WO2023203483A1

WO2023203483A1 - Chlor-triazine nanoemulsions

Info

Publication number: WO2023203483A1
Application number: PCT/IB2023/053958
Authority: WO
Inventors: Felix Silvestre GALAN ROMANO
Original assignee: Surcos impact
Priority date: 2022-04-19
Filing date: 2023-04-18
Publication date: 2023-10-26
Also published as: AR125376A1

Abstract

An herbicidal chloro-triazine composition, in the form of an emulsion¬ forming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising chloro-triazine at a concentration from 15% to 21 % w/v, a solvent at a concentration from 50% to 70% w/v, an adjuvant at a concentration from 1 % to 20% w/v, and a surfactant at a concentration from 1 % to 21.00% w/v.

Description

CHLOR-TRIAZINE NANOEMULSIONS

Field of the Invention

The present invention pertains to the field of herbicidal compositions comprising chemical compounds of the chloro-triazine family, particularly to the field of micro- and nanoemulsions, having a highly efficient herbicidal action while preserving the environment.

Background

Atrazine and terbuthylazine are members of the chloro-triazine family of herbicides. They haveamainly systemic and residual action and are generally used as pre-emergence agents applied to the soil after planting the crop, although they may also be used as early post-emergence agents on recently emerged weeds (not more than 1 -2 leaves). However, in this case, their action is mainly “of contact” (and not systemic) and will require the addition of surfactants and/or oils, as well as a significant spray droplet coverage.

In general, these compounds are marketed as concentrated solutions (CS), emulsifiable concentrates (EC) or wettable powders (WP), which must be diluted in an aqueous medium prior to field application.

The product may be applied in the necessary amount to uniformly cover the area to be treated. Application may be carried out using aerial or ground, trailer or motorized spraying equipment, either broadcast or in bands.

Before starting any treatment, it is essential to verify correct calibration of the equipment and proper operation of the nozzles (filters and tips), replacing any defective parts to ensure a homogeneous dispersion. Usually it is necessary to keep the stirring system in continuous operation to favor homogenization of the formulation, as normally it is not stable for long periods. In the case of ground spraying, broadcast application requires the recommended rate to be diluted in 80-120 liters/ha of clean water, keeping a minimum coverage of 30 to 40 droplets/cm2 of leaf surface. The recommended tips are those of flat fan sprayers working at a pressure from 25 to 40 pounds/sq. in.

In the case of terrestrial band spraying, the recommended rate should be applied diluted in a volume of clean water of not less than 30 L/ha.

Finally, in the case of aerial spraying, the recommended rate should be applied diluted in a volume of clean water of not less than 20 L/ha.

Atrazine and terbuthylazine are widely used in preventive weed control of various crops such as com, sorghum, olive, sugarcane, tea, among others. By way of example, in the case of using Atrazine in the pre-treatment of maize crops, it is used for treating: alfalfa (Medicago sativa), pell itory (Parietariadebilis), bristly oxtongue (Picrisechioides), fleabane (Conyzabonariensis), globe amaranth (Gomphrenapulchella), common purslane (Portulacaoleracea), pigweed (Amaranthusquitensis), among others.

The mechanism of action is by cuticle penetration: to better understand the mechanisms by which herbicides such as atrazine and terbuthylazine reach their site of action, leaf physiology should be considered. The cuticle is an asymmetric membrane mainly composed of waxes, cutin and/or cutan, polysaccharides and small amounts of phenols. The epicuticular wax layer is in direct contact with the surrounding atmosphere and is substantiallyapolar. The different inner layers may be distinguished by electron microscopy in cross sections of the cuticle from different species and organs. These layers are composed of cutin and/or cutan, intracuticular waxes and polysaccharides, but may show different structures depending on the arrangement of the constituent molecules. Different polarity and hydrogen bond interactions that may occur among functional groups of waxes, polysaccharides, cutin, cutan or the phenolic compounds present in the cuticle, may facilitate or hamper the cuticular penetration process of predominantly polar or apolar agrochemical compounds (J. D. Mauseth, Botany: An Introduction to Plant Biology, Jones and Bartlett, 4th edition, 2009).

It has been proposed that penetration of apolar/lipophilic substances through the cuticle is followed by a dissolution-diffusion process (Riederer and Friedmann, 2006). This model assumes that the movement of a lipophilic molecule in a solution deposited on the plant cuticle involves a diffusion process through a pathway that takes advantage of composite zones of lipophilic substances, such as cuticular wax, until it reaches the cell membrane, which is also permeable to this type of substance. This process can be modeled according to Fick’s first law: The higher the Kow (n-octanol-water partition coefficient), the greater the product diffusion, but with very high Kow values plant lipids will strongly retain apolar molecules, so that a part is prevented from being absorbed.

Over the last years great efforts have been made to obtain stable formulations of compounds such as Atrazine and Terbuthylazine, two of the most important members of the chlorinated triazine family. Examples of these formulations can be found in the state of the art in the form of concentrated suspensions, wettable powders, dispersable granules or emulsifiable concentrates. Alternatively, it has been proposed to encapsulate the active principle in biodegradable polymers by generating an encapsulated suspension which is then dissolved to form an aqueous colloidal suspension for spraying or atomization.

Examples of these efforts can be found in patent document US2002016264, to Syngenta Participations AG, which discloses a concentrated aqueous suspension of Atrazine comprising 43.5% by weight of Atrazine.

In addition, patent documents such as US Patent No. US 4,824,475, to Dow Chemical Co., which disclosesemulsifiable concentrates of atrazine at concentrations of 36% of active principle. Said document teaches combinations of at least 2 herbicides. Particularly, in this example Atrazine is used as a post emergence herbicide, and used in combination with another compound having the same activity.

Other examples that may be mentioned are US Patents US 6,455,471 and US 8,445,405, Chinese Patent No. CN 103766330A, which disclose different formulations in the form of emulsifiable concentrates of atrazine and other herbicides or as combinations with other herbicides.

Other patent documents, such as AR 062169, to Bayer Crop Science AG, have been found. This document describes formulations in the form of microemulsions of herbicidal agents. Said Application, although mentioning atrazine as a possible herbicidal candidate, does not disclose a formulation showing stability and efficacy at the time of application. Another document of the state of the art is Patent Application AR 083776, to BASF SE, which describes an emulsifiable concentrate, with concentrations of at least 25% of herbicidal agents, where a possible agent may be Atrazine.

Among other problems to be solved in the state of the art, it is worth mentioning that the particular physicochemical features of compounds such as Atrazine make it necessary to apply higher concentrations in order to achieve the desired herbicidal effect, as well as the need to improve handling of the product to avoid crystallization or formation of heterogeneous solutions that may later hamper product dispersion on the field.

By way of example, currently, products available for application are marketed as a particulate formulation comprising particles of the active ingredient in suspension (CS) 90% of which are less than 10 microns in size. A use rate of 2,5 liters per hectare of a product with a concentration of active principle of 50% w/v results in a minimum deposition of active applied per hectare of 125 gr/ha.

Detection of residues of these herbicides in various countries has led regulatory agencies to impose different types of measures, for example, in the US they have been subject tovarious studies and controversial decisions, in the European Union Atrazine was banned (in 2004) when residual levels were found to be higher than those established by the regulatory standards.

An excessive use of this type of herbicides may cause environmental issues such as leaching, groundwater contamination, persistence in soil at variable depths and contamination of aquatic organisms, among other adverse effects.

