CONCENTRATED HERBICIDE COMPOSITION OF GLUFOSINATE AND DIURON, FORMULATION AND METHOD FIELD OF INVENTION [0001] The present invention relates to concentrated agricultural herbicide compositions and formulations containing glufosinate and diuron and a treatment method using said compositions and formulations in the management and control of weeds susceptible, tolerant and resistant to EPSPS inhibiting herbicides (glyphosate), ALS inhibitors (chlorimuron and others) and ACCase inhibitors (clethodim, haloxyfop and others) in different agricultural crops. STATE OF THE ART [0002] According to the Food and Agriculture Organization of the United Nations (FAO), the world’s population is currently 7 billion and is expected to reach 10 billion by 2050, requiring a 70% increase in food production. Brazil is the main player in meeting this global demand and needs to increase its production by 40%. The FAO warns that in order to meet this demand, countries will have to invest approximately US$44 billion a year in food production and distribution, five times more than the US$7.9 billion currently invested (FAO, 2020). [0003] With this investment, food production is expected to grow by 60%, and it is also estimated that the agricultural area will expand by 144 million hectares, 107 million of which will be in developing countries and another 37 million hectares in developed countries, which is what is needed to meet this demand (FAO, 2020). However, several regions of the world will face problems in expanding areas for farming, due to the limitations of physical space, low-fertility soils and scarce water sources, as well as constant climate change, all of which will be significant obstacles to food production in the future. Countries such as Brazil, the United States of America, Argentina
and China are becoming more important in the agricultural scene, especially considering the soybean crop, with USDA forecasts for the 2019/20 harvest of 124.50, 96.84, 52.00 and 18.10 million tons, respectively (USDA 2020). The United States, Brazil and Argentina are the three main producers and exporters of soybeans, guaranteeing 80.8% of the world’s supply (USDA 2020). [0004] In addition to these facts, the challenges of meeting the demand for food as the population expands are even greater, considering the need to have high agricultural yields, with maximum efficiency in the use of areas and agricultural inputs such as fertilizers and agrochemicals, thus reducing productivity losses due to pests, diseases and weeds. [0005] Weed interference can cause significant yield reductions in different agricultural crops (20 to 90%). In addition to interfering with productivity, as they compete with crops for water, light and nutrients, weeds can also affect the quality of agricultural products, as well as being hosts to pests and diseases, among other negative impacts. [0006] The evolution of the production system with soybean cultivars(Glycine max) tolerant to glyphosate herbicide has made it possible to widely use this herbicide in post-emergence soybeans, initially giving farmers the opportunity to control weeds easily, efficiently and at a relatively low cost (Vargas et al. 2007). [0007] Constantin et al (2013) and Toledo et al. (2014) report the existence of some cases in which the cost of herbicides was reduced by more than 80%, making it viable to grow soybeans in some difficult years, such as 2005. [0008] Researchers such as Vargas et al., 2007; Moreira et al., 2010; Constantin et al, 2013, among others, consider that glyphosate-tolerant soybean technology is an efficient alternative for managing weeds resistant to ALS-inhibiting herbicides, such as milkweed (Euphorbia heterophylla) and black jack (Bidens pilosa and Bidens subalternans) in soybean
cultivation, since glyphosate has a different mechanism of action (EPSP inhibitor) than those that have been used to selectively control these weeds in the soybean crop (Vargas et al, 2007, Constantin et al, 2013 and Toledo et al, 2014). [0009] However, in these production systems with glyphosate- tolerant soybeans and where crop rotation and alternative herbicides are not practiced, the exclusive and continuous use of glyphosate from 2005 onwards has shown significant increases in the process of evolution of resistant weed populations (Heap, 2015), as well as in the strong selection pressure of species that are tolerant or not very susceptible to glyphosate, such as different species of cordgrass (Ipomoea sp and Merremia sp), ragweed (Commelina bengalensis) and even some populations of milkweed (E. heterophylla), which can limit or compromise the benefits of this technology (Toledo et al, 2014). [0010] The evolution of herbicide-resistant weed biotypes is conditioned by a genetic change in the population, and these biotypes are selected through the selection pressure imposed by the herbicide applied repeatedly in the area, surviving the action of this product at the recommended dose. As a result, the population of resistant weeds increases to the point where the level of control is compromised. In less than 30 years, after the first case of resistance, there were more than 100 species confirmed as resistant in around 40 countries. Many other cases have been reported in different parts of the world as reported by Heap (2015). [0011] Farmers have thus been surprised by the rapid selection of weed species in response to the repeated use of glyphosate (Vargas et al. 2007), despite the arguments and the classification of glyphosate as a low-risk product for the selection of resistant weed species, today there are already more than 20 species resistant to this herbicide in the world, with nine of them identified in the last four years (Constantin et al, 2013).
[0012] Among the species with resistance to glyphosate, horseweed (Conyza sp) is very important in some regions of the world, such as the United States, where the resistant biotype occurs in a large part of the so-called “corn, cotton and soybean belts”, and in Brazil, where resistance to glyphosate has already been confirmed in populations of both Conyza bonariensis and Conyza canadenses (Vargas et al, 2007; Moreira et al, 2010). It is known that horseweed appears with great frequency in most soybean and corn-growing regions in our country, which further increases concern about this problem (Vargas et al. 2007; Constantim et al. 2013; Toledo et al., 2014). [0013] It is important to note that in Brazil, as in the United States of America, horseweed (Conyza sp) was not considered important for agriculture and is now widespread in practically all producing regions, from the states of Rio Grande do Sul, Paraná, São Paulo to the Cerrado regions. Due to its high competitive potential, significant reductions in soybean yields of up to 40% have been observed (Toledo et al, 2014). However, there are reports in the literature of weeds of the species Conyza bonariensis, Conyza canadenses and Conyza sumatrensis, popularly known as horseweed, which, when in very high densities, reduced the yield of soybeans grown in direct sowing by 83%. [0014] Autumnal management of glyphosate-resistant horseweed (Conyza sp) should be carried out in fallow areas after the harvest, i.e. in the off-season, when the period between harvesting the crop and sowing soya is relatively long (40 to 90 days). This management is essential to reduce the seed production of resistant weed plants. However, there is a need to study the possible effects of this management on other weeds that are difficult to control, tolerant and/or with different levels of susceptibility to glyphosate, thus allowing for clean sowing of soybeans (Oliveira Junior et al, 2011; Constantin et al, 2013). [0015] The application of herbicides in autumn and/or off-
season management should be carried out in the early stages of horseweed development, when the plants are more sensitive to these herbicides (Oliveira Junior et al, 2011). [0016] In summary, autumn and pre-sowing management of soybeans using the herbicide paraquat in association or not with other pre-emergent herbicides (diclosulam, sulfentrazone, flumioxazin and others) is an alternative for managing and controlling weeds susceptible, tolerant and resistant to glyphosate and other herbicides. [0017] The herbicide paraquat is a water-soluble salt that rapidly desiccates all green tissue it comes into contact with. It is widely used in agriculture and is not volatile, explosive or flammable in aqueous solution (PERON et al., 2003). Its salts are strong electrolytes which, in solution, dissociate into a large number of positive and negative ions (SERRA et al., 2003). [0018] Its common name is paraquat, with a chemical nomenclature of 1,1’-dimethyl4,4’-bipyridinium, a gross formula of C12H14N2 and a structural formula:
[0019] This herbicide belongs to the bipyridyl chemical group, molecules with activity related to the formation of superoxide radicals (O
2-), whose detoxification by the enzyme superoxide dismutase results in the formation of hydrogen peroxide (H
2O
2), which peroxidizes lipids and damages chloroplast membranes and cells (VIDAL, 1997). [0020] Paraquat acts in the presence of light, dehydrating the green parts of all plants it comes into contact with, and after application penetration occurs almost immediately. Paraquat’s site of action is the chloroplast containing the plant’s photosynthetic systems that absorb the light energy used to produce sugars. This herbicide is known to act on the photosynthetic membrane system, called Photosystem I. The free
electrons in Photosystem I react with the paraquat ion, resulting in the form of a free radical. Oxygen quickly reconverts this radical and in the process produces highly reactive superoxide, which attacks the unsaturated fatty acids in the membranes, rapidly opening up and dehydrating the cell membranes and tissues. The free radical paraquat ion process then recycles itself, producing greater quantities of superoxide until the supply of free electrons ceases. [0021] Studies have shown that when paraquat residues come into contact with soil, the active ingredient of paraquat is rapidly absorbed and binds strongly to soil and soil organic matter, becoming biologically inert and, as a result, cannot be absorbed by plant roots or other organisms. Soils treated with paraquat continue to maintain an active ecosystem in the soil, with no adverse effects on soil microorganisms and earthworms. Paraquat cannot be released from the soil or reactivated by the application of water or other agrochemicals. All agricultural soils have a high capacity to absorb paraquat. [0022] The herbicide paraquat is very fast-acting and has a broad spectrum of control of annual weeds and suppresses perennials. Its rapid action can make it possible to plant more than one crop in the same season. Despite the extensive use of paraquat (mechanism of action inhibition of photosystem I) there are few resistant weeds in Brazil, especially when compared to more recent product launches, for example, herbicides from the sulphonylurea or imidazolinone chemical groups (mechanism of action inhibition of ALS). There are proven cases of resistance to paraquat in the state of Paraná, as horseweed plants (Conyza sp) are spreading to other soybean and corn producing regions. [0023] The other important broad-spectrum ‘non-selective’ herbicide, glyphosate, presents a growing problem with resistant weeds (EPSPs). Paraquat was seen by many farmers and scientists as an essential element in managing this issue, as it provided a non-selective alternative.
