can be found in the literature.

[0069] Plant growth modulating agent: As used herein, the term "growth modulating agent" refers to an ingredient, or combinations of ingredients, that modulate, that is, alter, plant growth. This definition includes, but is not limited to, agents that promote plant growth, or plant sub-structures, such as roots, leaves, etc. vegetable.

[0070] In short, the present invention presents an advance over the state of the art, since it reveals formulations in the form of suspo-emulsions and a process for producing suspo-emulsions, allowing stable suspo-emulsions to be produced even without solvents (residues) and with surprisingly small diameter reverse micelles. The smaller diameter of the reverse micelles provides greater stability to the system even in the presence of high amounts of immiscible and water-insoluble actives. The invention also provides higher concentrations of active ingredients in their compositions and/or combinations of chemically incompatible or difficult to mix active ingredients, since they are spatially separated in the formulation. Furthermore, the knowledge disclosed herein provides alternatives of green processes, which allow the elimination of the use of solvents (waste), for the production of suspo-emulsions of agricultural interest.

Examples - Herbicide Suspo-emulsions

[0071] The examples shown here are intended only to exemplify one of the numerous ways to carry out the invention, however without limiting its scope.

Example 1 - Preparation of the organic phase in the absence of solvents

[0072] The preparation of the organic phase was considered as the first step for formulating a suspo-emulsion as described in the present patent application.

[0073] To a vessel, 183.93g of S-METOLACCHLORINE (2-Chloro-N-(2-ethyl-6-methyl Iphenyl)-N-(1-methoxypropan-2-yl)acetamide) was added. an active component, 98.7% pure.

[0074] Then, to the same container, 4.73g of the emulsifier SOPROPHOR 796, an ethoxypropoxylated polyarylphenol and 2.84g of the emulsifier ATLOX 4912, a block copolymer of polyethylene glycol and 12-hydroxystearic acid, were added. As substituents for ATLOX 4912, ATLOX 4914 or ATLOX 4916 can be used.

[0075] Finally, 8.51 g of the ATLAS G5000 emulsifier, a polyalkylene oxide block copolymer, were added to the container. Examples of other emulsifiers that could be used instead of ATLAS G5000 and SOPROPHOR 796 comprise PO EO block copolymers such as: TOXIMUL 8320, PLURONIC PE 10500, ATLAS G5002L.

Table 1. Formulation of the organic phase with S-metolachlor.

Example II - Preparation of the water-in-oil emulsion

[0076] The formation of reverse micelles took place with the slow addition of the organic phase (10 to 15 mL per second), as formulated in the previous example, in water.

[0077] Various proportions of oil phase:water phase were tested, from 50:50 to 70:30. After the addition was completed, the mixtures were placed in a high shear mixer for 10min at 8000RPM. The average particle sizes were measured in triplicate and presented as the average of the values obtained. The proportions used in the experiment refer to the proportion of the oil phase (S-Metolachlor Base): aqueous phase (water). The mean particle size (TMP) indicates that at least 50% (D50), or at least 90% (D90), of the reverse micelles are smaller than indicated.

Table 2. Formulation of the water-in-oil emulsion preparation.

[0078] From Table 2, we see that in the use of compositions comprising above 30% of water, a substantial reduction in the particle size of the emulsion begins to be observed. Interestingly, from the proportion of 35%, which is just above 30%, the particle size gradually increased.

[0079] In general, the reverse micelles were obtained with mean particle size (D50) below 129.05 pm (Standard Deviation [SD] = 1.51 ), 1.06 pm (SD = 0.08), 1.62 pm (SD=0.1) and 2.74 (SD=0.01) pm and with 90% of the particles with average size (D90) below 221.66 pm (SD=7.86), 1 .88 pm (SD=0.14), 2.86 pm (SD=0.14) and 4.71 pm (SD=0.08). The reduced size and homogeneous granulometric distribution of the reverse micelles for proportions of up to 70% in the oil phase resulted in stable and effective emulsions.

[0080] When using proportions of 70:30 (oil phase: water phase) in the preparation of water-in-oil emulsions, the average particle size obtained was much higher and above 100 pm. These emulsions, with an average particle size greater than 100 pm, would not be suitable for formulations of stable suspo-emulsions and with high amounts of water-immiscible actives, as described in the present patent application.

[0081] In tests of rapid addition of the oil phase, in the proportion 65:35, a significant increase in mean particle size was detected (D90 from 15 to 30 µm).