Using an excess of compounds such as Atrazine also causes drawbacks to the farmer or user. For example.usually they must be used as application broths with heterogeneous mixtures causing clogging of sprinkler nozzles. They may also generatesedimentation in tanks, and antagonize with glyphosate (loss of effectiveness of glyphosate in broths when mixed with Atrazine).

The present invention solves the problems of the state of the art by providing a herbicidal composition capable of forming a nanoemulsion, having sufficient stability in time so as to allow the end user to work safely, favoring a homogeneous dispersion of the active principle, thereby achieving a reduction of the amount applied per hectare, without affecting efficacy of the final product relative to products in use today. In addition, the formulation of the present invention slides over the stubble, thus allowing all the dispensed matter to reach the site of action when used as a pre-emergence agent.

Brief description of the invention

The subject-matter of the present invention is a herbicidal chloro-triazine composition, in the form of an emulsion-forming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising chloro-triazine at a concentration from 15% to 21 % w/v, a solvent at a concentration from 50% to 70% w/v, an adjuvant at a concentration from 1 % to 20% w/v, and a surfactant at a concentration from 1 % to 21.00% w/v, wherein said chloro-triazine is selected from the group consisting of atrazine, terbuthylazine and mixtures thereof. Furthermore, said solvent is selected from the group consisting of N-methylpyrrolidone, isophorone, dimethylsulfoxide, cyclohexanone, 1 ,3-dioxolane (1 ,3-dioxacyclopentane), Solketal (2,2-dimethyl- 1 ,3-dioxolan-4-yl)methanol, soybean and coconut fatty acid aminoamide, ethanol, dimethylacetamide, dimethylamide, ethanol, ethyl lactate and mixtures thereof. Said adjuvant is selected from the group consisting of xylene, soy aminoamide of fatty acid methyl esters, 15 mole ethoxylated coconut fatty amine, 15 mole ethoxylatedfatty amine, 15 mole and 20 mole ethoxylated tallow fatty amine (EmulsogenT150), ethoxylated castor oil with 36 moles of ethoxylation (Emulsogen EL360), soy fatty acid methyl esters, 60% calcium phenylsulfonate, n-butanolalkoxylate, 36 mole ethoxylated castor oil (EmulsogenEL360); fatty alcohol polyglycol ether, 6 mole ethoxylatedisotridecyl alcohol (GENAPOL X060), tristyrylethoxylate (Emulsogen TS 200), tristyrylphenolethoxylate (Emulsogen TS 540), azeotropic mixture of ethyl acetate:ethanol, 2,4,6-Tri-(1-phenylethyl)- phenol ester phosphoric polyglycol ether triethanolamine salt (Emolsogen 3475) and mixtures thereof. And said surfactant is selected from the group consisting of 6 mole ethoxylatedisotridecyl alcohol, N,N-dimethyldecan-1 -amide and N,N- dimethyloctaneamide, 20 mole and 54 mole ethoxylatedtristyrylphenol, 10 mole ethoxylatednonylphenol and mixtures thereof.

Furthermore, the composition of the invention may or may not contain water.

Another object of the present invention is a nanoemulsion which is stable for at least 12 hs comprising the composition of the present invention emulsified in water at a concentration from 2 to 5% (v/v). The nanoemulsion of the invention has a particle size from 40 to 100 nanometers, is stable and maintains stability for at least 1 hour and its redispersion ability, even if it contains other agrochemicals selected from the group consisting of 2,4D, glyphosate, glyphosate potassium salt, and mixtures thereof.

Another object of the present invention is a nanoemulsified herbicide formulation comprising the composition of the invention emulsified in water, at a concentration from 2 to 5% (v/v). Further, it maintains its stability and redispersion ability for at least 1 hour, even if it contains other agrochemicals selected from the group consisting of 2,4D, glyphosate, glyphosate potassium salt, and mixtures thereof.

Another object of the present invention is a treatment of crops selected from the group consisting of corn, soybean, wheat, rice, rapeseed, sugarcane, sorghum, flax, fallow and tea, comprising dispersing the formulation of the invention over the crop-producing fields at a concentration of less than 108 g of atrazine per hectare. Furthermore, the treatment of the invention is selected from the group consisting of a pre-emergence treatment and a post-emergence treatment for reducing weeds. Further, the weeds are selected from the group consisting of common purslane (Portulacaoleracea), nettle (Urticaurens), swinecress (Coronopusdidymus), chamomile (Anthemiscotula), sowthistle (Sonchusoleraceus), shepherd’s purse (Capsellabursa-pastoris), common knotgrass (Polygonumaviculare), climbing buckwheat (Polygonum convolvulus), chickweed (Stellaria media), foxtail (Setariaspp), fierce thornapple (Daturaferox), pigweed (Amaranthusspp), turnip (Brassicaspp), curled dock (Rumexcrispus), large thistle (Xanthium cavanillesi), annual bluegrass (Poaannua), goosefoot (Chenopodiumspp), sticky nightshade (Solanumsisymbriifolium), hoary bowlesia (Bowlesiatenera), black clover (Medicagolupulina), Rhodes grass (Chlorisgayana), knotgrass (Paspalumdistichum), spiny cocklebur (Xanthium spinosum), pinweed (Erodiumcicutarium), barnyardgrass (Echinochloaspp).

Another object of the present invention is a manufacturing process of the composition of the invention comprising the steps of: a. obtaining said chloro-triazine; b. mixing the chloro-triazine of step a. with at least one solvent and a surfactant under stirring and heating until complete dissolution; c. adding adjuvants to the mixture of step b. under stirring and optionally heating; d. allowing to cool.

Said solvent is selected from the group consisting of N-methylpyrrolidone, isophorone, dimethylsulfoxide, cyclohexanone, 1 ,3-dioxolane (1 ,3- dioxacyclopentane), Solketal (2,2-dimethyl-1 ,3-dioxolan-4-yl)methanol, soy and coconut fatty acid aminoamide, ethanol, dimethylacetamide, dimethylamide, ethanol, ethyl lactate and mixtures thereof. Preferably, the solvent is N- methylpyrrolidone. Furthermore, said adjuvant is selected from the group consisting of xylene, soy aminoamide of fatty acid methyl esters, 15 mole ethoxylated coconut fatty amine, 15 mole ethoxylated T150 fatty amine, 15 mole and 20 mole ethoxylated tallow fatty amine, ethoxylated castor oil with 36 moles of ethoxylation, soy fatty acid methyl esters, 60% calcium phenylsulfonate (60% FSCa), n-butanolalkoxylate, 36 mole ethoxylated castor oil (EL360); fatty alcohol polyglycol ether (X060), 6 mole ethoxylatedisotridecyl alcohol, tristyrylethoxylate (Emulsogen TS 200), tristyrylphenolethoxylate (Emulsogen TS 540), azeotropic mixture of ethyl acetate:ethanol, 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt and mixtures thereof. And said non-ionic surfactant is selected from the group consisting of 6 mole ethoxylatedisotridecyl alcohol, N,N-dimethyldecan-1 -amide and N,N- dimethyloctaneamide (Genagen 4166), 20 mole and 54 mole ethoxylatedtristyrylphenol, 10 mole ethoxylatednonylphenol and mixtures thereof. Also, water may be optionally added during the process of the invention, preferably at a temperature of 50°C.