[0024] The herbicide paraquat quickly penetrates the leaves before the rain can remove significant amounts of the product. [0025] Unlike most herbicides, paraquat is also effective at low temperatures, when weeds have little active growth. Paraquat only acts on contact. The sprayed plant tissues are destroyed so quickly that no significant amount translocates from the leaves to the more distant unsprayed parts, such as roots, vegetative points and grains. [0026] In the soil, paraquat is deactivated biologically by being rapidly and strongly absorbed by soil particles. The absence of ‘residual’ activity in the soil means that paraquat can be applied before crops are planted or seedlings emerge. [0027] Despite the beneficial aspects of the herbicide paraquat in weed management, there are critical aspects related to health and safety for workers that led to the product being banned in Brazil in September 2020. This has made the management of glyphosate-resistant weeds more complex and difficult, requiring significant investment in research and development so that new herbicides can be introduced as an alternative for controlling weeds susceptible, tolerant and resistant to glyphosate and other herbicides. [0028] To this end, a concentrated herbicide composition was developed containing the active ingredients glufosinate + diuron and formulations and method for controlling susceptible, tolerant and resistant weeds to the main herbicides and in different agricultural crops. As used in this document, the term “and/or any and all combinations” of one or more of the associated listed elements. On the combination of active ingredients [0029] Glufosinate is a broad-spectrum herbicide used to control various weed species in post-emergence and is also used as a pre-harvest desiccant for some crops such as soya, cotton, beans and sugar cane. Glufosinate is an ammonium salt derived from phosphinothricin, a natural microbial toxin isolated from
two species of Streptomyces fungi. This product is an amino acid containing phosphorus. The mode of action of glufosinate is contact action on weeds and by altering the ammonium metabolism, in the first case it destroys the tissues of the epidermis of the leaves, and in the second case as a mechanism of action this herbicide acts by inhibiting the activity of the enzyme glutamine synthetase (GS), which is responsible for the reaction of ammonia (NH
3) formed in the cell (in the process of nitrate reduction, photorespiration and aminoacid metabolism) such as glutamic acid for the formation of glutamine,which results in an increase in the concentration of NH
2 in the cell and consequent cell death, since ammonia is mainly produced during the reaction related to photosynthetic electron transport, and accumulation is greater in plants exposed to light than in the absence of light. The first symptom of phytotoxicity in the plant is yellowing of the leaves and other green tissues of the plant followed by wilting and death of the weed, a process that takes approximately 1 to 2 weeks. [0030] With regard to glufosinate, it should also be noted that it is a herbicide that is rapidly degraded by microorganisms in the soil or on the surface of the water to 3- methylsphinicorpropionic acid and finally to CO
2, making it very safe for planting various crops, with no residual that harms the development of these crops, i.e. no carryover effect. [0031] Another important point that was considered when selecting this active ingredient in the herbicide composition was its physicochemical characteristics, such as not being flammable, having high solubility in water (SW), density, vapour pressure, pKa and Kow, which characterize a product with excellent behaviour in the soil and in the plant. In other words, despite its high solubility and the fact that it is weakly adsorbed in the soil and has high mobility in the soil, glufosinate has not been detected with leaching problems, due to its rapid microbial degradation.
[0032] Another important piece of information in the selection process for this active ingredient (glufosinate) is the fact that it is classified as moderately toxic. [0033] The herbicide glufosinate is moderately persistent in the soil, with a half-life ranging from 3 to 42 days in some studies and up to 70 days in others (BEHRENDT et.al. 1990; FABER et al. 1997; TOMLIN, 2000; DEVOS et al. 2008). [0034] After application, a large proportion of glufosinate will be deposited on the soil. Adsorption is one of the most important factors affecting the destination of pesticides in the soil and, consequently, determining their distribution in the soil and water system (GILES et al. 1960). Glufosinate is highly soluble in water and behaves like a weak acid. On the other hand, ammonium glufosinate can be strongly adsorbed by soil rich in clay and poorly adsorbed in soil with low clay content (BEHRENDT et al. 1990; BUFFIN, 2001; AUTIO et al. 2004), showing its low mobility in soil. There is still little information available on how glufosinate dissipates in the soil. Glufosinate degrades very quickly in the soil. Field experiments with carbon-14- labeled glufosinate showed that there is no translocation in soil layers deeper than 15 cm, which is attributed to rapid biodegradation (GOETZ et al. 1983.). [0035] Photolysis of the herbicide glufosinate in water occurs relatively quickly (half-life of 8.3 days, in buffered solution at pH 7 and 25°C) when substances capable of stimulating phototransformation are absent. [0036] In relation to plant behavior, glufosinate is a substrate analogous to glutamate, inhibiting the enzyme glutamine synthetase (GS; E. C. 6.3.1.2), a central enzyme in ammonia metabolism in plants (Manderscheid & Wild, 1986). It competes for the sites where glutamate binds to glutamine synthetase where, once glufosinate succeeds, the binding becomes irreversible (Logusch et al., 1991). The irreversible binding between glufosinate ammonium and glutamine synthetase results in
the rapid accumulation, at toxic levels, of ammonia inside the cell (Kishore & Shah, 1988; Tachibana et al., 1986a). Effects such as inhibition of protein synthesis (especially the Qb protein involved in electron transport in the photosystem), toxic levels of glyoxylate, insufficient production of glutamate, aspartate and alanine, and insufficient regeneration of intermediate compounds in the C3 cycle are the main factors responsible for cell death (Lea, 1991). Studies point to differences in the susceptibility of plants to glufosinate ammonium, both due to differences in movement (absorption and translocation) and metabolism (Everman et al., 2009b; Steckel et al., 1997; Skora-Neto et al., 2000). In most species in which glufosinate absorption has been studied, peak absorption is reached 24 hours after its application (Sellers et al., 2004). Due to the similarity of glufosinate (ammonium glufosinate) with amino acids such as glutamate, it is believed that its absorption is carried out through proton cotransporters (Ullrich et al., 1990). Its action is light-dependent on various weeds (Wild & Manderscheid, 1984; Köcher, 1983). [0037] In summary, ammonium 4-[hydroxy(methyl)phosphinoyl]- DL-homoalaninate or ammonium DL-homoalanin-4- (methyl)phosphinate (glufosinate or ammonium glufosinate) is an extremely safe active ingredient to be used as an alternative in herbicides proposed for the management of weeds susceptible, tolerant and resistant to different herbicides, making it an interesting alternative for various crops. [0038] The herbicide diuron belongs to the chemical group of ureas (Group C2 - HRAC), and its mechanism of action is related to Hill synthesis, by inhibiting the evolution of oxygen from water in the presence of chloroplasts and an electron acceptor, i.e. it acts to inhibit photosystem II. Herbicides that inhibit photosynthesis are considered electron transport inhibitors (Blake, 1985), since they result in the removal or inactivation of one or more intermediate electron carriers.