Example III - Formation of suspo-emulsion

[0082] An aqueous suspension was prepared from the addition of 8.88g of mono ethylene glycol and 4.44g of Polyfon H((2R)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy- 4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid) in 156.69g of water. In addition, 5.77g, 3.55g, 2.66g of the dispersants SOPROPHOR 4D384, PLURONIC PE10500 and SOKALAN HP53 were added, respectively, followed by the addition of 1.69g of SILFOAM S.R.E. Finally, the preparation of the suspension was completed with the addition of 0.4g of the bactericide PROXEL GXL and 156.69g of the solid active ingredient Flumioxazin and 2.66g of the anti-caking agent CABOSIL M5.

Table 3. Formulation of the aqueous suspension containing Flumioxazin.

[0083] Examples of other dispersants for suspension production include ATLOX 4913, ATLOX 4894, SOPROPHOR FLK and SURFOM 1322.

[0084] Examples of other antifreezes for making the suspension comprise glycerins, propylene glycol, propylethylene glycol and diethylene glycol.

[0085] For the formation of the suspo-emulsion, 131.04g of the 65:35 emulsion obtained at the end of example II were added to a container containing 10.78g of the aqueous suspension containing Flumioxazin.

[0086] Then 1.34g of water was added, as a diluent, and 6.71g of gel thickener (KELZAM AP 2% + 1% BIT).

[0087] Finally, 0.13g of SAG 1572 defoamer was added, which is a dimethyl polysiloxane emulsion.

Table 4. Suspo-emulsion preparation formulation.

[0088] From the procedures described, it was possible to obtain a herbicide suspo-emulsion with a continuous water-immiscible phase, comprising S METOLACLORO, the polymeric emulsifiers ATLOX 4912, ATLAS G5000 and SOPROPHOR 796P. Furthermore, the aqueous discontinuous phase comprises the solid particulate herbicide Flumioxazin.

Example IV - Suspo-emulsion stability and characterization tests

[0089] From a suspo-emulsion of S-metolachlor and Flumioxazin (as described in example III, above), a new test, according to CIPAC method MT 36.3, was used to verify the average particle size, and this average size was monitored at different temperatures for different storage times. TMP and syneresis measurements were performed after the storage time (in days) indicated in the table.

Table 5. Suspo-emulsion stability tests after storage at different temperatures.

[0090] As can be seen in table 5, the suspo-emulsion remained stable and with reduced particle size even after storage at different temperatures (from 0 °C to 54 °C) and for up to 56 days.

[0091] The suspo-emulsions were still evaluated in relation to their stability with the CIPAC method MT 36.3. Basically, the suspo-emulsions were diluted in water with different hardness (20 ppm and 342 ppm), and the formation of “oil” and/or “free foam” was verified.

Table 6. CIPAC MT 36.3 stability tests at 30 °C.

[0092] Composition A was stored at 25°C for 0 days prior to testing. Composition B was stored at 0 °C for 7 days before testing. Composition C was stored at 54 °C for 14 days before testing. Composition D was stored at 40 °C for 56 days before testing. The time indicated in the table refers to the time waited after dilution to perform the test.

[0093] As can be seen in table 6, the suspo-emulsion remained stable even after dilution in water, which shows the ability to use the composition in different forms of application.

[0094] Also, according to the CIPAC method MT 36.3, the viscosities of the composition under rotation were analyzed. Composition A was stored at 25°C for 0 days before testing. Composition B was stored at 0 °C for 7 days before testing. Composition C was stored at 54 °C for 14 days before testing. Composition D was stored at 40 °C for 56 days before testing.

Table 7. CIPAC MT 36.3 viscosity tests.

Example V - Application of Suspo-emulsion in Soybean Crops

[0095] Assays of herbicidal activity of the suspo-emulsion of the present invention were carried out in pre-emergent treatments in soybean, for the control of different unwanted vegetation. In none of these, the suspo-emulsions showed significant phytotoxicity against soybean cultivation.

Control of Amaranthus hybridus in soybean

[0096] Suspo-emulsions of S-metolachlor and flumioxazin were applied in treatments of pre-emergent soybean crops, according to table 8 below. Control results are presented as a percentage relative to the control (no herbicide treatment).

Table 8. Doses of treatments in soybean crop.

Table 9. Results of Amaranthus hybridus control in soybean.

[0097] At 7 and 14 ADI (days after application), no birth of unwanted vegetation was recorded in any of the treatments. Even after 60 ADI the treatments were efficient in controlling Amaranthus hybridus.