Another object of the present invention is a process for making the formulation of the invention comprising the steps of: a. providing water in a tank; b. adding the composition of the invention to the water of step a., under stirring; c. stirring until a homogeneous nanoemulsified ready-to-use formulation is obtained.

In a preferred embodiment, the atrazine herbicidal composition, in the form of an emulsion-forming concentratethat generates a nanoemulsion having an extended stability of at least 12 hours of the present invention; comprises atrazine at a concentration from 15% to 21 % w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, xylene at a concentration from 0 to 20% w/v, and 10 mole ethoxylatednonylphenol at a concentration from 1 % to 21 % w/v.

In a preferred embodiment, the atrazine herbicidal composition, in the form of an emulsion-forming concentrate that generates a nanoemulsion having an extended stability of at least 12 hours of the present invention, comprises atrazine at a concentration from 15% to 20% w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, N,N dimethyldecan-1 -amide and N,N dimethyloctaneamide at a concentration from 1 % to 3% w/v, 2,4,6-Tri-(1 - phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration from 1 % to 3% w/v and ethoxylated T150 fatty amine at a concentration from 10% to 16% w/v.

In a preferred embodiment, the atrazine herbicidal composition, in the form of an emulsion-forming concentrate that generates a nanoemulsion having an extended stability of at least 12 hours of the present invention, comprises atrazine at a concentration of 18% w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, N,N dimethyldecan-1 -amide and N,N dimethyloctaneamide at a concentration of 2% w/v, 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration of 2% w/v and ethoxylated fatty amine (Genamin T150).at a concentration of 13% w/v.

In a preferred embodiment, the atrazine herbicidal composition in the form of an emulsion-forming concentrate that generates a nanoemulsion having an extended stability of at least 12 hours of the present invention, comprises atrazine at a concentration of 18% w/v, N-methylpyrrolidone at a concentration from 50% to 79% w/v, N,N-dimethyldecan-1 -amide and N,N-dimethyloctaneamide at a concentration from 1 % to 3% w/v; soy fatty acid methyl esters at a concentration from 1 % to 3% w/v, 15 mole ethoxylated coconut fatty amine at a concentration from 10% to 16% w/v and 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration from 1 % to 3% w/v.

In a preferred embodiment, the atrazine herbicidal compositionin the form of an emulsion-forming concentrate that generates a nanoemulsion having an extended stability of at least 12 hours of the present invention, comprises atrazine at a concentration of 18% w/v, N-methylpyrrolidone at a concentration of 68% w/v, N,N-dimethyldecan-1 -amide and N,N-dimethyloctaneamide at a concentration of 2% w/v; soy fatty acid methyl esters at a concentration of 2% w/v, 15 mole ethoxylated coconut fatty amine at a concentration of 13% w/v and 2,4,6-Tri-(1-phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration of 2% w/v.

In a preferred embodiment, the atrazine herbicidal composition in the form of an emulsion-forming concentrate that generates a nanoemulsion having an extended stability of at least 12 hours of the present invention, comprises atrazine at a concentration from 15% to 20% w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, a mixture of ethyl acetate:ethanol (50:50) at a concentration from 1 % to 10% w/v, 10 mole nonylphenol at a concentration from 1 % to 3% w/v, 36 mole ethoxylated castor oil at a concentration of 2.5% w/v, n- butanolalkoxylate at a concentration of 7% w/v, soy and coconut aminoamide of fatty acid methyl esters at a concentration of 7% w/v, 2,4,6-Tri-(1 -phenylethyl)- phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration of 1 % w/v.

Description of the Drawings

Figure 1 is a micrograph of the emulsion of the present invention where particle size of the nanoemulsion comprises a size of the order from 40 nm to 100 nm in diameter.

Figure 2 is an enlargement of Figure 1

Figure 3 shows the assay of example 9, in which the percentage of formulation retained on the stubble, generating loss of active matter, is determined.

Detailed description of the invention

The herbicidal composition in the form of an emulsion-forming concentrate of the present invention has been designed to be applied in the form of a preemergence treatment and its activity is increased due to its novel preparation where the chloro-triazines, as the active principle, in particular Atrazine, is present in very small particles of nanometric size.

Many active agents, such as insecticides, herbicides and fungicides are relatively insoluble in aqueous media. In order to be efficiently used, appropriate compositions for each type of active matter must be developed so as to facilitate their dissolution in aqueous media suitable for aerosolization or spray dispersion by the end user.

The present invention provides a herbicidal composition in the form of emulsion-forming concentrates or dispersions that have demonstrated an extraordinary stability when dissolved in an aqueous medium and surprisingly maintain their herbicidal effect even when applied at much lower concentrations than those at which this active matter is usually applied. Preferably, the present invention provides a composition capable of generating a formulation in the form of a microemulsion, or microdispersion, when dissolved in an aqueous medium; more preferably the composition of the invention generates a formulation in the form of a nanoemulsion stable in an aqueous medium.

Another object of the present invention is a nanoemulsion formed by mixing the herbicidal composition of the present invention with water. Said herbicidal nanoemulsion comprises an emulsion or dispersion in the form of nanoparticles of a size from 10 to 500 nm in diameter; preferably, from 20 to 300 nm in diameter, more preferably from 30 to 200 nm; even more preferably from 40 to 100 nm in diameter.

In a preferred embodiment, the active principle belongs to the chloro- triazine herbicide family, such as simazine, propazine, atrazine, cianazina, and ciprazine, terbuthylazine and derivatives thereof. Preferably, within the chloro- triazine family, the composition of the present invention comprises an active principle selected from Atrazine and Terbuthylazine.

The herbicidal composition of the present invention comprises, at least, one active principle dissolved in a solvent. In one embodiment, said solvent is selected from the group consisting of N-methylpyrrolidone, isophorone, dimethylsulfoxide, cyclohexanone, 1 ,3-dioxolane (1 ,3-dioxacyclopentane), Solketal (2,2-dimethyl-1 ,3-dioxolan-4-yl)methanol, soy and coconut fatty acid aminoamide (Wetting Agent G), ethanol, dimethylacetamide, dimethylamide, ethanol, ethyl lactate; preferably it is N-methylpyrrolidone.

In a preferred embodiment, the herbicidal composition of the present invention further comprises at least one adjuvant selected from the group consisting of: soy aminoamide of fatty acid methyl esters, 15 mole ethoxylated coconut fatty amine, 15 and 20 mole ethoxylated tallow fatty amine, 15 mole ethoxylated T 150 fatty amine, ethoxylated castor oil with 36 moles of ethoxylation, Emag (soy fatty acid methyl esters), 60% FSCa (60% calcium phenylsulfonate), n-butanolalkoxylate (Emulsogen 4901 ), 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt (Emulsogen 3475), dimethylacetamide, dimethylamide, azeotropic mixture of ethyl acetate:ethanol, 36 mole ethoxylated castor oil (EmulsogenEL360); fatty alcohol polyglycol ether (Genapol X060), 6 mole ethoxylatedisotridecyl alcohol, tristyrylethoxylate (Emulsogen TS 200) and tristyrylphenolethoxylate (Emulsogen TS 540), xylene and combinations thereof.

In another embodiment, alternatively the herbicidal composition of the present invention may comprise at least one surfactant, preferably a non-ionic surfactant, selected from the group consisting of N,N-dimethyldecan-1-amide and N,N-dimethyloctaneamide (Genagen 4166), 10 mole ethoxylatednonylphenol, 20 mole and 54 mole ethoxylatedtristyrylphenol; and combinations thereof.