[0039] The rate of CO
2 fixation declines a few hours after the application of diuron in treated susceptible plants. In tolerant plants, the rate of fixation does not drop to such low levels and returns to normal within a few days. In this case, the association with other herbicides, such as glufosinate, is essential. In sensitive cases, the rate drops to close to zero in 1 or 2 days and there is no recovery. The herbicide diuron is absorbed predominantly via the roots when applied to the soil, but can also be absorbed by the leaves when applied to the aerial part of the weeds. In the case of post-emergence weed applications, complete coverage of the plants is necessary, as translocation is limited. The fact that diuron is associated with glufosinate in a single formulation containing specific surfactants enhances the post-emergence action, as it increases foliar action in terms of absorption and translocation. [0040] Photosynthesis is inhibited by the binding of the herbicide diuron to the QB action site in the D1 protein of photosystem II, which is located in the membranes of the chloroplast thylakoids, thus blocking the transport of electrons from QA to QB. This interrupts CO
2 fixation and the production of ATP and NADPH
2, which are essential elements for plant growth. However, in most cases plant death occurs as a result of other processes, especially when combined with other herbicides such as glufosinate. [0041] Early works suggested that plants died of starvation as a result of the inhibition of the light reaction of photosynthesis. However, plants treated with diuron die faster when placed in the light than when placed in the dark. This proves that something other than the inhibition of photosynthesis is responsible for the herbicidal effect observed. The leaf chlorosis that develops after treatment is thought to be caused by lipid peroxidation, which is enhanced when combined with glufosinate in a single formulation with exclusive surfactants.
[0042] Lipids and proteins are oxidized, resulting in membrane rupture, which causes cells and organelles to dehydrate and disintegrate rapidly. [0043] Lipid peroxidation is autocatalytic and spreads to other membrane constituent lipids, such as those of the chloroplast and other structures and the loss of chlorophyll, resulting in an increase in size and disorganization of thylakoids and other cell membranes (Bartels, 1985ª). The peroxidation process basically occurs due to the interruption of energy promoted by the carotenoid pigments. The excess of triplet chlorophyll can initiate the process of lipid peroxidation through two mechanisms (Dan Hess, 1194b): the first is the direct formation of lipid radicals in the unsaturated fatty acids that make up the membranes. The second is that triplet chlorophyll can react with oxygen to produce singlet oxygen. Oxygen can then react with these radicals to initiate the peroxidation process that results in membrane damage. [0044] It is thought that there are three ways in which herbicides bind to the D1 protein, which form subgroups within this mechanism of action. The first by-product is made up of herbicides from the phenylcarbamate, pyridazinone, triazine, triazolinone and uracil chemical groups (Group C1 - HRAC), the second of herbicides from the amide and urea groups, such as diuron (Group C2 - HRAC) and the benzothiadiazinone, nitrile and phenylpyridazine groups (Group C3 - HRAC). Regardless of the specific binding site, diuron shows symptoms similar to other photosystem II inhibiting herbicides of injury progression in susceptible plants; however, when associated with glufosinate in a single formulation with exclusive surfactants, this process is accelerated. [0045] Diuron and other urea derivatives bind to proteins of a defined molecular weight at the urea site, while other herbicides, especially triazines, bind to proteins in a different way.
[0046] Diuron is a herbicide with low water solubility (42 mg/L at 25 ºC), non-ionizable (pKa = 0) and its octanol-water partition coefficient (log Kow) is 2.77 and Kow 589 mL/g. It is adsorbed by clay colloids and organic matter, and its main degradation is microbial. [0047] On the other hand, the selection of the active ingredient diuron was due to several factors: [0048] In summary, from an agronomic and health and environmental safety point of view, diuron is an extremely safe active ingredient to be used as an alternative in herbicides proposed for the management of weeds susceptible, tolerant and resistant to different herbicides, making it an interesting alternative for various crops. [0049] Patent document WO2020/188983 describes a herbicide composition comprising a PPO inhibitor and glufosinate or its salt, where the weight ratio of the PPO inhibitor to glufosinate or its salt is 1/2,000 or less. The herbicide composition can effectively control weeds with reduced damage to the crop. [0050] Document WO2018078478 describes stable agrochemical compositions comprising 2-amino-4- [hydroxy (methyl) phosphinoyl] butyric acid (glufosinate), an organosilicone adjuvant, a non-ionic surfactant and, optionally, one or more other active ingredients. A process for the preparation of such compositions and their use in weed control is also provided. [0051] Document CN108935507 describes an active farm-oriented composition and its application. The farm-oriented active composition comprises an active component A and an active component B, where active component A is fine ammonium glufosinate and active component B is selected from one or more of a weed-killing activator, an insecticidal activator and a sterilization activator. The mass ratio of active component A to active component B is (1-800):(800-1). The farm-oriented active composition can be used to prevent and treat agricultural weeds, harmful insects, fungi and the like. By combining several active
components, drug resistance can be prolonged, the spectrum of control can be expanded, the influence on the environment can be reduced and the cost of the pesticide can be lowered. [0052] Document WO2018078478 describes stable agrochemical compositions comprising 2-amino-4- [hydroxy (methyl) phosphinoyl] butyric acid (glufosinate), an organosilicone adjuvant, a non-ionic surfactant and, optionally, one or more other active ingredients. A process for the preparation of such compositions and their use in weed control is also provided. [0053] Document JP2012162477 describes a herbicidal composition that has a high herbicidal effect on various weeds. The composition comprises: a compound A-87774 or its salt isolated from a substance produced by microorganisms of the genus Streptomyces; and a second herbicide compound, and an amino acid- based herbicide compound, such as glyphosate, glufosinate and bialafos, or a herbicide compound from the bipyridium system, such as paraquat. It is formulated as a wettable powder and can be used for soil or foliage treatment. [0054] Document DE10351214 describes a synergistic herbicidal composition for selective weed control in herbicide-tolerant cotton plantations containing an optionally solvated alkali (earth) metal salt (I) of N- (4,6-dimethoxypyrimidin-2-yl) -N ‘- (3- ( 2,2,2-trifluoroethoxy) -pyridin-2-ylsulfonyl) -urea and a compound (II) selected from glyphosate (or its salt), metolachlor, S-metolachlor, prometryn, pyrithiobac-sodium, fluometuron, clomazone, glufosinate ammonium, MSMA, carfentrazone ethyl, sulfentrazone, oxyfluorfen, ametryn, pendimethalin and trifluralin. A synergistic herbicide composition for selective weed control in herbicide-tolerant cotton crops comprises (in addition to conventional inert formulation aids) an active agent mixture of: (a) a sulfonylurea salt of formula (I); and (b) a synergistic amount of a selected compound (II) of glyphosate (or its ammonium, isopropylammonium, sodium, potassium, dimethylamine, isopropylamine,