[0098] In other tests of pre-emergent application in soybean crop, paraquat (3 L/ha) was added before application of the suspo-emulsion. The results can be seen in the table below. Control results are presented as a percentage relative to the control (no herbicide treatment). Table 10. Control of Amaranthus hybridus in soybean.

[0099] As can be seen in Table 10, the suspo-emulsions showed excellent results in the control of Amaranthus hybridus, even after 60 ADI in combination with another agrochemical composition. Control of Digitaria sanguinalis in soybean

[0100] Suspo-emulsions of S-metolachlor and flumioxazin were applied in pre-emergent treatments in soybean crops, according to table 11 below. Control results are presented as a percentage relative to the control (no herbicide treatment).

Table 11. Doses of treatments in soybean crop.

Table 12. Results of Digitaria sanguinalis control in soybean.

[0101] At 7 and 14 ADI (days after application), no birth of unwanted vegetation was recorded in any of the treatments. After 30 ADI, a control of 40 to 70% was observed, in relation to the control, of unwanted vegetation.

[0102] New tests were carried out in pre-emergent treatments of soybean crops, with joint application of paraquat. Control results are presented as a percentage relative to the control (without treatment of herbicide).

Table 13. Results of Digitaria sanguinalis control with combined application of paraquat in soybean.

[0103] As can be seen, the combination of suspo-emulsion with paraquat treatment, presents excellent controls of unwanted vegetation, even after 60 ADI.

Control of Brassica rapa in soybean

[0104] Suspo-emulsions of S-metolachlor and flumioxazin were applied in pre-emergent treatment in soybean crops, according to table 14 below. Prior to the application of the suspo-emulsions, the cultures were treated with paraquat (3 L/ha). Control results are presented as a percentage relative to the control (no herbicide treatment).

Table 14. Treatments to control Brassica rapa in soybean.

[0105] As can be seen, the suspo-emulsion showed great efficacy for the control of Brassica rapa in soybean, even after 60 ADI.

Control of Chloris elata in soybean

[0106] Suspo-emulsions of S-metolachlor and flumioxazin were applied in pre-emergent treatment in soybean crops, according to table 15 below. Before treatment with the suspo-emulsion, the soil was treated with paraquat (2 l/ha) + AMS (0.2 l/ha). Control results are presented as a percentage relative to the control (no herbicide treatment).

Table 15. Treatments to control Chloris elata in soybean.

[0107] The suspo-emulsion showed highly efficient control of Chloris elata, even after 45 ADI. After 60 ADI, the results were control of 40 to 55% of unwanted vegetation.

Amaranthus palmeri control in soybean

[0108] Suspo-emulsions of S-metolachlor and flumioxazin were applied in pre-emergent treatment in soybean crops, according to table 16 below. Control results are presented as a percentage relative to the control (no herbicide treatment).

Table 16. Treatments to control Amaranthus palmerie in soybean crop.

[0109] The suspo-emulsion compositions of the present invention showed excellent control of Amaranthus palmeri in soybeans, even after 60 ADI.

Control of Eleusine Indica in Soybean

[0110] Suspo-emulsions of S-metolachlor and flumioxazin were applied in pre-emergent treatment in soybean crops, according to table 17 below. Control results are presented as a percentage relative to the control (no herbicide treatment).

Table 17. Treatments to control Eleusine indica in soybean.

[0111] Again an effective vegetation control can be observed undesired by the application of the suspo-emulsion of the present patent application, even after 55 ADI.

[0112] Those skilled in the art will value the knowledge presented herein and may reproduce the invention in the modalities presented and in other variants and alternatives, covered by the scope of the claims below.

Claims

claims

1 . Suspo-emulsion characterized in that it comprises: a) from 50% to 95% by mass of a continuous, water-immiscible phase, comprising: i) at least one water-immiscible active ingredient, and ii) at least one water-in-oil emulsifier with HLB in the range 3 to 9; b) from 5% to 50% by mass of an aqueous discontinuous phase comprising: i) dispersed solid particles of at least one water-insoluble active ingredient, wherein said discontinuous phase is formed by reverse micelles, wherein the diameter of at least at least 90% of said reverse micelles are in the range between 0.1 pm to 50 pm.

Suspo-emulsion, according to claim 1, characterized in that it additionally comprises in the continuous phase at least one emulsifier with HLB in the range of 12 to 18.

Suspo-emulsion, according to claim 1 or 2, characterized in that the diameter of at least 90% of said reverse micelles is in the range between 0.1 pm to 20 pm.

4. Suspo-emulsion according to any one of claims 1 to

3, characterized in that the diameter of at least 90% of said reverse micelles is in the range between 1 pm to 10 pm.