The herbicidal composition, one of the objects of the present invention, comprises an active agent at a concentration from 10% to 25% w/v, more preferably from 15% to 21 % w/v, more preferably from 15% to 20% w/v, even more preferably at a concentration of 18% w/v.

In a preferred embodiment, the herbicidal composition of the present invention comprises from 15% w/v to 20% w/v, more preferably 18% w/v Atrazine; from 50% to 75% w/v, more preferably from 55% to 70% w/v N-methylpyrrolidone; from 0% to 12% w/v, more preferably from 3% to 10% w/v xylene; from 0% to 5% w/v, more preferably from 0% to 3% w/v, 10 mole nonylphenol; from 0% to 3% w/v, more preferably from 0% to 2.5% w/v, 36 mole ethoxylated castor oil (Emulsogen EL 360); from 0% to 8% w/v, more preferably from 0% to 7% w/v, n- butanolalkoxylate (Emulsogen 4901 ); from 1 % to 13% w/v, more preferably from 1 % to 7% w/v, soy and coconut aminoamide of fatty acid methyl esters (Wetting agentE21 F7030); from 0% to 3% w/v, more preferably from 1 % to 2% w/v, 2,4,6- Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt (Emulsogen 3475).

In another preferred embodiment, the herbicidal composition of the present invention comprises from 15% w/v to 20% w/v, more preferably 18% w/v, Atrazine; from 50% to 75% w/v, more preferably from 55% to 70% w/v, N- methylpyrrolidone; 2% w/v N,N-dimethyldecan-1 -amide and N,N- dimethyloctaneamide (Genagen 4166); an adjuvant selected from the group consisting of from 11 % to 15% w/v, preferably 13% w/v, ethoxylated fatty amine and 15 mole ethoxylated coconut fatty amine; from 0% to 3% w/v, more preferably from 1 % to 2% w/v, 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt (Emulsogen 3475). In another preferred embodiment, the above-mentioned herbicidal composition further comprises from 0% to 2% w/v EMAG (soy fatty acid methyl esters).

The above percentages are expressed as % w/v relative to the total formulation of the herbicidal composition of the invention.

The formulated active or formulation, which is also an object of the present invention, comprises an aqueous dilution of the herbicidal composition of the present invention, and may be applied at a use rate from 3 to 6 liters per hectare. In this way, the amount of active per hectare is from 54 g/ha to 108 g/ha, which is less than the currently applied rates, where the amount of active principle is in the order of 125 g/ha to 250 g/ha per hectare. A reduction of about 50% of the applied range values of this active principle is achieved.

The formulation of 18% w/v Atrazine of the present invention keeps the active in a lipophilic environment within the micelles of the microemulsion, preferably nanoemulsion, which generates a permeability that enables the lipophilic pathway. Another object of the present invention is a nanoemulsion formed when combining the herbicidal composition of the invention with water. This nanoemulsion has a particle size, given by the particle diameter, from 30 to 150nm, more preferably a particle size from 40 to 100nm.

Surprisingly, the herbicidal composition of the present invention provides a stable emulsion, which is homogeneous for at least 2 hs, more preferably for at least 4 hs, more preferably for at least 6 hs, more preferably for at least 12 hs, even more preferably for at least 24 hs, with the ability to form a cream when emulsion tests are performed but that is rapidly reconstituted under stirring, for example, as described in example 7. These features of the new herbicidal composition of the invention reduce the need of qualified labor for preparing the emulsion for field application. However, it is more surprising that the herbicidal composition of the present invention achieves the same herbicidal effect but using about half of active principle relative to formulations currently available on the market, which have a concentration of 50% w/v. Therefore the advantages of the present invention are: lower use rate, protection against physicochemical losses (evaporation, drifting, etc.), improvement of the absorption rate, significantly lower environmental impact variables, drastic reduction of solvent evaporation, actives maintained in the liquid phase, allowing solubilizing hydrophobic actives in water, generation of a great increase in the surface/volume ratio and controlled release of actives. Moreover, the formulation of the present invention, provides higher efficiency when applied at a concentration of active matter of 81 g/ha for combattingPorfu/acao/eracea as compared to a chemical control of 200 g/L Atrazine (50% w/v Atrazine). This assay clearly shows that the special properties of the formulation of the invention achieve surprising results over the state of the art, which go far beyond of what a person skilled in the art could have expected when combining the knowledge of the prior art.

Another object of the present invention is to provide a formulation for treating crops selected from the group consisting of corn, soybean, wheat, rice, rapeseed, sugarcane, sorghum, flax, fallow, and tea, among others.

The formulation of the present invention may be used as a pre-emergence or post-emergence treatment of weeds such as Portulacaoleracea (common purslane), Urticaurens (nettle), Coronopusdidymus (swinecress), Anthemiscotula (chamomile), Sonchusoleraceus (sowthistle), Capsellabursa-pastoris (shepherd’s purse), Polygonumaviculare (common knotgrass), Polygonum convolvulus (climbing buckwheat), Stellaria media (chickweed), Setariaspp (foxtail), Daturaferox (fierce thornapple), Amaranthusspp (pigweed), Brassicaspp (turnip), Rumexcrispus (curled dock), Xanthium cavanillesi (large thistle), Poaannua (annual bluegrass), Chenopodiumspp (goosefoot), Solanumsisymbriifolium (sticky nightshade), Bowlesiatenera (hoary bowlesia), Medicagolupulina (black clover), Chlorisgayana (Rhodes grass),

Paspalumdistichum (knotgrass), Xanthium spinosum (spiny cocklebur), Erodiumcic utari urn (pinweed), Echinochloasp (barnyardgrass). Working Examples:

Example 1 : Preparation of a herbicidal composition in the form of an 18% w/v Atrazine emulsion-forming concentrate

In a first container 60.5 g of N-methylpyrrolidone and 5 g of xylene, 18.5 g of Atrazine (97% pure), were added, heated to 50°C and mixed until complete dissolution of the active was achieved.

Into a second container, 2 g of 10 mole nonylphenol, 2.5 g Emulsogen EL 360, 7 g of Emulsogen 4901 , 7 g of Wetting agent E21 F7030 and 1 g of Emulsogen 3475 were added and stirred until homogeneous.

The content of the second container was added to the first container and temperature was kept at 50°C, stirring until homogeneous. The final volume was of 100 mL.

Example 2: Preparation of a herbicidal composition in the form of an 18% w/v Atrazine emulsion-forming concentrate

Using the method of preparation of example 1 , in a first container containing 70 g N-methylpyrrolidone and 2 g Genagen 4166 (N,N-dimethyldecan- 1 -amide and N,N-dimethyloctaneamide), 18.5 g of Atrazine (97% purity) were added, heated to 50°C and mixed until complete dissolution of the active.

In a second container, 13 g of 15 mole ethoxylated T150 fatty amine and 2 g of Emulsogen 3475 were added and stirred until homogeneous.

Example 3: Preparation of a herbicidal composition in the form of an 18% w/v Atrazine emulsion-forming concentrate Using the method of preparation of example 1 , in a first container containing 68 g of N-methylpyrrolidone and 2 g of Genagen 4166 (N,N- dimethyldecan-1 -amide and N,N-dimethyloctaneamide), 18.5 g of Atrazine were added, heated to 50°C and mixed until complete dissolution of the active was achieved.

In a second container 2 g of EMAG (soy fatty acid methyl esters), 13 g of 15 mole ethoxylated coconut fatty amine and 2 g of Emulsogen 3475 were added and stirred until homogeneous.

Example 4: Preparation of a herbicidal composition in the form of an 18% w/v Atrazine emulsion-forming concentrate

Using the method of preparation of example 1 , in a first container containing 2 g of 10 mole nonylphenol, 60.5 g of N-methylpyrrolidone, 18.5 g of Atrazine (97% purity) were added, heated to 50°C and mixed until complete dissolution of the active was achieved.

In a second container containing, 5 g of an azeotropic mixture of ethyl acetate: ethanol (50:50), 2.5 g of Emulsogen EL 360, 7 g of Emulsogen 4901 , 7 g of Wetting agent E21 F7030 and 1 g of Emulsogen 3475 were added and stirred until homogeneous.

The content of the second container was added to the mixture of adjuvants in the first container with the active dissolved in a solvent and temperature was kept at 50°C, stirring until homogeneous. The final volume was of 100 mL.

Example 5: RANGE TRIALS The following formulations were obtained using the procedure described in example 1 .

Table 1 :

Atrazine of the invention

Table 1

Composition B (18.6% w/v, 97% purity) showed the best performance, achieving a final concentration of 18% w/v per 100 mL, whereas the stability of the 21% w/v tank mixtures was lower, and the 15% w/v formulation required a higher fieldapplication rate , which makes its use impractical for farmers. Even so, all three still meet the advantages of the present invention.

Example 6: Determination of particle size of the aqueous nanoemulsion of the composition of the invention:

A sample of a nanoemulsion obtained by emulsifying the composition of example 1 in 30% water was characterized by determining the average size of particles present therein. Micrographs were taken showing the corresponding scale.

Observation was performed by transmission electron microscopy techniques. The sample was prepared within one hour prior to observation with a transmission electron microscope (TEM). To this end, a 30% v/v emulsion was prepared in distilled water. Thirty 30 pL of sample were measured using a micropipette, making up 100 pL with distilled water, then 5 pL of uranyl acetate was added followed by stirring. Finally, a droplet of the resulting solution was seeded in a grid of 3 mm in diameter, removing any excess with filter paper and drying with an IR lamp before placing the grid in the sample holder of the TEM.

A Philips CM 200 transmission electron microscope, operated at 160 kV, was used.

Results:

As may be seen in figures 1 and 2, particle size in the nanoemulsionwas from 40 nm to 100 nm in diameter.

Example 7: Stability assays of the formulations of the present invention.

Into a 250 mL beaker, 60.5 g of N-methylpyrrolidone and 5 g of xylene, then 18.5 g of Atrazine were added, heated to 50°C and mixed until complete dissolution of the active was achieved. A Velp - AREC X magnet and magnetic stirrer were used.

Into another beaker, 2 g of 10 mole nonylphenol, 2.5 g of Emulsogen EL 360, 7 g of Emulsogen 4901 , 7 g of Wetting agent E21 F7030 and 1 g of Emulsogen 3475 were added and stirred until homogeneous. A Velp - AREC X magnet and magnetic stirrer were used.

The mixture of adjuvants was poured into the beaker containing the active dissolved in a solvent and surfactant and temperature was kept at 50°C, stirring until homogeneous. The herbicidal composition of the present invention was thereby obtained.

This procedure was repeated with 15 g of Atrazine and 20 g of Atrazine, thus obtaining three nanoemulsion-forming herbicidal compositions of the invention, with a concentration of 18.5, 15, and 20 g/100 mL.

Emulsion and stability assays were performed using CIPAC MT 36.1 and MT46 methods:

ADAPTED CIPAC MT 36.1 METHOD (CIPAC F Manual): Emulsion values of emulsifiable concentrates

Preparation®

Five mL of the emulsifying concentrate were brought up to 100 mL of aqueous emulsion by adding standard C (500 ppm) and D (342 ppm) water at 30°C. In the case of using a final volume of 60 mL, the ratio was of about 55:5 mL water/emulsifiable composition.

Stability of this emulsion was evaluated in terms of free amounts of "oil" or "cream" in the emulsion after standing undisturbed for 30 min., 2 h, and 24 h in a bath at 30°C. The ability of the system to re-emulsify at the end of the 24 hs period was also determined. To achieve this, 10 inversions were carried out.

Initial emulsion

A 100 mL cylinder was filled with 95 mL of standard water at 30±1°C, the emulsifying concentrate was carefully poured onto the surface of the water (5 mL at the same temperature as the water). The cylinder wass capped and inverted once.

Emulsion stability

The cylinder was inverted 10 times and left to stand undisturbed at constant temperature in a bath at 30±1 °C for 24 hs. The sample was kept if there was free oil, foam or cream on the surface or at the bottom of the emulsion after standing for 30 min., 2 hs, and 24 hs.

Re-emulsion after 24h

After the 24 hs period was completed, the material was inverted times andleft to stand for 30 sec. Presence of free oil, foam, cream or solid matter was verified 24 hs after re-emulsion, resulting in 100 mL of an emulsion that was uniform by visual examination.

Final stability of the emulsion

The emulsion was left to stand for additional 30 minutes to analyze and save the volume if free oil, foam, cream or solid matter appeared.

ADAPTED CIPAC MT 46 METHOD (CIPAC F Manual): Process of accelerated storage):

Emulsifying concentrates

Introduction to the method:

The concentrate was stored in a bottle with screw cap in an oven at a certain temperature and time.

Equipment: Thermostat-controlled oven at a predetermined temperature of 54°C ± 2°C.

125 mL glass bottles with screw caps and a polyethylene insert.

Procedure

The emulsifying concentrate (about 100 mL) was placed in the bottle, with the polyethylene insert, and left uncapped in the oven; after half an hour the bottle was capped and allowed to stand for a specific time of 2 weeks. Once this period was completed, the bottle was removed from the oven and allowed to naturally reach room temperature, then the cap was removed. Specific assays were performed corresponding to the general methods for emulsifying concentrates within 24 hs of cooling.

Embodiment of the present example:

The herbicidal composition of the present invention, in the embodiment detailed in this example, was emulsified in water, by inverting the tube as specified by the cited standards. These assays of emulsion formation and determination of stability and quality were carried out in containers to which water had been added to complete 60 mL.

The results of comparative assays carried out with the composition of the present invention (4, 11 , and 18) emulsified in water to obtain the formulations of the present invention are shown in Table 2.

Formulations 1 to 3 were obtained with the commercial 50% Atrazine which, as may be seen, has very limited stability properties.

The combination formulations of the present invention were prepared as in the field, because Atrazine is usually applied together with glyphosate and 2,4D.

Table 2 shows how the different formulations of the present invention were prepared by combining the emulsified composition of the present invention with other herbicides, such as glyphosate (as a liquid solution or as a microemulsion) and 2,4D (as a microemulsion).

Table 2:

Table 2

50% w/v Atrazine CS: Concentrated suspension of 50% w/v Atrazine from Red Surcos (Brand: Maizal®).

66.2% w/v Glyphosate Potassium salt SL: Soluble liquid concentrate of 66.2% w/v glyphosate from Red Surcos (Eskoba full®).

30% w/v 2,4 D; ME: Microemulsion of 30% w/v 2,4-D dichlorophenoxyacetic acid from Red Surcos (Dedalo Elite®).

11 % w/v Glyphosate; ME: Microemulsion of 11 % glyphosate from Red Surcos (formulation of Patent AR111685A1 ). Result:

The composition of the present invention comprises a range of Atrazine concentrations from 15% to 21 %. Table 2 shows that at this range of concentrations formulations in water comprise a very stable nanoemulsion for 24 hs at concentrations from 15% to 18% and for 12 hs at concentrations of 20% Atrazine. This indicates that at higher concentrations stability will continue decreasing. That is, in the claimed range the nanoemulsion of the invention has a stability of at least 12 hs.

And for formulations including 2,4D and/or glyphosate, the stability is of more than three hours when Atrazine concentration is 15% and 18.0% w/v, whereas for the composition of 20% (w/v) stability of the combinations is of more than an hour, preferably of more than two hours.

In all cases, the nanoemulsion is homogeneous and has cream-forming ability. The stability times indicated for the formulations of the present invention correspond to an oily part that rises to the surface forming a cream, but two phases are not completely formed without appearance of sediments or precipitates, which demonstrates that the obtained formulation may rapidly form the emulsion once again.

Other relevant data observed in this assay is that the composition of the present invention forms a nanoemulsion which is stable and compatible with other formulations as may be the case of liquid suspensions (LS), microemulsions (ME) and emulsifiable concentrates (EC), for example.

Example 8: Preparation of a terbuthylazinenanoemulsion-forming herbicidal composition of the invention, at a final concentration of 20.0% w/v The terbuthylazine herbicidal composition of the present invention is prepared by adding it to the solvent (N-methylpyrrolidone, Wetting agent G and Wetting agent F respectively (as may be seen in table 3) of this example, heating to 50°C and stirring up to complete dissolution. Then the other adjuvants and water are added to the corresponding formulations, maintaining temperature and stirring. Final volume was of 100 mL.

Table 3:

The same stability assays were applied as in example 7 and all the formulations of the invention maintained a nanoemulsion stability of at least 12 hours.

Example 9: Retention assay of 18% w/v Atrazine of the present invention on soybean stubble Materials

250 mL beaker - Mosquito net - mesh #14 (prepared with a concave shape having a central depth of about 3 cm and total diameter of 8 cm)

Soybean stubble Hard water (500 mg/kg as CaCO3)

Magnetic stirrer

Magnet

Preparation:

Stubble was cut to a length of 3 cm, trying to select different diameters, but discarding thick stalks. Stubbles were arranged in the net so as to achieve a central height of 2.5 cm, but with a minimum layer at the borders. Diameter of stubbles should not exceed 7 cm in diameter. Weight added per stubble was controlled to be 2.30 g in all trials.

One hundred mL of the formulation of the invention were prepared, al 5% w/v of the composition of example 3, which was nanoemulsified in water. It was homogenized in the beaker with the magnet and an aliquot was taken and stored (taken as an initial sample of 10 mL to verify concentration by HPLC).

Methodology

The formulation of the invention, prepared in the previous paragraph, was poured onto the prepared stubble bed taking care that it was all wet and that it was not all in the center, as may be seen in the photograph of figure 3.

It was left to drain until no falling droplets were observed, and the stubble filter was removed; a magnet was placed in the beaker to homogenize the remaining formulation and then a sample was taken (it is taken as a 10 mL final sample to verify concentration by HPLC).

A comparison was carried out once the two concentration readings were obtained, one of the prepared formulation and the other of the formulation that passed through the stubble filter. For concentrated suspensions, which are those currently marketed, such as, for example 50% w/v Atrazine CS from Red Surcos, all the final samples resulted in lower concentration of active as compared to initial samples.

Percentages of loss of active is calculated and reported as % retained on stubble.

Table 4:

MAIZAL® is a 50% concentrated suspension (50% w/v Atrazine CS, from REDSURCOS, 50% w/v 500 g/L atrazine concentrated suspension).

The advantage of the herbicidal composition of the present invention is clearly noted when compared to a standard commercial formulation regarding amount of active matter retained on the stubble not reaching the soil. This is a result of the excellent physicochemical properties achieved by the composition of the present invention. By applying the composition of the present invention it is possible to save at least 5% of active matter in the application because the resulting emulsion runs down the stubble and does not stick to it, thus reaching its site of action in its entirety.

EXAMPLE 10: EFFICACY EVALUATION OF THE HERBICIDAL COMPOSITION OF THE PRESENT INVENTION CONTAINING 18% W/V ATRAZINE, FOR WEED CONTROL IN A MAIZE CROP.

A. IDENTIFICATION OF THE TRIAL

Agricultural campaign: 2017/2018

Locations: Balcarce and Ferre, Buenos Aires, Argentina; Margarita, Santa Fe, Argentina. B. OBJECTIVE: Determination of efficacy of the herbicidal composition of the present invention- The active ingredientwas Atrazine at a concentration of 18% w/v, prepared according to example 2 for pre-emergence weed control in a maize crop. C. EXPERIMENTAL CONDITIONS

C.1 : Information about the crop used in the trial.

Table 5:

C.2: Geographic location and agroecological characteristics.

Geographic location of the trials: Trial Location and Province

Balcarce, Buenos Aires

Ferre, Buenos Aires

Margarita, Santa Fe

C.3: Experimental design In a completely randomized block design with four repetitions, three meters wide and seven meters long plots were marked with one meter matched controls and the treatments described below were applied:

Table 6: Description of tested treatments

C.4: Application

C.4.1 : Application details

The tested herbicides were broadcast sprayed using an application volume of 120 L ha-1. A CO2 spraying backpack and four flat fan tips TTI 110- 015 were used for this purpose. In all cases, working pressure was of 2 bars and the distance between nozzles was 0.52 m. No unusual weather events affecting quality of the trial occurred.

D.1.2: Efficacy

Efficacy of control of the treatments on weeds 15, 20, and 45 days after the day of application (DDA) was evaluated. The percentage of herbicidal control was determined by counting the seedlings that emerged in the plot relative to seedlings emerging in the matched control.

D.2: Statistical Analysis

An analysis of variance (ANOVA) was performed using as rating variables the treatments and test replicates, and as dependent variable the control exerted on the weeds. Means were compared using Fisher’s test for p < 0.05. The statistical program InfoStat was used (2016).

Table 7: Results of control by the 18% Atrazine herbicide on weeds present in a maize crop located in Balcarce (Buenos Aires). Action onViola arvensis was particularly evaluated:

*1 Mean comparison test

The formulation of the present invention (Atrazine 18 g/L) corresponding to example 2, shows results comparable to those obtained with the control using 50% w/v Atrazine (Maizal®) and thus the efficacy of the present invention is observed, where at a lower concentration a similar effect on the weed Viola arvensis is observed.

Results of the control exerted by the 18% Atrazine herbicide of the present invention on weeds present in a maize crop located at Ferre (Buenos Aires) were evaluated. In particular action on Chenopodium album was evaluated (Table 8). Table 8:

*1 Mean comparison test

Results of control by the 18% Atrazine herbicide of the present invention on weeds present in a maize crop located at Margarita (Santa Fe) were evaluated. Action on Portulacaoleracea was particularly evaluated (Table 9). Table 9:

*1 Mean comparison test

Surprisingly the formulation of the invention achieved a higher efficiency when applied at a concentration of active matter of 81 .0 g of Atrazine per hectare (EC4500) and 90.0 g/ha (EC5000) for removing Portulacaoleracea, whereas the rate of the chemical control was 200 g/ha.

This assay clearly shows that the special properties of the formulation of the invention provide surprising results over the state of the art, which go far beyond of what a person skilled in the art could have expected when combining the knowledge of the prior art.

EXAMPLE 11 : EFFICACY EVALUATION OF THE COMPOSITION OF

THE INVENTION CONTAINING 18% W/V ATRAZINE, FOR WEED CONTROL IN A MAIZE CROP.

Late seeding.

Tested crop: Maize DM2771 VT3Pro.

Location: San Guillermo, San Cristobal dept., Santa Fe province.

Efficacy was evaluated for the following weeds: Conyzabonariensis, Amaranthusquitensis, Medicago sativa, and Gomphrenapulcella:

Crop: Late seeding maize crop DM2771VT3Pro, planted on January 6, 2016, with degraded pasture as predecessor. Plot with reduced tillage and superficial removal in early spring. Application performed on January 8, 2016.

SITE: San Guillermo, San Cristobal dept., Santa Fe province, soil use class IVw, type II environment. Weed monitoring: the survey was carried out by exploring the 58 ha plot bi-weekly, walking along an X-shaped path and taking readings within a radius of 2 meters per sample, for a total of 1 sample every 10 hectares.

In each sampling unit, species were identified at the moment of application, and quantified:

Abundance: Scarce: 1 individual

Not very abundant: 2-3 individuals

Abundant: more than 3 individuals per sampling unit

Status: Young/adult (vegetative/reproductive) Frequency: Number of samples where the species is found/total Number of samples.

Sampling 15 days after application. Percentage of survival of each species susceptible to the tested product and percentage of damage of vegetative structures remaining after the application. Tabla 10: RESULT OF THE INITIAL SURVEY:

Tabla 11 : EVALUATION 15 DAYS AFTER APPLICATION (01/23/2016):

(S): Percentage of individuals surviving application of each tested species, average of each repetition.

(DR): Damage to remaining vegetative structures of surviving weeds 15 days post-application, average of each repetition. Scale from 0 (no damage) to 5 (weed alive but without healthy remaining structures).

From this test it is clear that the composition of the invention (the composition corresponding to example 2), as a formulation nanoemulsified in water has a higher herbicidal power than the standard commercial product of 50% Atrazine (Maizal®). Consequently, the present invention has more power at a lower concentration of active matter, showing an evident synergy among the components used in the present invention.

EXAMPLE 12: WEED CONTROL OF THE COMPOSITION OF THE INVENTION ON EARLY SEEDING MAIZE CROP DOW 507 PW

Tested crop: MAIZE DOW 507 PW.

Location: Eusebia, Castellanos dept., Santa Fe province.

Efficacy was evaluated for the following weeds: Conyzabonariensis, Amaranthusquitensis, Parietariadebilis, and Gomphrenapulcella.

CROP: Early seeding maize crop Dow 507 PW, planted on September 20, 2016, on second ’15-’16 wheat/soybean predecessor. Direct seeding plot, with glyphosate-based applications on long fallow and water logging symptoms at preharvest of the predecessor crop. Application performed on September 20, 2016.

SITE: Eusebia, Castellanos Department, Santa Fe Province, soil use class lllwe, type II environment.

Table 12: PROPOSED TREATMENTS:

In this example 18% Atrazine EC corresponds to the composition obtained in example 3.

WEED MONITORING: the survey was carried out by exploring the complete 32 ha plot, bi-weekly, walking along an X-shaped path and taking readings within a radius of 2 meters per sample, for an approximate total of 1 sample every 10 hectares.

Abundance: Scarce: 1 individual

Not very abundant: 2-3 individuals

Abundant: more than 3 individuals per sampling unit

Status: Young/adult (vegetative/reproductive)

Frequency: Number of samples where the species is found/total number of samples

Sampling is carried out 20 days after application. Percentage of survival of each species susceptible to the tested product and percentage of damage of vegetative structures remaining after the application.

Table 13: RESULT OF THE INITIAL SURVEY:

Species found Abundance Status Occurrenc

(ave/sample) frequency

(S): Percentage of individuals surviving application of each tested species, average of each repetition. (DR): Damage to remaining vegetative structures of surviving weeds 15 days post-application, average of each repetition. Scale from 0 (no damage) to 5 (weed alive but without healthy remaining structures).

It should be noted that 5.5 L/ha of the composition of the invention according to example 3 are equivalent to 102 g of Atrazine per ha, whereas 4 L/ha of commercial 50% Atrazine are equivalent to 200 g/ha. Then it is clear that the formulation of the invention, prepared with the composition of the invention, comprises half of the active matter to achieve the same effect in the field. A truly unexpected technical effect for any expert in the art is thus demonstrated.

Claims

1. An herbicidal chloro-triazine composition, in the form of an emulsion-forming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising chloro-triazine at a concentration from 15% to 21 % w/v, a solvent at a concentration from 50% to 70% w/v, an adjuvant at a concentration from 1 % to 20% w/v, and a surfactant at a concentration from 1 % to 21 .00% w/v.

2. The herbicidal composition of claim 1 , wherein said chloro-triazine is selected from the group comprising atrazine, terbuthylazine and mixtures thereof.

3. The herbicidal composition of claim 1 , wherein said solvent is selected from the group comprising N-methylpyrrolidone, isophorone, dimethylsulfoxide, cyclohexanone, 1 ,3-dioxolane (1 ,3-dioxacyclopentane), Solketal (2,2-dimethyl-1 ,3-dioxolan-4-yl)methanol, soy and coconut fatty acid aminoamide, ethanol, dimethylacetamide, dimethylamide, ethanol, ethyl lactate and mixtures thereof.

4. The herbicidal composition of claim 1 , wherein said adjuvant is selected from the group comprising xylene, soy aminoamide of fatty acid methyl esters, 15 mole ethoxylated coconut fatty amine, 15 mole ethoxylated T150 fatty amine, 15 mole and 20 mole ethoxylated tallow fatty amine, ethoxylated castor oil with 36 moles of ethoxylation, soy fatty acid methyl esters, 60% calcium phenylsulfonate, n-butanolalkoxylate, 36 mole ethoxylated castor oil, fatty alcohol polyglycol ether , 6 mole ethoxylatedisotridecyl alcohol, tristyrylethoxylate , tristyrylphenolethoxylate , azeotropicmixture of ethyl acetate:ethanol, 2,4,6-Tri- (1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt and mixtures thereof .

5. The herbicidal composition of claim 1 , wherein said surfactant is selected from the group comprising 6 mole ethoxylatedisotridecyl alcohol, N,N- dimethyldecan-1 -amide and N,N-dimethyloctaneamide, 20 mole and 54 mole ethoxylatedtristyrylphenol, 10 mole ethoxylatednonylphenol and mixtures thereof.

6. The herbicidal composition of claim 1 , comprising water.

7. The herbicidal composition of claim 1 , not comprising added water.

8. A nanoemulsion stable for at least 12 hs, comprising the composition of claim 1 emulsified in water at a concentration from 2% to 5% (v/v).

9. The nanoemulsion of claim 8, comprising a particle size from 40 to 100 nanometers.

10. The nanoemulsion of claim 8, stable for at least 1 hour, characterized in that it maintains its redispersing ability, even if it contains other agrochemicals selected from the group comprising 2,4D, glyphosate, glyphosate potassium salt, and mixtures thereof.

11. A nanoemulsified herbicide formulation, comprising the composition of claim 1 emulsified in water, at a concentration from 2% to 5% (v/v).

12. The nanoemulsified herbicide formulation of claim 11 , characterized in that it maintains its stability for at least 1 hour and its redispersing ability, even if it contains other agrochemicals selected from the group comprasing of 2,4D, glyphosate, glyphosate potassium salt, and mixtures thereof.

13. A treatment of crops selected from the group comprising corn, soybean, wheat, rice, rapeseed, sugarcane, sorghum, flax, fallow, and tea, comprising dispersing the formulation of claim 11 over the crop-producing fields at a concentration of less than 108 g of atrazine per hectare.

14. The treatment of crops according to claim 13, wherein said treatment is selected from the group comprising a pre-emergence treatment and a post-emergence treatment for reducing weeds.

15. The treatment of crops according to claim 14, wherein said weeds are selected from the group comprising common purslane (Portulacaoleracea), nettle (Urticaurens), swinecress (Coronopusdidymus), chamomile (Anthemiscotula), sowthistle (Sonchusoleraceus), shepherd’s purse (Capsellabursa-pastoris), common knotgrass (Polygonumaviculare), climbing buckwheat (Polygonum convolvulus), chickweed (Stellaria media), foxtail (Setariaspp), fierce thornapple (Daturaferox), pigweed (Amaranthusspp), turnip (Brassicaspp), curled dock (Rumexcrispus), large thistle (Xanthium cavanillesi), annual bluegrass (Poaannua), goosefoot (Chenopodiumspp), sticky nightshade (Solanumsisymbriifolium), hoary bowlesia (Bowlesiatenera), black clover (Medicagolupulina), Rhodes grass (Chlorisgayana), knotgrass (Paspalumdistichum), spiny cocklebur (Xanthium spinosum), pinweed (Erodiumcicutarium), barnyardgrass (Echinochloaspp).

16. A manufacturing process of the composition of claim 1 , comprising the following steps: a. obtaining said chloro-triazine; b. mixing the chloro-triazine of step a. with at least one solvent and a surfactant under stirring and heating until complete dissolution; c. adding adjuvants to the mixture of step b. under stirring and optionally heating; d. allowing to cool.

17. The process of claim 16, wherein said solvent is selected from the group comprising N-methylpyrrolidone, isophorone, dimethylsulfoxide, cyclohexanone, 1 ,3-dioxolane (1 ,3-dioxacyclopentane), Solketal (2,2-dimethyl- 1 ,3-dioxolan-4-yl)methanol, soy and coconut fatty acid aminoamide, ethanol, dimethylacetamide, dimethylamide, ethanol, ethyl lactate and mixtures thereof.

18. The process of claim 16, wherein said solvent comprises N- methylpyrrolidone.

19. The process of claim 16, wherein said adjuvant is selected from the group comprising xylene, soy aminoamide of fatty acid methyl esters, 15 mole ethoxylated coconut fatty amine, 15 mole ethoxylated fatty amine , 15 mole and 20 mole ethoxylated tallow fatty amine, ethoxylated castor oil with 36 moles of ethoxylation, soy fatty acid methyl esters, 60% calcium phenylsulfonate, n- butanolalkoxylate, 36 mole ethoxylated castor oil ; fatty alcohol polyglycol ether, 6 mole ethoxylatedisotridecyl alcohol, tristyrylethoxylate, tristyrylphenolethoxylate , azeotropicmixture of ethyl acetate:ethanol, 2,4,6-Tri- (1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt and mixtures thereof.

20. The process of claim 16, wherein said non-ionic surfactant is selected from the group comprising 6 mole ethoxylatedisotridecyl alcohol, N,N- dimethyldecan-1 -amide and N,N-dimethyloctaneamide, 20 mole and 54 mole ethoxylatedtristyrylphenol, 10 mole ethoxylatednonylphenol and mixtures thereof.

21. The process of claim 16, characterized in that further water is added.

22. The process of claim 16, characterized in that it is carried out at a temperature of 50°C.

23. A manufacturing process of the formulation of claim 11 , comprising the following steps: a. disposing water in a tank; b. adding the composition of claim 1 to the water of step a., under stirring; c. stirring until a homogeneous nanoemulsified ready-to-use formulation is obtained.

24. An atrazine herbicidal composition, in the form of an emulsionforming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising atrazine at a concentration from 15% to 21 % w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, xylene at a concentration from 0% to 20% w/v, and 10 mole ethoxylatednonylphenol at a concentration from 1 % to 21 % w/v.

25. An atrazine herbicidal composition, in the form of an emulsionforming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising atrazine at a concentration from 15% to 20% w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, N,N dimethyldecan-1 -amide and N,N dimethyloctaneamide at a concentration from 1 % to 3% w/v, 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration from 1 % to 3% w/v and ethoxylated T150 fatty amine at a concentration from 10% to 16% w/v.

26. An atrazine herbicidal composition, in the form of an emulsionforming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising atrazine at a concentration of 18% w/v, N- methylpyrrolidone at a concentration from 50% to 70% w/v, N,N dimethyldecan- 1 -amide and N,N dimethyloctaneamide at a concentration of 2% w/v, 2,4,6-Tri- (l -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration of 2% w/v and ethoxylated T150 fatty amine at a concentration of 13% w/v.

27. An atrazine herbicidal composition, in the form of an emulsionforming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising atrazine at a concentration of 18% w/v, N- methylpyrrolidone at a concentration from 50% to 79% w/v, N,N-dimethyldecan- 1 -amide and N,N-dimethyloctaneamide at a concentration from 1 % to 3% w/v; soy fatty acid methyl esters at a concentration from 1 % to 3% w/v, 15 mole ethoxylated coconut fatty amine at a concentration from 10% to 16% w/v and 2,4,6-Tri-(1-phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration from 1 % to 3% w/v.

28. An atrazine herbicidal composition, in the form of an emulsionforming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising atrazine at a concentration of 18% w/v, N- methylpyrrolidone at a concentration of 68% w/v, N,N-dimethyldecan-1 -amide and N,N-dimethyloctaneamide at a concentration of 2% w/v; soy fatty acid methyl esters at a concentration of 2% w/v, 15 mole ethoxylated coconut fatty amine at a concentration of 13% w/v and 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration of 2% w/v.

29. An atrazine herbicidal composition, in the form of an emulsionforming concentrate, that generates a nanoemulsion having an extended stability of at least 12 hours, comprising atrazine at a concentration from 15% to 20% w/v, N-methylpyrrolidone at a concentration from 50% to 70% w/v, a mixture of ethyl acetate: ethanol (50:50) at a concentration from 1 % to 10% w/v, 10 mole nonylphenol at a concentration from 1 % to 3% w/v, 36 mole ethoxylated castor oil at a concentration of 2.5% w/v, n-butanolalkoxylate at a concentration of 7% w/v, soy and coconut aminoamide of fatty acid methyl esters at a concentration of 7% w/v, 2,4,6-Tri-(1 -phenylethyl)-phenol ester phosphoric polyglycol ether triethanolamine salt at a concentration of 1 % w/v.