monoethanolammonium or trienium salt), metolachlor, S- metolachlor, prometryn, pyrithiobac-sodium, fluometuron, clomazone, glufosinate ammonium, MSMA, carfentrazone ethyl, sulfentrazone, oxifluorfem, ametryn, pendimethalin and trifluralin. M = alkali metal or alkaline earth metal; n = 1 or 2; r, s = 0.5, 1, 1.5, 2, 2.5 or 3; and L = ethyl acetate, acetonitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, dichloromethane, trichloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, diuronethane, methyl-tert. butyl ether, chlorobenzene, toluene or xylene. [0055] Several studies have been carried out in order to evaluate the results of these associations. SUMMARY OF THE INVENTION [0056] The present invention relates to a concentrated composition based on the herbicides glufosinate plus diuron in high concentrations, comprising a surfactant system plus components in the formulation in association with different concentrations of the active ingredients and high loading. [0057] In particular, the invention relates to compositions of glufosinate plus diuron with a high load that show reductions in herbicide losses through washing off by rainwater after application and through spray drift, deposition and spreading on the leaf surface, easier absorption and penetration of the herbicides into the leaves, and better action and speed of weed control, thus promoting greater effectiveness in the management of weeds in agricultural crops. [0058] The main objective of the present invention is to develop a composition that promotes an increase in the concentration of the herbicides glufosinate plus diuron to be applied to plants, so that in addition to their contact herbicide effect and faster control action, it also aims to reduce the
possible loss of the active ingredients present in the formulation through rainwater, thus reducing the environmental impact, as well as minimizing transport, storage and, above all, packaging disposal costs. [0059] More specifically, combinations comprising different concentrations of high-load glufosinate + diuron and a surfactant system were explored, with the aim of increasing the concentration of the herbicides, i.e. improving their efficacy and dynamics on weeds in terms of speed and final control efficacy in different production systems, for example in autumn and pre-plant management for soybean crops. [0060] However, the present invention, despite increasing the concentration of the herbicides glufosinate plus diuron, promotes greater efficacy and speed of weed control and does not compromise the planting of soybean, corn, cotton and other crops, as none of the herbicides used have a negative residual effect (carryover) on the crops, in addition to promoting greater safety for farmers, consumers and the environment. [0061] More specifically, the components of the composition of the present invention are presented in appropriately balanced proportions, thus resulting in greater agronomic efficiency in the management of weeds in different production systems, thus contributing to the preservation of the productive potential of these crops. [0062] In addition, the composition of the present invention also has low toxicity to humans and the environment, as well as low production costs. [0063] The present invention also relates to a formulation derived from said composition in the form of an Oil Dispersion (OD), so as to obtain in a single package, a ready-made formulation that is dissolved in situ, directly in the water tank suitable for spraying in the field. [0064] More specifically, therefore, the present invention also includes concentrated herbicide formulations, containing
glufosinate + diuron of high loading and suitably balanced components using a surfactant system, said formulation aimed at facilitating the deposition and spreading of the herbicides on the surface of the leaves, absorption and penetration into the leaves of the weeds, as well as greater translocation of the glufosinate in the plant. [0065] In addition, the present invention also relates to the method of eliminating or treating and controlling different weed species that are susceptible, tolerant and resistant to different herbicides in agricultural crops, through the use of formulations derived from the aforementioned herbicide composition of the present invention. BRIEF DESCRIPTION OF THE FIGURES [0066] Figure 01 illustrates the management of sourgrass (Digitaria insularis) resistant to the herbicide glyphosate. [0067] Figure 02 illustrates the management of Indian goosegrass (Eleusine indica). [0068] Figure 03 illustrates the management of black jack (Bidens pilosa). [0069] Figure 04 illustrates the management of milkweed (Euphorbia heterophylla). [0070] Figure 05 illustrates weed management considering the combinations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone on the different weeds at the 2 to 4 leaf stage. [0071] Figure 06 illustrates the graph for the management of sourgrass (Digitaria insularis) considering the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0072] Figure 07 illustrates the graph of the management of Indian goosegrass (Eleusine indica) considering the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone.
[0073] Figure 08 illustrates the graph of the management of black jack (Bidens pilosa) considering the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0074] Figure 09 illustrates the graph of milkweed (Euphorbia heterophylla) management considering the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0075] Figure 10 illustrates the management of sourgrass (Digitaria insularis) and milkweed (Euphorbia heterophylla) considering the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0076] Figure 11 illustrates the management of Indian goosegrass(Eleusine indica) and black jack (Bidens pilosa) considering the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0077] Figure 12 illustrates weed management considering the different herbicides and the associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0078] Figure 13 illustrates the graph of Morning Glory (Merremia aegyptia) management with the different associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0079] Figure 14 illustrates the graph of the management of Morning Glory (Ipomoea grandifolia) with the different associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0080] Figure 15 illustrates the graph of the management of marmalade grass (Brachiaria plantaginea) with the different associations of glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone. [0081] Figure 16 illustrates the graph of actual vs. expected control for sourgrass (Digitaria insularis), considering the Colby Equation.
[0082] Figure 17 illustrates the graph of actual vs. expected control for Indian goosegrass (Eleusine indica), considering the Colby Equation. [0083] Figure 18 illustrates the graph of actual vs. expected control for milkweed (Euphorbia heterophylla), considering the Colby Equation. [0084] Figure 19 illustrates the graph of actual vs. expected control for black jack (Bidens pilosa), considering the Colby Equation. [0085] Figure 20 illustrates the performance graph for the control of Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), blackjack (Bidens pilosa) and morning glory (Ipomoea sp.). [0086] Figure 21 illustrates the graph of the performance of glufosinate + diuron (Prototype 10) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0087] Figure 22 illustrates the graph of the performance of glufosinate + diuron (Prototype 11) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0088] Figure 23 illustrates the graph of the performance of glufosinate + diuron (Prototype 12) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0089] Figure 24 illustrates the graph of the performance of glufosinate + diuron (Prototype 13) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0090] Figure 25 illustrates the graph of the performance of glufosinate + diuron (Prototype 14) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.).