5. Suspo-emulsion according to any one of claims 1 to

4, characterized in that the active ingredient is an agrochemical selected from the group of pesticide, insecticide, fungicide, herbicide, acaricide, molluscicide, nematicide and/or plant growth modulating agent.

6. Suspo-emulsion according to any one of claims 1 to

5, characterized in that the emulsifier is non-ionic polymeric and/or phosphate ester emulsifier.

Suspo-emulsion, according to the preceding claims, characterized in that it comprises, in the continuous phase, from 0.5 g/L to 800 g/L of water-immiscible active ingredient.

Suspo-emulsion, according to claim 7, characterized in that it comprises in the continuous phase from 300 g/L to 800 g/L of water-immiscible active ingredient.

Suspo-emulsion according to any one of the preceding claims, characterized in that the water-immiscible active ingredient is a herbicide from the group of acetamides comprising acetochlor, alachlor, butachlor, butenachlor, delachlor, diethyl, dimethachlor, dimethenamid, dimethenamid-P, mephenacet, metazochlor, metolachlor, napropamide, pretilachlor, pronamide, propachlor, propisochlor, prinachloryl, terbuchlor and salts, esters, isomers, stereoisomers and combinations thereof.

10. Suspo-emulsion, according to claim 9, characterized in that the water-immiscible active ingredient is S-metolachlor.

Suspo-emulsion, according to any one of the preceding claims, characterized in that it comprises in the discontinuous aqueous phase from 10 g/L to 400 g/L of dispersed solid particles of a water-insoluble active ingredient.

Suspo-emulsion, according to claim 11, characterized in that it comprises in the discontinuous aqueous phase from 30 g/L to 200 g/L of dispersed solid particles of a water-insoluble active ingredient.

Suspo-emulsion according to any one of the preceding claims, characterized in that the water-insoluble active ingredient is a herbicide from the phenylphthalimide group, comprising cinidon-ethyl, flumezin, flumiclorac, flumioxazin and flumipropyn.

14. Suspo-emulsion, according to claim 13, characterized in that the water-insoluble active ingredient is flumioxazin.

15. Suspo-emulsion according to any one of claims above characterized in that the ratio between water-immiscible active ingredient and water-insoluble active ingredient is 12:1 to 1:1.

Process for preparing a suspo-emulsion, as defined in any one of the preceding claims, characterized in that it comprises the steps: a) Preparing a water-in-oil emulsion comprising: i) Mixing 50% to 95% by mass of at least one water-immiscible active ingredient with 5% to 40% by mass of at least one water-in-oil emulsifier with HLB in the range of 3 to 9; ii) Add in a high shear mixer 50% to 70% by mass of the mixture obtained in i) and from 35% to 50% by mass of water, and mix until obtaining a water-in-oil emulsion in which 90% of said micelles reverse is in the range between 0.1 m to 40 pm; b) Preparing an aqueous suspension comprising 50% to 80% by mass of dispersed solid particles of a water-insoluble active ingredient; c) Mix 50% to 95% by mass of the emulsion obtained in a) with 5% to 50% by mass of the suspension obtained in b).

17. Process according to claim 16, characterized by step a) ii taking place for 5 to 30 minutes at a rotation of 5000 to 15000 rpm.

Process according to claim 16 or 17, characterized in that in step "c" the water-in-oil emulsion is added at a rate of 5 to 20 ml/s in the aqueous suspension.

19. Method of controlling unwanted vegetation and/or pests characterized by the application of a suspo-emulsion, as defined in any one of claims 1 to 15.

Control method, according to claim 19, characterized in that it comprises a step of diluting the suspo-emulsion in water before the application step.

21. Control method according to claim 19 or 20, characterized in that it additionally comprises the application of a diverse agrochemical composition before or after the application of said suspo-emulsion, as defined in any one of claims 1 to 15.

22. Control method, according to any one of claims 19 to 21, characterized in that the suspo-emulsion application step is pre-planting, pre-emergence or post-emergence.

A control method according to any one of claims 19 to 22, characterized in that the unwanted vegetation is at least one selected from the group consisting of Amaranthus sp, Brassica sp, Digitaria sp, Elusine sp, Echinochloa sp and Chloris sp.

24. Control method, according to any one of claims 19 to 23, characterized in that the suspo-emulsion is applied at a dose of 40 L/ha to 100 L/ha.

25. A method for treating seeds, characterized in that it comprises applying, to at least one seed, a suspo-emulsion as defined in any one of claims 1 to 15.