[0091] Figure 26 illustrates the graph of the performance of glufosinate + diuron (Prototype 15) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0092] Figure 27 illustrates the graph of the performance of glufosinate + diuron (Prototype 16) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0093] Figure 28 illustrates the graph of the performance of glufosinate + diuron (Prototype 17) in controlling Indian goosegrass (Eleusine indica), crabgrass (Digitaria nuda), black jack ( Bidens pilosa) and morning glory (Ipomoea sp.). [0094] Figure 29 illustrates the graph of paraquat’s performance in controlling Indian goosegrass(Eleusine indica), crabgrass (Digitaria nuda), black jack (Bidens pilosa) and morning glory (Ipomoea sp.). [0095] Figure 30 illustrates the performance of the different compositions of the glufosinate + diuron formulation (Prototypes 10 to 17) when compared to glufosinate, diuron, glufosinate combined with diuron in a tank mix and paraquat without the addition of mineral oil in controlling soybean plants (Glycine max). [0096] Figure 31 illustrates the performance of the different compositions of the glufosinate + diuron formulation (Prototypes 10 to 17) when compared to glufosinate, diuron, glufosinate combined with diuron in a tank mix and paraquat with the addition of mineral oil in controlling soybean plants (Glycine max). [0097] Figure 32 illustrates the performance of the different compositions of the glufosinate + diuron formulation (Prototypes 10 to 17) when compared to glufosinate, diuron, glufosinate combined with diuron in a tank mix and paraquat with the addition of mineral oil in controlling milkweed (Euphorbia heterophylla) plants. DETAILED DESCRIPTION OF THE INVENTION
[0098] The combination of these two active ingredients (glufosinate + diuron) in the formulations proposed and developed, with emphasis on the OD formulation – Oil Dispersion, with the concentrations developed and not limited to these limits of 50 g/L to 200 g/L, preferably 100 g of glufosinate + 10 g to 100 g, preferably 50 g of diuron per L of the formulated product. [0099] In the present invention, three types of formulation have been developed, a water-dispersible granule (WG), Oil Dispersion (OD) and concentrated suspension (SC). [0100] The advantages of developing a WG formulation are: the possibility of having a high concentration of the active ingredients, no powder formation, better chemical stability of the active ingredients and the use of components in the formulation that have the characteristic of improving the product’s performance in the field, as well as environmental safety, given the reduction in the volume of packaging and its disposal. [0101] The advantage of the SC formulation is the possibility of having a liquid formulation, little powder formation, better chemical stability of the active ingredients and the use of components in the formulation that improve the product’s performance in the field, as well as environmental safety. [0102] On the other hand, the OD formulation is based on natural and/or mineral oils, or even blends, with no organic solvents being used, which provide better homogenization of the perfectly balanced active ingredients, using components in the formulation that have the characteristic of improving the performance of the herbicide (glufosinate and diuron) in relation to speed and weed control when compared to other herbicides or to the combination of glufosinate and diuron in the spray tank in the field. [0103] In the present invention, research carried out in field conditions has shown the best performance of the product developed with the OD (Oil Dispersion) type of formulation. This
is due to the fact that we use a combination of an appropriately balanced surfactant system, with surfactants that have dispersant characteristics, wetting agents and components in the formulation with characteristics that improve the physicochemical stability of the formulation, such as dispersibility, agglomerating properties, rheological control, emulsion stabilization, humidification, suspensibility, redispersibility, ease in the manufacturing process, inhibition of crystal growth, antioxidant and formation of complexes. [0104] For the WG formulation, the formulation contains a set of surfactants based on sodium salt lignosulphonate , formaldehyde-condensed sodium alkyl naphthalene sulphonate, sodium salt diisopropylnaphthalenesulphonic acid and sodium lauryl sulphate. [0105] For the OD-type formulation we use a combination of a properly balanced surfactant system, with surfactants that have a dispersing and wetting function, consisting of a set of surfactants based on ethoxylated castor oil, dodecylbenzenesulfonic acid, calcium salt, dimethyl silicone polymer with silica and phenyl oxirane polymer with oxirane mono (dihydrogenaphosphate) decyl ethers. [0106] For the SC formulation, the formulation contains a set of surfactants based on sodium salt lignosulphonate, sulphated aromatic condensation product sodium salt and sodium lauryl sulphate. [0107] An embodiment of the present invention is a herbicidal composition characterized in that it contains (a) glufosinate or its salts at a concentration of 5.00 to 50.00 %w/w per liter of the composition; (b) diuron or its salts at a concentration of 0.50 to 30.0O %w/w per liter of the composition; (c) at least one surfactant selected from diisopropylnaphthalenesulfonic acid sodium salt, do decylbenzenesulfonic acid calcium salt, sodium lauryl sulfate, lignosulfonate sodium salt , ethoxylated castor oil, dimethyl silicone polymer with silica, phenyl oxirane
polymer with mono oxirane decyl ethers, sulphated aromatic sodium salt condensation product, sodium alkyl naphthalene sulphonate condensed from formaldehyde, at a concentration of 1.00 to 32.0%w/w per liter of the composition; (d) optionally, at least one solvent selected from soy methyl ester and water at a concentration of 7.00 to 91.65 %w/w per liter of the composition; (e) optionally, at least one defoamer selected from polydimethylsiloxane at a concentration of 0.20 to 8.00 %w/w per liter of the composition; (f) optionally, at least one filler selected from kaolin at a concentration of 5.00 to 91.00 %w/w per liter of the composition; (g) optionally, at least one thickener selected from xanthan gum at a concentration of 0.05 to 0.50 %w/w per liter of the composition; (g) optionally, at least one biocide selected from 1,2-benzisothiazolin-3-one at a concentration of 0. 10 to 0.50 %w/w per liter of the composition; (g) optionally, at least one antifreeze selected from propylene glycol at a concentration of 1.00 to 10.00 %w/w per liter of the composition; and (h) optionally, at least one flow agent selected from dimethyl silicone polymer with silica at a concentration of 2.00 to 12.00 %w/w per liter of the composition. [0108] A further embodiment of the present invention is a herbicidal composition in the form of an Oil Dispersion (DO) characterized in that it contains (a) 5.00 to 20.00%w/w of glufosinate or its salts per liter of the composition; (b) 1.00 to 10.00%w/w of diuron per liter of the composition; (c) 1.00 to 7.00 % m /m of ethoxylated castor oil; (d) 2.00 to 10. 00 %w/w of dodecylbenzenesulfonic acid or its salts; (e) 2.00 to 10.00 %w/w of dimethyl silicone polymer with silica; (f) 2.00 to 10.00 %w/w of phenyl oxirane polymer with decyl ethers of oxirane mono (dihydrogenaphosphate); and (g) 33.00 to 87.00 %w/w soy methyl ester. [0109] A further embodiment of the present invention is a herbicidal composition, in Oil Dispersion (DO) form, characterized in that it contains (a) 5.00 to 20.00%w/w of
glufosinate or its salts per liter of the composition; (b) 1.00 to 10.00%w/w of diuron per liter of the composition; (c) 1.00 to 7.00 % m /m of ethoxylated castor oil; (d) 1.00 to 10. 00 %w/w of dodecylbenzenesulfonic acid or its salts; (e) 2.00 to 12.00 %w/w of dimethyl silicone polymer with silica; (f) 2.00 to 15.00 % m /m of phenyl oxirane polymer with decyl ethers of oxirane mono (dihydrogenaphosphate); and (g) 33.00 to 87.00 %w/w soy methyl ester. [0110] Another embodiment of the present invention is a herbicide composition, in the form of a concentrated suspension (SC) characterized by containing (a) 5.00 to 40.00%w/w of glufosinate or its salts per liter of the composition; (b) 1.00 to 20.00%w/w of diuron per liter of the composition; (c) 1.00 to 10.00%w/w of propylene glycol per liter of the composition; (d) 0.50 to 5.00%w/w of sodium salt lignosulfonate per liter of the composition; (e) 0.50 to 8.00%w/w of sulfated aromatic condensation product, sodium salt per liter of the composition; (f) 0. 10 to 0.50%w/w of 1,2-benzisothiazolin-3-one per liter of the composition; (g) 0. 05 to 0.50%w/w of xanthan gum per liter of the composition; and (h) 12.00 to 91.65%w/w of water per liter of composition. [0111] A further embodiment of the present invention is a herbicidal composition according to claim 1, in the form of a concentrated suspension (CS) characterized by containing (a) 5.00 to 40.00%w/w of glufosinate or its salts per liter of the composition; (b) 1.00 to 20.00%w/w of diuron per liter of the composition; (c) 1.00 to 7.00%w/w of propylene glycol per liter of the composition; (d) 0.50 to 10.00%w/w of sodium salt lignosulfonate per liter of the composition; (e) 1.00 to 10.00%w/w of sulfated aromatic condensation product, sodium salt per liter of the composition; (f) 0.20 to 4.00% m /m of polydimethylsiloxane per liter of the composition; (g) 0. 10 to 0.50%w/w of 1.2-benzisothiazolin-3-one per liter of the composition; (h) 0. 05 to 0.50%w/w of xanthan gum per liter of
the composition; and (h) 8.00 to 91.15%w/w of water per liter of composition. [0112] A further embodiment of the present invention is a herbicidal composition according to claim 1, in the form of a concentrated suspension (SC) characterized in that it contains (a) 5.00 to 40.00%w/w of glufosinate or its salts per liter of the composition; (b) 1.00 to 20.00%w/w of diuron per liter of the composition; (c) 1.00 to 10.00%w/w of propylene glycol per liter of the composition; (d) 0.50 to 5.00%w/w of sodium salt lignosulfonate per liter of the composition; (e) 0.50 to 8.00%w/w of sulfated aromatic condensation product, sodium salt per liter of the composition; (f) 0.20 to 4.00%w/w of polydimethylsiloxane per liter of the composition; (g) 0.50 to 5.00%w/w of sodium lauryl sulfate per liter of the composition; (h) 0.10 to 0.50%w/w of 1.2-benzisothiazolin-3-one per liter of the composition; (i) 0. 05 to 0.50%w/w of xanthan gum per liter of the composition; and (j) 7.00 to 91.15%w/w of water per liter of composition. [0113] A further embodiment of the present invention is a herbicidal composition according to claim 1, in water dispersible granule (WG) characterized in that it contains (a) 10.00 to 50.00 %w/w of glufosinate or its salts per liter of the composition; (b) 1.00 to 30.0O %w/w of diuron per liter of the composition; ( c) 2.00 to 12.00 %w/w of sodium salt lignosulfonate per liter of the composition; (d) 1.00 to 10.00 %w/w of sodium alkyl naphthalene sulfonate, formaldehyde condensate per liter of the composition; (e) 1.00 to 4.00 %w/w of diisopropylnaphthalenesulfonic acid, sodium salt per liter of the composition; (f) 0.20 to 2.00 %w/w of polydimethylsiloxane per liter of the composition; and (g) 5.00 to 85.00 %w/w of kaolin per liter of composition. [0114] A further embodiment of the present invention is a herbicidal composition according to claim 1, in water dispersible granule (WG) characterized in that it contains (a) 10.00 to 50.00 %w/w of glufosinate or its salts per liter of the
composition; (b) 1.00 to 30.0O %w/w of diuron per liter of the composition; ( c) 5.00 to 12.00 %w/w of sodium salt lignosulfonate per liter of the composition; (d) 0.50 to 10.00 %w/w of sodium alkyl naphthalene sulfonate, formaldehyde condensate per liter of the composition; (e) 1.00 to 4.00 %w/w of diisopropylnaphthalenesulfonic acid, sodium salt per liter of the composition; (f) 0.20 to 2.00 %w/w of polydimethylsiloxane per liter of the composition; and (g) 5.00 to 84.00 %w/w of kaolin per liter of composition. [0115] A further embodiment of the present invention is a herbicidal composition according to claim 1, in water dispersible granule (WG) characterized in that it contains (a) 10.00 to 40.00 %w/w of glufosinate or its salts per liter of the composition; (b) 0.50 to 20.0 %w/w of diuron per liter of the composition; (c) 2.00 to 12.00 %w/w of sodium salt lignosulfonate per liter of the composition; (d) 1.00 to 10.00 %w/w of sodium alkyl naphthalene sulfonate, formaldehyde condensate per liter of the composition; (e) 0.50 to 2.00 %w/w/ of sodium lauryl sulfate per liter of the composition; (f) 0.20 to 8.00 %w/w/ of polydimethylsiloxane per liter of the composition; and (g) 5.00 to 91.00 %w/w kaolin per liter of composition. [0116] A further embodiment of the present invention is a method to eradicate weeds characterized by applying the compositions defined in the above paragraphs to the plant locus. [0117] The weeds killed using the method of the present invention are Bidens pilosa, Conyza bonariensis, Conyza canadensis, Conyza sumatrensis ,Digitaria nuda, Eleusine indica, Euphorbia heterophylla, Ipomoea spp. [0118] The weeds controlled by this method are susceptible, tolerant or resistant to EPSPS-inhibiting (glyphosate), ALS- inhibiting (chlorimuron and others) and/or ACCase-inhibiting (clethodim, haloxyfop and others) herbicides in different agricultural crops, such as soybeans, corn, cotton and others.
[0119] Some of the formulations of the present invention are described below. Table 01: Examples of prototypes developed of agricultural herbicides containing glufosinate + diuron, OD, SC and WG formulation type prototypes. [0120] Table 01A: Glufosinate + Diuron, OD and SC formulation prototypes.
[0121] Table 01B: Glufosinate + Diuron, prototypes of the WG formulation type.
[0122] Table 02. Example of the composition of the herbicide of the present invention - OD formulation.
[0123] The most critical stage in the development of the present invention was the selection of the active ingredients glufosinate and diuron, when compared to other options such as glufosinate and carfentrazone or glufosinate and ametrine or glufosinate and diquat, among others, as presented above and formulations and method to control weeds susceptible, tolerant and resistant to the main herbicides and in different agricultural crops. As used in this document, the term “and/or” means any and all combinations of one or more of the associated listed elements. Based on this definition and with sustainability and risk reduction as the main objectives, the main points for improvement that should be incorporated into the new product were identified:
1) concentration of the active ingredients glufosinate and diuron in the formulation, reducing consumption of raw materials and transportation costs; 2) use of safer raw materials in toxicological and environmental terms; 3) development of formulations that are stable during storage and transportation; 4) increased deposition with reduced spray drift losses; 5) development of formulations with the dynamics and persistence of each of the active ingredients best suited to the control of weeds susceptible, tolerant and resistant to other herbicides in different agricultural crops; and 6) high effectiveness in comparative tests under practical conditions of use. [0124] The six items mentioned follow a logical and chronological order. [0125] In fact, the circuit they represented was covered several times, obtaining new information and continually improving the prototypes produced. [0126] Several experimental studies were carried out with the association in a spray tank considering various herbicides and later with glufosinate and diuron, dozens of experimental formulations (prototypes) were developed and evaluated, including various combinations between a surfactant system with other components comprising a fixing agent and a flow agent for use in herbicide formulations comprising glufosinate + diuron compositions at high load, until it was possible to arrive at the definitive formulation that allows all the established objectives to be achieved simultaneously. [0127] More specifically, the components of the composition of the present invention are presented in suitably balanced proportions and thus reduce losses of the herbicides by washing off by rainwater after application and by spray drift, favoring
the deposition and spreading of the formulated product on the leaf surface, promoting greater ease of absorption and penetration of the herbicides into the leaves, and better translocation in the plants. In addition, the formulation contributes to the spray application process, providing less evaporation on the way from the spray tip to the biological target, the formation of liquid films on leaf surfaces due to droplet coalescence, thus promoting greater effectiveness in weed control in autumn and pre-plant management, and in post- emergence in different crops, such as soya. [0128] The combination of a properly balanced surfactant system, a fixing agent and a flow agent used in this herbicide consists of a set of surfactants that greatly influence the performance of the formulated herbicide, resulting in excellent performance in weed control in different agricultural crops. [0129] This dispersant improves the stability of the emulsion or dispersion, reduces foaming and is stable in systems containing electrolytes, being a non-ionic surfactant that has excellent compatibility with the active ingredients. [0130] In the present invention, two types of formulation have been developed, a water-dispersible granule (WG) and an Oil Dispersion (OD). [0131] The advantages of developing a WG formulation are: the possibility of having a high concentration of the active ingredients, little powder formation, better chemical stability of the active ingredients and the use of components in the formulation that have the characteristic of improving the product’s performance in the field, as well as environmental safety, given the reduction in the volume of packaging and its disposal. [0132] On the other hand, the OD formulation is based on natural and/or mineral oils, or even blends, without the use of organic solvents, which provide a better homogenization of the perfectly balanced active ingredients, using components in the
formulation that have the characteristic of improving the performance of the herbicide (glufosinate and diuron) in terms of speed and weed control when compared to other herbicides or to the combination of glufosinate and diuron in the spray tank in the field. [0133] In the present invention, research carried out in field conditions has shown the best performance of the product developed with the OD (Oil Dispersion) type of formulation. This is due to the fact that we use a combination of an appropriately balanced surfactant system, with surfactants that have dispersant characteristics, wetting agents and components in the formulation with characteristics that improve the physicochemical stability of the formulation, such as dispersibility, agglomerating properties, rheological control, emulsion stabilization, humidification, suspensibility, redispersibility, ease in the manufacturing process, inhibition of crystal growth, antioxidant and formation of complexes. [0134] For the WG formulation, the formulation contains a set of surfactants based on ethoxylated castor oil, calcium salt of dodecylbenzenesulfonic acid, ethoxylated polyarylphenol, residues (petroleum), fractionating sulfonated polymers from the catalytic reformer with sodium formaldehyde salts and sodium lauryl sulfate. [0135] For the OD-type formulation we used a combination of an appropriately balanced surfactant system, with surfactants that have a dispersing and wetting function, consisting of a set of surfactants based on ethoxylated castor oil, calcium salt of dodecylbenzenesulfonic acid, oxirane phenyl-polymer with oxirane mono (dihydrogen phosphate) decyl ethers and dimethyl silicone polymer flow agent with silica. [0136] Ethoxylated castor oil is an ethoxylated non-ionic emulsifier suitable for a wide variety of agrochemical applications, providing emulsification and solubilization functionality.
[0137] Dodecylbenzenesulfonic acid is an anionic surfactant developed primarily to act as an emulsifier in agrochemical formulations. They are versatile and are combined with other surfactants to balance the HLB of the solvent in formulations. [0138] Ethoxylated polyarylphenol is an ethoxylated non-ionic surfactant with emulsifying and dispersing properties. It is effective over a wide range of pH, lipophilicity and ionic strength. [0139] Residues (petroleum), sulphonated polymers from the catalytic reformer fractionator with formaldehyde, sodium salts, is a dispersant having a performance standard for dispersants used in suspension concentrates and dispersed granule formulations. [0140] Compared to others, condensed alkyl naphthalene sulphonate is more effective in dispersing a wide variety of active ingredients in a wide range of water hardness applications. The use of this dispersant also helps to ensure that the active ingredients can be easily suspended in the spray tank. [0141] Sodium lauryl sulfate is an anionic surfactant used in agrochemical formulations. It is a sodium lauryl sulphate derived from sulphated alcohol through a continuous process. [0142] Phenyl oxirane polymer with oxirane mono (dihydrogenaphosphate) decyl ethers, is a polyetherphosphate with pigment affinic groups. Can be used as a dispersant agent in OD (oil Dispersion) formulations. [0143] Dimethyl silicone polymer with silica, is a polydimethylsiloxane-treated fumed silica with excellent thickening properties and has the function of inhibiting the sedimentation of solid active ingredients in the liquid. [0144] Table 03 below describes some of the formulations of the present invention. [0145] Table 03. Compositions of glufosinate and diuron. TREATMENTS
[0146] Prototype 10 was prepared as an SC Formulation at a concentration of 200 L/ha + 100 L/ha, prototype 11 was prepared as an SC Formulation at a concentration of 200 L/ha + 100 L/ha, prototype 12 was prepared as an SC Formulation at a concentration of 200 L/ha + 100 L/ha, prototype 13 was prepared as an OD Formulation at a concentration of 200 L/ha + 100 L/ha, prototype 14 was prepared as an OD Formulation at a concentration of 100 L/ha + 50 L/ha, prototype 15 was prepared as a WG Formulation at a concentration of 400 L/ha + 200 L/ha, prototype 16 was prepared as a WG Formulation at a concentration of 400 L/ha + 200 L/ha, and prototype 17 was prepared as a WG Formulation at a concentration of 200 L/ha + 100 L/ha. [0147] In general, it was possible to see from these studies that certain formulations of the ready mix of glufosinate + diuron stand out over others, both in terms of rapid control (3 days after application) and consistent control 14 days after application, with these prototypes of glufosinate + diuron showing superior results to paraquat 7 days after application. [0148] The prototypes with the best results include prototype 10 (SC formulation) and prototype 13 (OD formulation), as shown in Table 03. The weeds evaluated in these trials were Indian
goosegrass(Eleusine indica), crabgrass (Digitaria nuda), black jack(Bidens pilosa) and morning glory (Ipomoea spp). [0149] Table 04. Results of the tests carried out with prototype formulations 10 to 17 in the management of weeds: Indian goosegrass(Eleusine indica), crabgrass(Digitaria nuda), black jack (Bidens pilosa) and morning glory(Ipomoea sp).
Caption:
[0150] Figure 01 shows the results of the herbicides diquat, haloxyfop, carfentrazone, paraquat, glufosinate and diuron in the management of sourgrass (Digitaria insularis) resistant to the herbicide glyphosate. [0151] Figure 02 shows the results of the different herbicides alone in the management of Indian goosegrass(Eleusine indica). [0152] The results of the herbicides diquat, haloxyfop, carfentrazone, paraquat, glufosinate and diuron in the management of black jack (Bidens pilosa) and milkweed (Euphorbia heterophylla) can be seen in Figures 03 and 04, respectively. [0153] Figure 05 shows the main associations with glufosinate, i.e. glufosinate + diquat, glufosinate + diuron and glufosinate + carfentrazone, the respective concentrations of each active ingredient and the times of application in relation to the vegetative stage of the different weeds (2 to 4 leaves).
[0154] Figures 06 and 07 show the control efficiencies of bitterroot grass(Digitaria insularis) and Indian goosegrass(Eleusine indica) provided by the combinations of glufosinate + diquat, glufosinate + carfentrazone and glufosinate + diuron, respectively. [0155] The performance of the combinations of glufosinate + diquate, glufosinate + carfentrazone and glufosinate + diuron in the management of broad-leaved weeds, such as black jack (Bidens pilosa) and milkweed (Euphorbia heterophylla) can be seen in Figures 08 and 09, respectively. [0156] Figures 10 and 11 show the visual results at 03 and 14 days after application (DAA), considering the different associations with glufosinate. [0157] Figure 12 summarizes the efficacy results for sourgrass (Digitaria insularis), milkweed (Euphorbia heterophylla), Indian goosegrass (Eleusine indica) and black jack (Bidens pilosa) considering different herbicide treatments, including the associations with glufosinate + diuron, glufosinate + carfentrazone and glufosinate + diquat. [0158] Figures 13 and 14 show the results of the different combinations of glufosinate (glufosinate + diuron, glufosinate + carfentrazone and glufosinate + diquat) when compared to paraquat in the management of Morning Glory (Merremia aegyptia) and littlebell (Ipomoea grandifolia), important weeds present in different agricultural crops. [0159] On the other hand, Figure 15 shows the results of the different glufosinate combinations (glufosinate + diuron, glufosinate + carfentrazone and glufosinate + diquat) when compared to paraquat in the management of marmalade grass (Brachiaria plantaginea). [0160] An analysis of Figure 16 shows the high performance of the different glufosinate associations (glufosinate + diuron, glufosinate + carfentrazone and glufosinate + diquate) in the management of sourgrass (Digitaria insularis). It is also
possible to compare the actual controls obtained and the expected controls of the different treatments by applying Colby’s formula for the expected value, VE = Y1+(Y2((100-Y1))/100) and the actual values collected in the tests for the herbicides or herbicide mixtures. [0161] Figure 17 shows the high performance of the different glufosinate combinations (glufosinate + diuron, glufosinate + carfentrazone and glufosinate + diquat) in the management of Indian goosegrass(Eleusine indica), as well as the actual controls obtained and the expected controls of the different treatments by applying Colby’s formula for the expected value, VE = Y1+(Y2((100-Y1))/100). [0162] Figures 18 and 19 show the actual and expected controls of the different associations with glufosinate in the management of milkweed (Euphorbia heterophylla) and black jack(Bidens pilosa). [0163] The control performance of a weed community made up of Eleusine indica, Digitaria nuda, Bidens pilosa and Ipomoea sp can be seen in Figure 20. [0164] Figure 21 shows the efficacy of the formulation containing glufosinate + diuron (Prototype 10) when compared to the control in the management of important weeds such as Indian goosegrass (Eleusine indica), crabgrass(Digitaria insularis), black jack (Bidens pilosa) and stringy morning glory (Ipomoea sp). [0165] The efficacy of the different compositions of the formulation containing glufosinate + diuron (Prototype 11 to 18) when compared to the control in the management of important weeds such as Indian goosegrass (Eleusine indica), crabgrass(Digitaria insularis), black jack (Bidens pilosa) and morning glory(Ipomoea sp) can be seen in Figures 22 to 28, respectively. [0166] On the other hand, Figure 29 shows the performance of the herbicide paraquat in managing the weeds mentioned above when compared to the control.
[0167] The compositions developed in this invention containing glufosinate and diuron with a high load, in an appropriate balance of concentration ranges associated with the surfactant system together with other components comprising a fixing agent and a flow agent, as mentioned above, promote greater efficiency in weed management and greater safety for the environment, since they reduce herbicide losses by washing off by rainwater after application and by spray drift, deposition and spreading on the leaf surface, easier absorption and penetration of herbicides into the leaves of weeds, and better translocation in these plants, resulting in greater speed and effectiveness of control and also contributing to spray application by providing less evaporation on the way from the spray tip to the biological target, formation of liquid films on leaf surfaces, by coalescence of droplets, thus promoting greater effectiveness in the control of weeds susceptible, tolerant and resistant to other herbicides in different agricultural crops. [0168] In this context, it is important to note that spray drift and deposition are opposite phenomena. Spray drift indicates losses during the application process and deposition indicates how much of the applied product was actually deposited on the target (soybean plants in this case). [0169] Today, spray drift is identified as the main cause of losses and environmental contamination related to the application of pesticides. [0170] Reducing spray drift is essential to increase deposition and efficacy, reduce environmental contamination and, by reducing the amount of droplets in suspension, reduce the exposure of workers involved in the application. [0171] When flat targets such as the soil surface are used, making a mass balance of the application by accurately determining deposition and spray drift is relatively simple.
[0172] However, in plants with great variation in architecture, leaf area and morphology, it is not possible to carry out a mass balance and the most appropriate procedure is to measure the deposition or deposit of the applied compounds per unit area or mass of the plant. [0173] It is very important to conduct the evaluations under conditions that are representative of practical application conditions in terms of application technology and the characteristics of the application solutions. [0174] In this case, the information produced in the comparative dynamics studies conducted with the aim of comparing the prototype formulations with each other and with the main commercial standard was used. [0175] To this end, several experiments were set up under greenhouse and field conditions, with the treatments described below. [0176] In general, these studies showed that the basic product used to replace paraquat was glufosinate, which, when mixed with other herbicides, gave similar results and was often superior to paraquat itself. Among the possible partners which, in combination with glufosinate, had additive or even synergistic effects, the herbicides diquat, diuron, 2,4 D and carfentrazone were identified. Below is a summary table of both pot and field results, as well as photos of the pots showing their efficiency. [0177] Table 05. Tests carried out with various products and combinations
[0178] Table 06. Treatments with the products in table 05 and their results.
Caption:
[0179] To carry out the study with formulations of the herbicides glufosinate + diuron, experiments were conducted at the Center for Advanced Research in Matology of the School of Agronomic Sciences of the Universidade Estadual Paulista “Júlio de Mesquita Filho”, Botucatu-SP campus, between November and December 2018. [0180] In the experiment, the experimental units corresponded to 350 mL and 1.7 L pots filled with commercial substrate and sown with Euphorbia heterophylla and Soya, grown in a greenhouse. [0181] The formulations tested were applied using a stationary sprayer installed indoors, fitted with four XR110.02VS spray tips, spaced 0.5 m apart and positioned at a height of 0.5 m from the surface of the targets. The system was operated at a travel speed of 3.6 km/h, with a spray volume of 200 L/ha and a constant pressure of 1.5 bar pressurized by compressed air. Time of application of treatments on Euphorbia heteropylla and soybean plants). [0182] The experiment was carried out with the application of 6 prototypes of the glufosinate + diuron mixture, 3 commercial herbicides, and 1 additional control without application, with 5 repetitions (Table 05), applied in addition to the adjuvant
Mineral oil (0.2%), on Euphorbia heteropylla plants; and in soybean plants, the same treatments, with and without the addition of mineral oil (Table 14). [0183] Table 07. List of treatments carried out in experiment 2 with soybean plants.
[0184] Table 08. List of treatments carried out in experiment 2 with soybean plants.
[0185] After the treatments were applied, the experimental plots were kept in the greenhouse.
[0186] At 3, 7 and 14 days after application, visual assessments of phytointoxication were carried out on soybean plants(Glycine max) and milkweed (Euphorbia heterophylla), as shown in Figures 30 to 32. [0187] For the visual evaluations carried out, 5 replicates were used per treatment, in each of the rainfall simulation periods, and as a basis for the level of damage caused by the products on the plants, 0 was considered to be the absence of symptoms and 100 was considered to be the death of the plants (SBCPD, 1995). Photographs were also taken during all the evaluation periods. FINAL CONSIDERATIONS: [0188] The herbicide glufosinate + diuron was more effective than the commercial standards on the market glufosinate, paraquat, carfentrazone, diquat and others in controlling the main weeds. [0189] In summary, the most critical stage in the development of the present invention was the selection of the active ingredients glufosinate and diuron, when compared to other options such as glufosinate and carfentrazone or glufosinate and ametrine or glufosinate and diquat, among others, as presented above and formulations and method to control susceptible, tolerant and resistant weeds to the main herbicides and in different agricultural crops. As used in this document, the term “and/or” means any and all combinations of one or more of the associated listed elements. Based on this definition and with sustainability and risk reduction as the main objectives, the main points for improvement that should be incorporated into the new product were identified: 1) The formulation of glufosinate and diuron shows high performance in the management of weeds resistant and tolerant to the herbicide glyphosate, as well as high efficacy in weed control;
2) concentration of the active ingredients glufosinate and diuron in the formulation, reducing consumption of raw materials and transportation costs; 3)use of safer raw materials in toxicological and environmental terms; 4) development of formulations that are stable during storage and transportation; 5) increased deposition with reduced spray drift losses; 6) development of formulations with the dynamics and persistence of each of the active ingredients best suited to the control of weeds susceptible, tolerant and resistant to other herbicides in different agricultural crops; and 7) high effectiveness in comparative tests under practical conditions of use. BIBLIOGRAPHY [0190] ADEGAS, F.S. et al. Alternativas de controle químico de Digitaria insularis resistente ao herbicida glyphosate. In: XXVII Congresso Brasileiro da Ciência das Plantas Daninhas. Ribeirão Preto, São Paulo. Sociedade Brasileira da Ciência das Plantas Daninhas p.756-760, 2010. [0191] ADEGAS, F.S. et al. Impacto econômico da resistência de plantas daninhas a herbicidas no Brasil. Circular Técnica Embrapa, n. 132, 11p., 2017. [0192] AGROFIT. Sistema de Agrotóxicos Fitossanitários. Disponível em: http://agrofit.agricultura.gov.br/agrofit_cons/principal_agrof it_cons. Acesso em: 04 de Julho, 2018. [0193] BIANCHI, L. Efeito de glyphosate e clethodim isolados e em mistura em Digitaria insularis. 2018. 79 f. Dissertação (Mestrado em Agronomia) – Universidade Estadual Paulista “Júlio de Mesquita Filho”, Botucatu, 2010. [0194] Cesco VJS, Nardi R, Krenchinski FH, Albrecht AJP, Rodrigues DM, Albrecht LP. 2019. Management of resistant Conyza spp. during soybean pre-sowing. Planta Daninha 37:e019181064.
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[0122] Table 02. Example of the composition of the herbicide of the present invention - OD formulation.
Caption: