MODULATION OF THE RELEASE RATE OF MICROENCAPSULATED PESTICIDES

Abstract

Aqueous pesticide mixtures comprising a microencapsulated pesticide and an agent that modulates the rate of pesticide release from the microcapsules are described. Several methods for modulating the release rate of a microencapsulated pesticide in a pesticide mixture are also described. In addition, several microencapsulated pesticide mixtures and a co-pesticide that provides improved crop safety are described.

Description

MODULATION OF THE RELEASE RATE OF MICROENCAPSULATED PESTICIDES FIELD OF INVENTION

[0001] The present invention relates generally to various aqueous pesticide mixtures comprising a microencapsulated pesticide and an agent that modulates the rate of pesticide release from the microcapsules. The present invention also relates to various methods for modulating the rate of release of a microencapsulated pesticide in a pesticide mixture. The present invention further relates to various pesticide mixtures comprising a microencapsulated pesticide and a co-pesticide that provides improved crop safety. BACKGROUND OF THE INVENTION

[0002] Microencapsulation of pesticides is a method for controlling pesticide release after application, particularly when a sustained or slow release is desired. For some herbicides, the release rate must be controlled to manage crop damage. For example, with acetamide herbicides, a sustained release is desirable because damage has been observed in certain susceptible crops with the application of sprays prepared from conventional emulsifiable concentrate formulations (non-encapsulated herbicide formulations). Furthermore, a slower release can advantageously provide greater residual activity for pest control.

[0003] To form the microcapsules, the pesticide is encapsulated in a coating wall of a polymeric material. The pesticide is released 1258154 of 80 microcapsules release pesticides at least in part through molecular diffusion across the coating wall. Several factors, including pesticide type, polymer type, coating thickness, coating porosity, particle size, and the presence of protectants, affect the pesticide release rate from the microcapsules. Modifying these factors to increase or decrease the pesticide release rate has definite limitations. Furthermore, once the microcapsules are formulated, the release rate is generally fixed and cannot be adjusted. Consequently, there remains a need for formulations containing microencapsulated pesticides in which the pesticide release rate is modulated or adjusted to provide the desired level of pest control and avoid negative effects such as crop damage in the case of herbicides.

[0004] With regard to herbicides, the emergence of certain herbicide-resistant weeds has generated interest in developing strategies to complement the action of primary herbicides, such as glyphosate. Acetamide herbicides are known as effective residual herbicides that reduce weed competition in the early stages of the growing season. In particular, acetamide herbicides, such as acetochlor, provide outstanding residual control of many grasses and broadleaf weeds, including redroot pigweed, amaranth, common chenopod, nightshade, foxtail, and others. Acetamides are generally classified as seedling growth inhibitors. Seedling growth inhibitors are absorbed and translocated in plants from germination to emergence, primarily by subsurface emerging shoots and / or seedling roots. Acetamide herbicides typically do not offer a 1258154 of 80 significant post-emergence activity, but as a residual herbicide it would provide control of small-seeded monocot and dicot weed species when they are newly emerged. This complements the activity of post-emergence herbicides that lack significant residual activity.

[0005] Crop damage caused by the application of acetamide herbicides required strategies to reduce this effect, including the microencapsulation of the herbicide. Methods for producing microencapsulated acetamides are described in several patents and publications, including U.S. Patent No. 5,925,595; U.S. Patent Publication No. 2004 / 0137031; and U.S. Patent Publication No. 2010 / 0248963.

[0006] Herbicide compositions containing a combination of herbicides with multiple modes of action that can supplement the action of primary herbicides, such as glyphosate, are particularly suitable for controlling the growth of unwanted plants, including those resistant to certain herbicides. However, the release properties of microencapsulated acetamide herbicide concentrates may be sensitive to the inclusion of additional additives, including co-herbicides. Therefore, there remains a need for highly concentrated herbicide compositions containing microencapsulated acetamide herbicides and co-herbicides that can be produced economically while preserving the release properties of the microencapsulated acetamide herbicide and that can be diluted to provide effective spray formulation solutions for application to unwanted plants. 1258154 of 80 SUMMARY OF THE INVENTION

[0007] Briefly, aspects of the present invention relate to aqueous pesticide concentrate compositions comprising: (a) at least one microencapsulated particulate pesticide comprising a water-immiscible core material comprising the pesticide and a polyurea coating wall containing said core material, wherein the concentration of the pesticide in the composition based on the active ingredient is at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight,at least approximately 30% by weight or at least approximately 35% by weight, wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea, wherein the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1; and (b) a release modulator comprising a polyvalent metal cation, wherein the molecular weight of the release modulator is not greater than approximately 1000 g / mol,and wherein the mole ratio of the polyvalent metal cation to the molar equivalents of amine contained in the polyamine component is between approximately 0.05:1 and approximately 10:1. 1258154 of 80 [00 08] Several aspects of the present invention are directed to concentrated aqueous herbicide compositions comprising: (a) at least one microencapsulated particulate acetamide herbicide comprising a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material, wherein the concentration of the acetamide herbicide in the active ingredient-based composition is at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight,at least approximately 30% by weight or at least approximately 35% by weight, wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea, wherein the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1; and (b) a release modulator comprising a polyvalent metal cation, wherein the molecular weight of the release modulator is not greater than approximately 1000 g / mol,and wherein the mole ratio of the polyvalent metal cation to the molar equivalents of amine contained in the polyamine component is between approximately 0.05:1 and approximately 10:1. [00 09] Other aspects of the present invention are directed to mixtures 1258154 of 80 liquid herbicides comprising: (a) at least one microencapsulated particulate acetamide herbicide comprising a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material; (b) a release modulator comprising a polyvalent metal cation, wherein the molecular weight of the release modulator is not greater than approximately 1000 g / mol; and (c) an acid coherbicide. [00 10] Other aspects of the present invention relate to concentrated aqueous herbicide compositions comprising: (a) at least one microencapsulated particulate acetamide herbicide dispersed in an aqueous liquid medium comprising a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material, wherein the concentration of the acetamide herbicide in the composition based on the active ingredient is at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight, at least approximately 30% by weight, or at least approximately 35% by weight, and (b) an alkaline salt of an auxin herbicide dissolved in the aqueous liquid medium, wherein the concentration of the auxin herbicide in the composition based on the acid equivalent is at least approximately 1% by weight, at least approximately 5% by weight, or at least 1258154 of 80 a 10% by weight.

[0011] The present invention is also directed to various methods for modulating the release rate of a microencapsulated pesticide in a pesticide mixture, wherein said method comprises: mixing the microencapsulated pesticide, a release modulator, and a solvent to form the pesticide mixture, wherein the microencapsulated pesticide comprises a water-immiscible core material comprising the pesticide and a polyurea coating wall containing the core material, wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea, and the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1.and wherein the molecular weight of the release-modulating agent is not greater than approximately 1000 g / mol and the mole ratio of the polyvalent metal cation to the amine molar equivalents contained in the polyamine component is between approximately 0.05:1 and approximately 10:1.

[0012] Furthermore, several methods of the present invention include methods for modulating the release rate of a microencapsulated acetamide herbicide in an aqueous herbicide mixture, wherein said method comprises: mix the microencapsulated acetamide herbicide, an agent 1258154 of 80 release modulator and water to form the aqueous herbicide mixture, wherein the microencapsulated acetamide herbicide comprises a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material, wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea and the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1,and wherein the molecular weight of the release-modulating agent is not greater than approximately 1000 g / mol and the mole ratio of the polyvalent metal cation to the amine molar equivalents contained in the polyamine component is between approximately 0.05:1 and approximately 10:1.

[0013] Other objects and features will be partly evident and partly indicated from here on. BRIEF DESCRIPTION OF THE FIGURES

[0014] Figures 1 and 2 show the results of the crop damage tests for soybeans and cotton, respectively.

[0015] Figures 3 and 4 show the effect of the release modulating agent on the release rate of an application mixture prepared from a commercial grade concentrate (encapsulated acetochlor). DETAILED DESCRIPTION OF THE FORMS OF REALIZATION 1258154 of 80 PREFERRED

[0016] Several aspects of the present invention relate to various liquid pesticide mixtures comprising a microencapsulated pesticide (e.g., an acetamide herbicide such as acetochlor) and an agent that modulates the rate of pesticide release from the microcapsules. In particular, the microencapsulated pesticide may include a polyurea coating wall containing the pesticide. The release-modulating agent generally comprises a polyvalent metal cation.

[0017] One aspect of the present invention relates to liquid pesticide mixtures comprising a microencapsulated pesticide and methods for preparing such mixtures, wherein a release-modulating agent is formulated with the microencapsulated pesticide. An agent that can variably modulate the release rate of the microencapsulated pesticide allows for a flexible solution to provide pesticide formulations with a range of different release rates without altering the microencapsulation process. Microencapsulation processes can be highly sensitive or optimized, in which additional components can significantly affect the quality or properties of the microcapsules. Release-modulating agents that can be added after the microencapsulation process are particularly advantageous because they allow for avoiding the effects on the microencapsulation process.

[0018] A further aspect of the present invention is directed to liquid herbicide mixtures comprising a microencapsulated pesticide (e.g., acetamides such as acetochlor) and methods of preparation of 1258154 of 80 of these mixtures, where a release modulator is formulated with the microencapsulated herbicide. An agent that can variably modulate the release rate of the microencapsulated herbicide can offer improved crop safety (for example, in the case of sensitive crops) and / or greater residual efficacy.

[0019] Another aspect of the present invention relates to liquid pesticide mixtures comprising a microencapsulated pesticide and a co-pesticide that increases the release rate of the microencapsulated pesticide when formulated (e.g., when formulated as a premixed concentrate), and to methods of preparing such mixtures wherein a release-modulating agent is formulated with the pesticide mixture. It has been found that some co-pesticides can increase the release rate of the microencapsulated pesticide when mixed. In several applications, an increased release rate of the microencapsulated pesticide would not be desirable. Therefore, for some applications, it is beneficial to employ a release-modulating agent that can control or reduce the effects on the release rate of the microencapsulated pesticide caused by the co-pesticide.

[0020] Yet another aspect of the present invention relates to liquid herbicide mixtures comprising a microencapsulated herbicide (e.g., acetamide herbicides such as acetochlor) and a coherbicide (e.g., an acid coherbicide such as dicamba) that increases the release rate of the microencapsulated herbicide when formulated (e.g., when formulated as a premixed concentrate), and methods for preparing these mixtures wherein a modulating agent is formulated. 1258154 of 80 release with the herbicide mixture. Some coherbicides have been found to increase the release rate of the microencapsulated pesticide when mixed. An increased release rate of the microencapsulated herbicide would not be desirable in applications where damage to sensitive crops is a concern or where prolonged residual efficacy against weeds is desired. Therefore, for some applications, it is beneficial to use a release modulator that can control or reduce the effects on the release rate of the microencapsulated herbicide caused by the coherbicide.

[0021] Still other aspects of the present invention are directed to various concentrated aqueous herbicide compositions comprising a microencapsulated acetamide herbicide in combination with an alkali metal salt of certain coherbicides. As indicated, some coherbicides (e.g., acidic coherbicides such as dicamba) have been found to increase the release rate of the microencapsulated acetamide herbicide, which could cause damage to sensitive crops. Surprisingly, it has been discovered that the use of alkali metal salts of the coherbicide can provide improved crop safety.

[0022] Microencapsulation

[0023] As indicated, several liquid pesticide mixtures of the present invention (e.g., aqueous concentrated herbicide compositions) comprise at least one microencapsulated particulate pesticide comprising a core material comprising the pesticide and a coating wall containing the core material. The microencapsulation process can be conducted according to techniques of 1258154 of 80 known interfacial polycondensations. The microencapsulation of water-immiscible materials employing an interfacial polycondensation reaction generally comprises dissolving a first monomeric or polymeric reactive material (first coating wall component) in the material to be encapsulated to form the oily or discontinuous liquid phase. The discontinuous liquid phase is then dispersed in an aqueous or continuous liquid phase to form an oil-in-water emulsion. The continuous (aqueous) phase liquid may contain a second monomeric or polymeric reactive material (second coating wall component) at the time it is dispersed in the continuous phase. If this is the case, the first and second coating wall components will immediately begin to react at the oil-in-water interface to form a polycondensed coating wall around the material to be encapsulated.However, the oil-in-water emulsion can also form before adding the second coating wall component to the emulsion.

[0024] At least a portion of the pesticide in the liquid pesticide mixture of the present invention is encapsulated with a polyurea coating wall. In general, the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea. See, for example, U.S. Patent No. 5,925,595; U.S. Patent Publication No. 2004 / 0137031; and U.S. Patent Publication No. 2010 / 0248963, which are incorporated herein by reference. 1258154 of 80

[0025] The pesticides encapsulated with a polyurea coating wall of the present invention can be prepared by contacting a continuous aqueous phase containing a polyamine component comprising a polyamine source and a discontinuous oil phase containing the pesticide and a polyisocyanate component comprising a polyisocyanate source. A polyurea coating wall is formed in a polymerization reaction between the polyamine source and the isocyanate source at the oil / water interface, thereby forming a capsule or microcapsule containing the pesticide.

[0026] The polyurea polymer coating wall of the microcapsules can be formed using one or more polyisocyanates, i.e., containing two or more isocyanate groups per molecule. A wide variety of polyisocyanates can be employed. For example, the polyisocyanate component can comprise an aliphatic polyisocyanate (e.g., DESMODUR W, DESMODUR N 3200, and DESMODUR N 3215). In some embodiments, the polyurea coating wall is formed using a mixture of at least two polyisocyanates. For example, the polyurea coating wall is formed in an interfacial polymerization reaction using at least one diisocyanate and at least one triisocyanate (e.g., a combination of DESMODUR W and DESMODUR N 3200 or N 3215).

[0027] The polyamine source may be a single polyamine species or a mixture of two or more different polyamine species. In some embodiments of the present invention, the polyamine source essentially consists of a main polyamine. As used herein, the main polyamine refers to a polyamine consisting essentially of a 1258154 of 80 single species of polyamine.

[0028] It is advantageous to select a polyamine component and a polyisocyanate component such that the polyamine has an amine functionality of at least 2, i.e., 3, 4, 5 or more, and at least one of the polyisocyanates has an isocyanate functionality of at least 2, i.e., 2.5, 3, 4, 5 or more, since high amine and isocyanate functionality increases the percentage of crosslinking that occurs between individual polyurea polymers comprising the coating wall. In some embodiments, the polyamine has an amine functionality of more than 2 and the polyisocyanate is a mixture of polyisocyanates, wherein each polyisocyanate has an isocyanate functionality of more than 2. In other embodiments, the polyamine comprises a trifunctional polyamine and the polyisocyanate component comprises one or more trifunctional polyisocyanates.In still other embodiments, the coating wall is formed by the reaction between a polyisocyanate, or a mixture of polyisocyanates, with a minimum average of 2.5 reactive groups per molecule, and a polyamine with an average of at least three reactive groups per molecule. Furthermore, it is advantageous to select concentrations of the polyamine and polyisocyanate components such that the polyisocyanate component reacts substantially completely to form the polyurea polymer. The complete reaction of the polyisocyanate component increases the percentage of crosslinking between the polyurea polymers formed in the reaction, thereby providing structural stability to the coating wall.

[0029] As described, the oil-in-water emulsion that forms 1258154 of 80. During the interfacial polymerization reaction, the emulsion can be prepared by adding the oil phase to the continuous aqueous phase to which an emulsifying agent has been added (for example, previously dissolved in it). The emulsifying agent is selected to achieve the desired oil droplet size in the emulsion. The size of the oil droplets in the emulsion is affected by numerous factors besides the emulsifying agent used and determines the size of the microcapsules formed by the process. The emulsifying agent is preferably a protective colloid. Polymeric dispersants are preferred as colloid protectors. Polymeric dispersants provide steric stability to the emulsion by adsorbing onto the surface of the oil droplets and by forming a highly viscous layer that prevents the droplets from coalescing.Polymeric dispersants can be surfactants and are preferred over non-polymeric surfactants because polymeric compounds form a stronger interfacial film around the oil droplets. If the protective colloid is ionic, the layer formed around each oil droplet will also electrostatically prevent the droplets from coalescing. A preferred protective colloid is SOKALAN (available from BASF), a maleic acid-olefin copolymer, as are INVALON (available from Huntsman) and AGNIQUE NSC 11NP (available from BASF), which are naphthalene sulfonate condensates.

[0030] Other colloid protectants that are useful in this invention include gelatin, casein, polyvinyl alcohol, alkylated polyvinylpyrrolidone polymers, maleic anhydride-methyl vinyl ether copolymers, styrene-maleic anhydride copolymers, maleic acid-butadiene and 1258154 of 80 copolymers of diisobutylene, sodium and calcium lignosulfonates, sulfonated naphthalene-formaldehyde condensates, modified starches and modified cellulosics such as hydroxyethyl or hydroxypropylcellulose and carboxymethylcellulose.

[0031] In several embodiments, the microencapsulation method includes encapsulating the core material in a coating wall formed by reacting the polyamine component and a polyisocyanate component in a reaction medium at concentrations such that the reaction medium comprises an excess of amine molar equivalents compared to isocyanate groups. That is, the amine molar equivalent to isocyanate molar equivalent ratio used in preparing the microcapsule coating wall is greater than 1:1. For example, a molar equivalent ratio of at least 1.01:1, or at least approximately 1.05:1, is used to ensure complete reaction of the isocyanate. The amine molar equivalent ratio in the polyamine component to the isocyanate molar equivalent ratio in the polyisocyanate component can range from 1.01:1 to approximately 1.05:1.7:1, between 1.01:1 and approximately 1.6:1, between 1.01:1 and approximately 1.5:1, between 1.01:1 and approximately 1.4:1, between 1.01:1 and approximately 1.3:1, between 1.05:1 and approximately 1.7:1, between 1.05:1 and approximately 1.6:1, between 1.05:1 and approximately 1.5:1, between 1.05:1 and approximately 1.4:1 or between 1.05:1 and approximately 1.3:1.

[0032] The molar equivalent ratio of amine molar equivalents to isocyanate molar equivalents is calculated according to the following equation: 1258154 of 80 Molar equivalent ratio = molar equivalents of amine / molar equivalents of isocyanate In the previous equation (1), the molar equivalents of amine are calculated according to the following equation: molar equivalents = Σ(weight of polyamine / equivalent weight). In the previous equation (1), the molar equivalents of isocyanate are calculated according to the following equation: molar equivalents of isocyanate = Σ(weight of polyisocyanate / equivalent weight). The equivalent weight is generally calculated by dividing the molecular weight in grams / mol by the number of functional groups per molecule and is expressed as grams / mol. For some molecules, such as triethylenetetramine (TETA) and 4,4'-diisocyanate-dicyclohexylmethane (DES W), the equivalent weight is equal to the molecular weight divided by the number of functional groups per molecule. For example, TETA has a molecular weight of 146.23 g / mol and 4 amine groups. Therefore, the equivalent weight is 36.6 g / mol. Generally speaking, this calculation is correct, but for some materials, the actual equivalent weight may vary from the calculated equivalent weight. In some components, for example, the biuret-containing (i.e., trimer) adduct of hexamethylene-1,6-diisocyanate, the equivalent weight of the commercially available material differs from the theoretical equivalent weight due, for example, to an incomplete reaction.The theoretical equivalent weight of the biuret-containing adduct (i.e., a trimer) of hexamethylene-1,6-diisocyanate is 159.5 g / mol. The actual equivalent weight of the hexamethylene-1,6-diisocyanate trimer (DES N3200), the commercially available product, is 183 g / mol. 1258154 of approximately 80. This actual equivalent weight is used in the calculations above. The actual equivalent weight can be obtained from the supplier or by titration with a suitable reagent using methods known in the art. The symbol, Σ, in the calculation of amine molar equivalents means that the amine molar equivalents comprise the sum of the amine molar equivalents for all polyamines in the reaction medium. Likewise, the symbol, Σ, in the calculation of isocyanate molar equivalents means that the isocyanate molar equivalents comprise the sum of the isocyanate molar equivalents for all polyisocyanates in the reaction medium.

[0033] In general, microcapsules can be characterized by having an average particle size of at least approximately 2, 3, 4, 5, 6, 7, 8, 9, or 10 μm. For example, microcapsules have an average particle size in the range of approximately 2 μm to approximately 15 μm, approximately 2 μm to approximately 12 μm, or approximately 6 μm to approximately 15 μm. Capsules or microcapsules are essentially spherical, such that the average cross-sectional dimension defined by any point on one surface of the microcapsule to a point on the opposite side of the microcapsule is essentially the diameter of the microcapsule. The average particle size of the microcapsules can be determined by measuring the particle size of a representative sample with a laser light scattering particle size analyzer known to specialists in the art.An example of a particle size analyzer is a Coulter LS particle size analyzer.

[0034] As reported in U.S. Patent Publication No.: 1258154 of 80 2010 / 0248963, it is believed, without considering any particular theory, that the combination of a larger average particle size and the coating characteristics resulting from a large excess of unreacted amine groups significantly reduces the release rate. In the case of a herbicide core material, this combination of characteristics reduces the amount of herbicide to which crop plants are exposed after application, thus providing improved crop safety and minimal crop damage. It is believed, without considering any particular theory, that the larger excess of amine groups results in a significant amount of unreacted amine functional groups, thus providing a coating with a large number of non-crosslinked amine functional groups.The resulting coating wall is believed to be flexible and resistant to rupture, thus reducing the amount of herbicide to which crop plants are initially exposed after application of a herbicide formulation containing the microcapsules. It is further believed that the unreacted amine groups may reduce the number of fissures or cracks in the coating wall, thereby reducing leakage and herbicide flow through the coating wall from the core.

[0035] Therefore, in various embodiments, the molar concentration of the amine groups of the polyamine component and the molar concentration of the isocyanate groups of said at least one polyisocyanate (i.e., one polyisocyanate, a mixture of two polyisocyanates, a mixture of three polyisocyanates, etc.) in the reaction medium is such that the ratio of the amine molar equivalent concentration to the isocyanate molar equivalent concentration is at least approximately 1.1:1. 1258154 of 80 In several embodiments, the molar equivalent ratio of amine molar equivalents to isocyanate molar equivalents can be at least approximately 1.15:1 or even at least approximately 1.20:1. In some embodiments, the molar equivalent ratio is less than approximately 1.7:1, less than approximately 1.6:1, less than approximately 1.5:1, less than approximately 1.4:1, or even less than approximately 1.3:1. In various embodiments, the molar equivalent ratio of amine molar equivalents to isocyanate molar equivalents in the polymerization medium is between 1.1:1 and approximately 1.7:1, between 1.1:1 and approximately 1.6:1, between 1.1:1 and approximately 1.5:1, between 1.1:1 and approximately 1.4:1, between 1.1:1 and approximately 1.3:1, between approximately 1.15:1 and approximately 1.7:1, between approximately 1.15:1 and approximately 1.6:1, between approximately 1.15:1 and approximately 1.5:1, between approximately 1.15:1 and approximately 1.4:1, between approximately 1.15:1 and approximately 1.3:1, between 1.2:1 and approximately 1.7:1, between 1.2:1 and approximately 1.6:1, between 1.2:1 and approximately 1.5:1, between 1.2:1 and approximately 1.4:1, or between 1.2:1 and approximately 1.3:1. Examples of typical ratios include 1.1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1 and 1.5:1.

[0036] Furthermore, according to the methods described in U.S. Patent Publication No. 2010 / 0248963, microencapsulated pesticides can be prepared wherein the particles (i.e., capsules or microcapsules) are characterized by having an average particle size of at least approximately 7 μm, at least approximately 8 μm, by 1258154 of 80 at least approximately 9 μm or at least approximately 10 μm, and less than approximately 15 μm or less than 12 μm. In various embodiments, the microencapsulated pesticide can be characterized by having an average particle size of between approximately 7 μm and approximately 15 μm, between approximately 7 μm and approximately 12 μm, between approximately 8 μm and approximately 12 μm, or between approximately 9 μm and approximately 12 μm. In particularly preferred embodiments, the range varies between approximately 9 μm and approximately 11 μm.

[0037] A diluent, such as a solvent, may be added to change the solubility parameter characteristics of the core material to increase or decrease the release rate of the active ingredients of the microcapsule once release has begun. For example, the core material may comprise from approximately 0% to 35% by weight of a diluent, such as from approximately 0.1% to 25% by weight, from approximately 0.5% to approximately 20% by weight, or from approximately 1% to 10% by weight. In particular, the core material may comprise 0%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 15%, 20%, 25%, 30%, or even 35% diluent. In some embodiments, the weight ratio of total core material to diluent may comprise, for example, between 8 and 1, between 10 and 1, between 15 and 1, or between 20 and 1.In some embodiments, the diluent is a water-insoluble organic solvent with a solubility of less than 10, 5, 1, 0.5, or even 0.1 grams per liter at 25 °C. Examples of suitable water-insoluble solvents include hydrocarbons. 1258154 of 80 paraffins. It is preferred that the paraffinic hydrocarbons be predominantly a linear or branched hydrocarbon. Examples include pentadecane and ISOPAR V and ISOPAR M. In addition, the weight ratio of the core material components compared to the weight of the coating wall components can be adjusted to further affect the release rate profile of the pesticide microcapsules.

[0038] A wide variety of pesticides can be microencapsulated. In general, the encapsulated pesticide particles may comprise a core material containing a water-immiscible agrochemical encapsulated by a polyurea coating wall, which is preferably substantially non-microporous, such that the release of the core material occurs by a molecular diffusion mechanism, as opposed to a flow mechanism through a pore or crack in the polyurea coating wall. As stated herein, the coating wall may preferably comprise a polyurea product of the polymerization of one or more polyisocyanates and a main polyamine (and optional auxiliary polyamines).

[0039] According to the present invention, the pesticide may comprise a herbicide. Encapsulation is particularly suitable for acetamide herbicides. Accordingly, several liquid herbicide mixtures of the present invention comprise at least one microencapsulated particulate acetamide herbicide comprising a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material, wherein the wall of 1258154 of 80 polyurea coating is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea and wherein the polyurea coating wall comprises excess amine, wherein the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.1:1.

[0040] Acetamide herbicides suitable for microencapsulation include herbicides such as acetochlor, alachlor, butachlor, butenachlor, delachlor, diethyl, dimetachlor, dimethenachlor, dimethenachlor, dimethenachlor-P, mefenacet, metazochlor, metolachlor, S-metolachlor, napropamide, pretylachlor, pronamide, propachlor, propisochlor, prinachlor, terbuchlor, tenylchlor, and xylachlor, salts and esters thereof, and combinations thereof. Some acetamide herbicides are available in free forms, as salts, or as derivatized materials, e.g., as esters. In several embodiments, the acetamide herbicide is selected from the group consisting of acetochlor, alachlor, metolachlor, S-metolachlor, dimethenamid, dimethenamid-P, butolachlor, and combinations thereof. In certain embodiments, the acetamide herbicide is selected from the group consisting of acetochlor, metolachlor, and S-metolachlor.In some embodiments, the acetamide herbicide comprises acetochlor.

[0041] Liquid pesticide mixtures

[0042] In general, encapsulated pesticide particles (e.g., capsules or microcapsules) are dispersed in a liquid medium, preferably 1258154 of 80 aqueous (e.g., water) to form the liquid pesticide mixture. The pesticide loading of the encapsulated pesticide in the liquid pesticide mixture is typically between approximately 5% and approximately 60% or between approximately 5% and approximately 50% by weight based on the active ingredient, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60% or ranges in between, by weight based on the active ingredient.

[0043] In various embodiments, the liquid pesticide mixture is an aqueous concentrated herbicide composition containing at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight, at least approximately 30% by weight, or at least approximately 35% by weight of a microencapsulated acetamide herbicide based on the active ingredient.In these and other embodiments, the concentrated aqueous herbicide composition contains between approximately 15% by weight and approximately 60% by weight, between approximately 15% by weight and approximately 50% by weight, between approximately 15% by weight and approximately 40% by weight, between approximately 20% by weight and approximately 60% by weight, between approximately 20% by weight and approximately 50% by weight, between approximately 20% by weight and approximately 40% by weight, between approximately 20% by weight and approximately 35% by weight, between approximately 20% by weight and approximately 30% by weight, between approximately 25% by weight and approximately 60% by weight, between approximately 25% by weight and approximately 50% by weight. 1258154 of 80 between approximately 25% by weight and approximately 40% by weight, between approximately 25% by weight and approximately 35% by weight, between approximately 30% by weight and approximately 60% by weight, between approximately 30% by weight and approximately 50% by weight, between approximately 30% by weight and approximately 40% by weight or between approximately 30% by weight and approximately 35% by weight of a microencapsulated acetamide herbicide based on the active ingredient.

[0044] The liquid pesticide mixture may be optionally, and / or preferably, formulated with the additives described elsewhere herein (e.g., a stabilizing agent, one or more surfactants, an antifreeze, an anti-caking agent, drift control agents, etc.).

[0045] The liquid pesticide mixture containing the microcapsule dispersion can be formulated to further optimize its shelf stability and safe use. Dispersants, stabilizers, and thickeners are useful for inhibiting agglomeration and settling of the microcapsules. This function is facilitated by the chemical structure of these additives, as well as by compensating for the densities of the aqueous and microcapsule phases. Anti-caking agents are useful when the microcapsules need to be redispersed. A pH buffer solution can be used to maintain the pH of the dispersion within a range that is safe for skin contact and, depending on the additives selected, within a narrower pH range than that required for dispersion stability.

[0046] Low molecular weight dispersants can solubilize the coating wall of microcapsules, particularly in the early stages of their formation, causing gelation problems. 1258154 of 80 Consequently, in some embodiments, the dispersants have relatively high molecular weights of at least approximately 1.5 kg / mol, more preferably at least approximately 3 kg / mol, and even more preferably at least approximately 5, 10, or even 15 kg / mol. In some embodiments, the molecular weight may vary in the range of approximately 3 kg / mol to approximately 50 kg / mol or approximately 5 kg / mol to approximately 50 kg / mol. The dispersants may also be nonionic or anionic. An example of a high molecular weight anionic polymeric dispersant is the sodium salt of polymeric naphthalene sulfonate, such as Invalon (formerly Irgasol, Huntsman Chemicals).Other dispersants and stabilizers that are useful include gelatin, casein, ammonium caseinate, polyvinyl alcohol, alkylated polyvinylpyrrolidone polymers, maleic anhydride-methyl vinyl ether copolymers, styrene-maleic anhydride copolymers, maleic acid-butadiene-diisobutylene copolymers, ethylene oxide-propylene oxide block copolymers, sodium and calcium lignosulfonates, sulfonated naphthaleneformaldehyde condensates, modified starches and modified cellulosics such as hydroxyethyl or hydroxypropylcellulose, sodium carboxymethylcellulose, and silica fume dispersions.

[0047] Thickeners are useful for retarding the settling process because they increase the viscosity of the aqueous phase. Pseudoplastic thickeners are preferred because they reduce the viscosity of the dispersion during pumping, which facilitates economical application and homogeneous coverage of the dispersion in an agricultural field using equipment commonly employed for this purpose. The viscosity of the dispersion of The viscosity of 80 microcapsules after formulation (1258154) preferably ranges from approximately 100 cps to approximately 400 cps, as determined using a Haake Rotovisco viscometer and measured at approximately 10 °C with a stem rotating at approximately 45 rpm. More preferably, the viscosity can range from approximately 100 cps to approximately 300 cps. A few examples of useful pseudoplastic thickeners include water-soluble guar or xanthan gums (e.g., Kelzan from CPKelco), cellulose ethers (e.g., ETHOCEL from Dow), cellulosics and modified polymers (e.g., Aqualon thickeners from Hercules), and microcrystalline cellulose anti-caking agents.

[0048] Adjusting the density of the aqueous phase to approximate the average weight-to-volume ratio of the microcapsules also retards the settling process. In addition to their primary purpose, many additives can increase the density of the aqueous phase. A further increase can be achieved by adding sodium chloride, glycol, urea, or other salts. The weight-to-volume ratio of microcapsules of preferred dimensions can be approximated by the density of the core material, where such density of the core material is between approximately 1.05 and approximately 1.5 g / cm³. Preferably, the density of the aqueous phase is formulated to be within approximately 0.2 g / cm³ of the average weight-to-volume ratio of the microcapsules.More preferably, the density of the aqueous phase varies in a range from approximately 0.2 g / cm3 less than the average weight-to-volume ratio of the microcapsules to approximately the average weight-to-volume ratio of the microcapsules. 1258154 of 80

[0049] In order to improve shelf life and prevent gelation of the aqueous microcapsule dispersion, particularly after storage in elevated temperature environments, the formulated microcapsule dispersions may further include urea or a structure-similar breaking agent at a concentration of up to approximately 20% by weight, typically approximately 5% by weight.

[0050] Optionally, surfactants may be included in the compositions of the present invention. Suitable surfactants are selected from nonionic, cationic, anionic, and mixtures thereof. Examples of surfactants suitable for the practice of the present invention include, but are not limited to: alkoxylated tertiary etheramines (such as the TOMAH E series of surfactants); alkoxylated quaternary etheramines (such as the TOMAH Q series of surfactants); alkoxylated etheramine oxides (such as the TOMAH AO series of surfactants); alkoxylated tertiary amine oxides (such as the AROMOX series of surfactants); and alkoxylated tertiary amine surfactants (such as the ETHOMEEN T and C series of surfactants). alkoxylated quaternary amines (such as the ETHOQUAD T and C series of surfactants);alkyl sulfates, alkyl ether sulfates and alkylaryl ether sulfates (such as the WITCOLATE series of surfactants); alkyl sulfonates, alkyl ether sulfonates and alkylaryl ether sulfonates (such as the WITCONATE series of surfactants); alkoxylated phosphate esters and diesters (such as the PHOSPHOLAN series of surfactants); alkylpolysaccharides (such as the AGRIMUL PG series of surfactants); alkoxylated alcohols (such as the BRIJ or HETOXOL series of agents; 1258154 of 80 surfactants); and mixtures thereof.

[0051] Anti-caking agents facilitate the redispersion of the microcapsules upon agitation of the formulation in which the microcapsules have settled. A microcrystalline cellulose material such as FMC Lattice is effective as an anti-caking agent. Other suitable anti-caking agents include, for example, clay, silicone dioxide, insoluble starch particles, and insoluble metal oxides (e.g., aluminum oxide or iron oxide). Preferably, anti-caking agents that alter the pH of the dispersion are avoided, at least in some embodiments.

[0052] Drift control agents suitable for the practice of the present invention are known to those skilled in the art and include the commercial products GARDIAN, GARDIAN PLUS, DRI-GARD, PRO-ONE XL ARRAY, COMPADRE, IN-PLACE, BRONC MAX EDT, EDT CONCENTRATE, COVERAGE and BRONC Plus Dry EDT.

[0053] The pH of the formulated microcapsule dispersion preferably ranges from approximately 4 to approximately 9 to minimize eye irritation in individuals who come into contact with the formulation during handling or application to crops. However, if components of the formulated dispersion are pH-sensitive, such as the blocking agent, buffer solutions such as disodium phosphate may be used to maintain the pH within the range where the components are most effective. Additionally, a pH buffer solution such as citric acid monohydrate may be particularly useful in some systems during microcapsule preparation to maximize the efficacy of a protective colloid such as SOKALAN CP9. 1258154 of 80

[0054] Other useful additives include, for example, biocides or preservatives (e.g., PROXEL, commercially available from Avecia), antifreeze agents (such as glycerol, sorbitol, or urea), and antifoaming agents (such as Antifoam SE23 from Wacker Silicones Corp.).

[0055] The compositions described herein may further comprise an additive to control or reduce the potential volatility of the pesticide. Under certain application conditions, some herbicides, such as auxin herbicides, may vaporize into the surrounding atmosphere and migrate from the application site to adjacent crops, such as soybeans and cotton, where damage to susceptible plants may occur. For example, as described in U.S. Patent Application Nos. 2014 / 0128264 and 2015 / 0264924, which are incorporated herein by reference, additives to control or reduce the potential volatility of the pesticide include monocarboxylic acids, or salts thereof (e.g., acetic acid and / or an agriculturally acceptable salt thereof).Representative monocarboxylic acids and monocarboxylates generally comprise a hydrocarbon or an unsubstituted hydrocarbon selected, for example, from linear or branched-chain alkyls, unsubstituted or substituted (e.g., C1-C20 alkyls, such as methyl, ethyl, n-propyl, isopropyl, etc.); linear or branched-chain alkenyls, unsubstituted or substituted (e.g., C2-C20 alkyls, such as ethenyl, n-propenyl, isopropenyl, etc.); unsubstituted or substituted aryls (e.g., phenyl, hydroxyphenyl, etc.); or unsubstituted or substituted arylalkyls (e.g., benzyl). In particular, the monocarboxylic acid may be selected from the group consisting of formic acid, acetic acid, propionic acid, and other acids. 1258154 of 80 benzoic. The monocarboxylate salt may be selected from the group consisting of formate salts, acetate salts, propionate salts, and benzoate salts. Monocarboxylate salts may include, for example, salts of alkali metals selected from sodium and potassium. Preferred monocarboxylate salts include sodium acetate and potassium acetate.

[0056] The molar ratio of the pesticide (for example, an auxin herbicide) to the monocarboxylic acid, or a monocarboxylate thereof, typically comprises between about 1:10 and about 10:1, between about 1:5 and about 5:1, between about 3:1 and about 1:3, or between about 2:1 and about 1:2 (for example, about 1:1).

[0057] In several concentrated herbicidal compositions of the present invention, the concentration of monocarboxylic acid and / or a salt thereof may be from approximately 0.25% to approximately 25%, from approximately 1% to approximately 20%, from approximately 2% to approximately 15%, from approximately 2% to approximately 10%, or from approximately 5% to approximately 15% by weight of the concentrated composition.

[0058] Release modulating agent

[0059] In several embodiments, the liquid pesticide mixtures of the present invention also comprise a release modulator that modulates the release rate of the microencapsulated pesticide. In general, the release modulator comprises a polyvalent metal cation. Typically, the release modulator is added to the liquid pesticide mixture as a water-soluble salt. 1258154 of 80 or a salt solution. Regardless of the theory, it is believed that polyvalent metal cations can form complexes with the polyamines in the polyurea coating wall and, as a result, increase the crosslinking density of the coating wall. An increase in the crosslinking density of the coating wall is expected to decrease the diffusion coefficient, resulting in a slower release rate. Furthermore, also regardless of the theory, the addition of the release modulator may alter the solution properties of the pesticide mixture, resulting in slower diffusion of the pesticide from the microcapsules and reducing the overall pesticide release rate.

[0060] The release modulating agent comprises a polyvalent metal cation. The polyvalent ions may be metal ions selected from the group consisting of magnesium, calcium, aluminum, manganese, iron, copper, zinc, and combinations thereof. In various embodiments, the polyvalent metal cation comprises Ca2+.

[0061] In general, the molecular weight of the release modulator is relatively low, not exceeding approximately 1000 g / mol, approximately 750 g / mol, approximately 500 g / mol, approximately 300 g / mol, or approximately 200 g / mol. The molecular weight of the release modulator may range from approximately 50 g / mol to approximately 1000 g / mol, between approximately 50 g / mol and approximately 750 g / mol, between approximately 50 g / mol and approximately 500 g / mol, between approximately 50 g / mol and approximately 300 g / mol, between approximately 50 g / mol and 1258154 of 80 approximately 200 g / mol, between approximately 100 g / mol and approximately 1000 g / mol, between approximately 100 g / mol and approximately 750 g / mol, between approximately 100 g / mol and approximately 500 g / mol, between approximately 100 g / mol and approximately 300 g / mol, or between approximately 100 g / mol and approximately 200 g / mol.

[0062] The release modulator may comprise an organic anion. For example, the release modulator may comprise an anion selected from the group consisting of acetate, citrate, carbonate, oxalate, and combinations thereof (e.g., calcium acetate). Alternatively, the release modulator may comprise an inorganic anion. For example, the release modulator may be a salt of a mineral acid, such as a salt halide (e.g., calcium chloride). In addition, the release modulator may comprise a sulfate anion (e.g., copper sulfate). A mixture of salts may be added to the herbicide mixture as a release modulator. For example, the release modulator may comprise a combination of a calcium salt, such as calcium chloride or calcium acetate, and a copper salt, such as copper sulfate.

[0063] In the case of a pesticide encapsulated with a polyurea produced using an excess of amine molar equivalents relative to the amount of isocyanate molar equivalents (e.g., an excess of at least approximately 10%, at least approximately 15%, or at least approximately 20%), polyvalent metal cations are believed to form complexes with the coating wall polyamines 1258154 of 80 of polyurea. Therefore, it is believed that supplying a sufficient amount of excess amine is favorable for the formation of complexes with the polyvalent metal cations of the release-modulating agent. Therefore, the mole ratio of a polyvalent metal cation to amine molar equivalents contained in the polyamine component is typically between approximately 0.05:1 and approximately 10:1, between approximately 0.05:1 and approximately 5:1, between approximately 0.05:1 and approximately 3:1, between approximately 0.05:1 and approximately 2:1, between approximately 0.05:1 and approximately 1.75:1, between approximately 0.05:1 and approximately 1.5:1, between approximately 0.05:1 and approximately 1:1, between approximately 0.1:1 and approximately 10:1, between approximately 0.1:1 and approximately 5:1, between approximately 0.1:1 and approximately 3:1, between approximately 0.1:1 and approximately 2:1, between approximately 0.1:1 and approximately 1.75:1, between approximately 0.1:1 and approximately 1.5:1, between approximately 0.1:1 and approximately 1:1, between approximately 0.2:1 and approximately 10:1, between approximately 0.2:1 and approximately 5:1, between approximately 0.2:1 and approximately 3:1, between approximately 0.2:1 and approximately 2:1, between approximately 0.2:1 and approximately 1.75:1, between approximately 0.2:1 and approximately 1.5:1, between approximately 0.2:1 and approximately 1:1, between approximately 0.3:1 and approximately 10:1, between approximately 0.3:1 and approximately 5:1, between approximately 0.3:1 and approximately 3:1, between approximately 0.3:1 and approximately 2:1, between approximately 0.3:1 and approximately 1.75:1, between approximately 0.3:1 and approximately 1.5:1, between, 1258154 of 80 approximately 0.3:1 and approximately 1:1, between approximately 0.4:1 and approximately 10:1, between approximately 0.4:1 and approximately 5:1, between approximately 0.4:1 and approximately 3:1, between approximately 0.4:1 and approximately 2:1, between approximately 0.4:1 and approximately 1.75:1, between approximately 0.4:1 and approximately 1.5:1, between approximately 0.4:1 and approximately 1:1, between approximately 0.5:1 and approximately 10:1, between approximately 0.5:1 and approximately 5:1, between approximately 0.5:1 and approximately 3:1, between approximately 0.5:1 and approximately 2:1, between approximately 0.5:1 and approximately 1.75:1, between approximately 0.5:1 and approximately 1.5:1 or between approximately 0.5:1 and approximately 1:1.

[0064] The release modulator is effective in reducing the release rate of the microencapsulated pesticide (e.g., an acetamide herbicide). For example, the addition of the release modulator can reduce the release rate of the microencapsulated pesticide over a 24-hour period after application by at least approximately 30%, at least approximately 40%, at least approximately 50%, at least approximately 60%, at least approximately 70%, or at least approximately 80% compared to a similar pesticide mixture formulated without the release modulator.

[0065] In embodiments where the microencapsulated pesticide comprises an acetamide herbicide, the molar ratio of the acetamide herbicide to a polyvalent metal cation can be from 1:1 to approximately 100:1, from approximately 2:1 to approximately 100:1, 1258154 of 80 between approximately 2:1 and approximately 80:1, between approximately 3:1 and approximately 80:1, between approximately 3:1 and approximately 60:1, between approximately 3:1 and approximately 40:1, between approximately 4:1 and approximately 100:1, between approximately 4:1 and approximately 80:1, between approximately 4:1 and approximately 60:1, between approximately 4:1 and approximately 40:1, between approximately 4:1 and approximately 25:1, between approximately 5:1 and approximately 100:1, between approximately 5:1 and approximately 80:1, between approximately 5:1 and approximately 60:1, between approximately 5:1 and approximately 40:1 or between approximately 5:1 and approximately 25:1.

[0066] In various embodiments where the liquid pesticide mixture is a concentrated composition comprising a microencapsulated acetamide herbicide, the concentration of the release modulator agent is between approximately 0.1% by weight and approximately 5% by weight, between approximately 0.1% by weight and approximately 3% by weight, between approximately 0.1% by weight and approximately 2% by weight, between approximately 0.2% by weight and approximately 5% by weight, between approximately 0.2% by weight and approximately 3% by weight, between approximately 0.5% by weight and approximately 5% by weight, or between approximately 0.5% by weight and approximately 3% by weight.

[0067] In various embodiments, the liquid pesticide mixtures according to the present invention include concentrated aqueous herbicidal compositions comprising: (a) at least one microencapsulated particulate acetamide herbicide comprising a water-immiscible core material that 1258154 of 80 comprises the acetamide herbicide and a polyurea coating wall containing the core material, wherein the concentration of the acetamide herbicide in the active ingredient-based composition is at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight,at least approximately 30% by weight or at least approximately 35% by weight, wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea, wherein the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1; and (b) a release modulator comprising a polyvalent metal cation, wherein the molecular weight of the release modulator is not greater than approximately 1000 g / mol,and wherein the mole ratio of the polyvalent metal cation to the molar equivalents of amine contained in the polyamine component is between approximately 0.05:1 and approximately 10:1.

[0068] Copeside

[0069] The liquid pesticide mixtures of the present invention may further comprise a co-pesticide. Typically, the co-pesticide is added to the liquid medium comprising the dispersed microencapsulated pesticide and is dissolved or dispersed therein. 1258154 of 80

[0070] Co-pesticides may comprise co-herbicides, particularly when the microencapsulated pesticide also comprises a herbicide. For example, in several embodiments, the liquid pesticide mixture is a herbicide mixture comprising a microencapsulated acetamide herbicide.In these and other embodiments, the coherbicide can be selected from the group consisting of acetyl CoA carboxylase (ACCase) inhibitors, enolpyruvyl shikimate-3-phosphate synthase (EPSPS) inhibitors, glutamine synthetase inhibitors, auxins, photosystem I (PS I) inhibitors, photosystem II (PS II) inhibitors, acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors, mitosis inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, cellulose inhibitors, oxidative phosphorylation uncouplers, dihydropteroate synthase inhibitors, fatty acid and lipid biosynthesis inhibitors, auxin transport inhibitors, and carotenoid biosynthesis inhibitors, salts and esters thereof, racemic mixtures, and isomers. solutions of the same and mixtures of the same.

[0071] When a herbicide is referred to by name herein, unless otherwise restricted, such herbicide includes all commercially available forms known in the art, such as salts, esters, free acids, and free bases, as well as stereoisomers thereof. For example, when the herbicide name glyphosate is used, glyphosate acid, salts, and esters are included within the scope of that name.

[0072] EPSPS herbicides include glyphosate or a salt or ester thereof.

[0073] Glutamine synthetase herbicides include glufosinate or 1258154 of 80 glufosinate-P, or a salt or / and an ester thereof.

[0074] ACCase inhibitors include, for example, aloxidim, butroxidim, clethodim, cycloxidim, pinoxaden, sethoxidim, tepraloxidim, and tralcoxidim, salts and esters thereof, and mixtures thereof. Another group of ACCase inhibitors includes chlorazifop, clodinafop, clofop, cyhalofop, diclofop, diclofop-methyl, fenoxaprop, fentiaprop, fluazifop, haloxyfop, isoxapirifop, metamifop, propaquizafop, quizalofop, and trifop, salts and esters thereof, and mixtures thereof. ACCase inhibitors also include mixtures of one or more dims and one or more fops, salts and esters thereof.

[0075] Auxin herbicides (i.e., synthetic auxin herbicides) include, for example, 2,4-dichlorophenoxyacetic acid (2,4-D), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), dichloroprop, 2-methyl-4-chlorophenoxyacetic acid (MCPA), 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), aminopyralide, clopyralide, fluroxypyr, triclopyr, diclopyr, mecoprop, dicamba, picloram, and quinclorac, salts and esters thereof, and mixtures thereof.

[0076] PS II inhibitors include, for example, ametryn, amicarbazone, atrazine, bentazone, bromacil, bromoxynil, chlorotoluron, cyanazine, desmedifam, desmetrin, dimefuron, diuron, fluometuron, hexazinone, ioxinil, isoproturon, linuron, metamitron, methibenzuron, methoxuron, metribuzine, monolinuron, phenmedifam, promethon, prometrine, propanyl, pyrazone, pyridate, siduron, simazine, symmetrine, tebutyuron, terbacil, terbumetone, terbuthylazine, and trietazine, salts and esters thereof, and mixtures thereof.

[0077] ALS and AHA inhibitors include, for example, amidosulfuron, azimsulfuron, bensulfuron-methyl, bispiribac-sodium, chlorimuron 1258154 of 80 ethyl, chlorsulfuron, cinosulfuron, chloransulam-methyl, cyclosulfamuron, diclosulam, etametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florazulam, flucarbazone, flucetosulfuron, flumetsulam, flupirsulfuron-methyl, foramsulfuron, halosulfuron-methyl, imazametabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, metsulfuron-methyl, nicosulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyritiobac, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, tifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron and triflusulfuron-methyl, salts and esters thereof and mixtures thereof.

[0078] Mitosis inhibitors include anilofos, benefin, DCPA, dithiopyr, etalfluralin, flufenacet, mefenacet, oryzalin, pendimethalin, thiazopyr and trifluralin, salts and esters thereof, and mixtures thereof.

[0079] PPO inhibitors include, for example, acifluorfen, azaphenidine, bifenox, butafenacil, carfentrazone-ethyl, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazine, fluoroglycophene, flutiacet-methyl, fomesafene, lactophene, oxadiargil, oxadiazone, oxyfluorfen, pyrafluphene-ethyl, saflufenacil and sulfentrazone, salts and esters thereof and mixtures thereof.

[0080] Carotenoid biosynthesis inhibitors include, for example, aclonifen, amitrole, beflubutamide, benzofenap, clomazone, diflufenican, fluridone, flurochloridone, flurtamone, isoxaflutol, mesotrione, norflurazone, picolinaphene, pyrazolinate, pyrazoxyphene, sulcotrione, tembotrione, and topramezone, salts and esters thereof, and mixtures thereof.

[0081] PS I inhibitors include diquat and paraquat, salts and esters thereof, and mixtures thereof.

[0082] Cellulose inhibitors include diclobenyl and isoxabene. 1258154 of 80

[0083] An uncoupler of oxidative phosphorylation is dinoterb and esters thereof.

[0084] Auxin transport inhibitors include diflufenzopyr and naptalam, salts and esters thereof and mixtures thereof.

[0085] An inhibitor of dihydropteroate synthase is asulam and salts thereof.

[0086] Fatty acid and lipid biosynthesis inhibitors include bensulide, butylate, cycloate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb, triallate and vernolate, salts and esters thereof, and mixtures thereof.

[0087] Some preferred coherbicides include flumioxazine, fluometuron, diuron, sulfentrazone, fomesafene, metribuzine, saflufenacil, thiencarbazone, mesotrione, atrazine, isoxaflutol, 2,4-D, dicamba, and glyphosate, salts and esters thereof, racemic mixtures and resolved isomers thereof, and mixtures thereof. In some embodiments, the coherbicide comprises fomesafene and / or a salt of fomesafene, such as sodium fomesafene.

[0088] Typically, the weight ratio of microencapsulated pesticide to co-pesticide can be from approximately 1:10 to approximately 10:1, from approximately 1:8 to approximately 8:1, or from approximately 1:6 to approximately 6:1. In several embodiments where the microencapsulated pesticide is an acetamide herbicide, the weight of the acetamide herbicide can be greater than the weight of the co-herbicide. In other embodiments, the weight ratio of acetamide herbicide to co-herbicide can be from approximately 1:10 to approximately 10:1. 1258154 of 80 between approximately 1:8 and approximately 8:1, between approximately 1:5 and approximately 5:1, between approximately 1:1 and approximately 10:1, between approximately 1:1 and approximately 8:1, between approximately 1:1 and approximately 5:1 or between approximately 1:1 and approximately 3:1.

[0089] Some co-pesticides have been found to increase the release rate of microencapsulated pesticides. However, the incorporation of the release-modulating agent according to the present invention controls or reduces the potentially negative effects of the microencapsulated pesticide's release rate. Consequently, a variety of co-pesticides can be included in the liquid pesticide mixture without significantly affecting the release rate of the microencapsulated pesticide.

[0090] In particular, it has been found that certain acid coherbicides, such as dicamba, significantly increase the release rate of encapsulated acetamide herbicides, such as acetochlor, especially when premixed in a concentrate containing the encapsulated acetamide herbicide. In this case, the increased release rate of the acetamide herbicide can be excessively detrimental to sensitive crops. However, the incorporation of the release-modulating agent of the present invention significantly reduces or eliminates this problem, thereby allowing the premixing of the microencapsulated acetamide and the acid coherbicide in a concentrated composition.

[0091] Therefore, a liquid herbicide mixture according to the present invention comprises (a) at least one microencapsulated particulate acetamide herbicide comprising a water-immiscible core material that 1258154 of 80 comprises the acetamide herbicide and a polyurea coating wall containing the core material; (b) a release modulator comprising a polyvalent metal cation, wherein the molecular weight of the release modulator is not greater than approximately 1000 g / mol; and (c) an acid coherbicide.

[0092] Other embodiments of the present invention include concentrated aqueous herbicidal compositions comprising: (a) at least one microencapsulated particulate acetamide herbicide comprising a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material, wherein the concentration of the acetamide herbicide in the active ingredient-based composition is at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight,at least approximately 30% by weight or at least approximately 35% by weight, and wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea, and wherein the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1; (b) a release modulating agent comprising a cation of 1258154 of 80 a polyvalent metal, wherein the molecular weight of the release modulating agent is not greater than approximately 1000 g / mol, and wherein the mole ratio of the polyvalent metal cation to amine molar equivalents contained in the polyamine component is between approximately 0.05:1 and approximately 10:1; and (c) an acid coherbicide (for example, a dicamba salt).

[0093] The coherbicide may comprise an auxin herbicide selected from the group consisting of 2,4-D, 2,4-DB, dichloroprop, MCPA, MCPB, aminopyralid, clopyralid, fluroxypyr, triclopyr, diclopyr, mecoprop, dicamba, picloram, and quinclorac, salts and esters thereof, and mixtures thereof. The acid coherbicide may comprise a dicamba salt (for example, a salt selected from the group consisting of dicamba sodium salt, dicamba monoethanolamine salt, dicamba diglycolamine salt, and combinations thereof). In addition, the acid coherbicide may comprise at least one herbicide selected from the group consisting of glyphosate, fomesafen, mesotrione, glufosinate, dicamba, salts and esters thereof, and combinations thereof.

[0094] In some embodiments, the weight of the acetamide herbicide may be less than the weight of the coherbicide on an acid equivalent basis. For example, the weight ratio of the acetamide herbicide to the coherbicide (on an acid equivalent basis) may be from approximately 1:1.5 to approximately 20:1, from approximately 1:1.5 to approximately 15:1, from approximately 1:1.5 to approximately 10:1, from approximately 1:1.5 to approximately 8:1, from approximately 1:1.5 to approximately 5:1, and from approximately 1:1.5 to 1258154 of 80 approximately 3:1, between approximately 1:15 and approximately 15:1. In various embodiments, the weight of the acetamide herbicide is greater than the weight of the coherbicide on an acid equivalent basis. For example, the weight ratio of the acetamide herbicide to the coherbicide (acid equivalent basis) is between approximately 1:10 and approximately 10:1, between approximately 1:8 and approximately 8:1, between approximately 1:5 and approximately 5:1, between approximately 1:1 and approximately 20:1, between approximately 1:1 and approximately 15:1, between approximately 1:1 and approximately 10:1, between approximately 1:1 and approximately 8:1, between approximately 1:1 and approximately 5:1, or between approximately 1:1 and approximately 3:1.

[0095] Compositions containing alkaline salts of an auxin coherbicide

[0096] As indicated, certain acidic coherbicides have been found to increase the release rate of microencapsulated acetamide herbicides, particularly when the coherbicide is premixed in a herbicide concentrate. In particular, certain auxin coherbicides, such as dicamba, have been found to increase the release rate of microencapsulated acetamide herbicides, such as acetochlor. The increased release rate of the acetamide herbicide from the microcapsules may cause damage to susceptible crops.

[0097] Surprisingly, it has been discovered that incorporating alkaline salts of auxin coherbicides into an aqueous concentrated herbicide composition (i.e., a premixed concentrate) comprising a microencapsulated acetamide herbicide provides an application mixture (is 1258154 of 80 (i.e., the dilution of the concentrated composition) which offers improved crop safety after application. That is, even though the release rate of the acetamide herbicide may increase as a result of the presence of the auxin coherbicide, the use of the alkali metal salt of the auxin coherbicide nevertheless provides improved crop safety compared to other salts, such as amine salts of the auxin herbicide.

[0098] In this concentrated aqueous herbicide composition, at least one microencapsulated particulate acetamide herbicide is dispersed in an aqueous liquid medium comprising a water-immiscible core material containing the acetamide herbicide and a polyurea coating wall containing the core material. The auxin coherbicide salt is dissolved in the aqueous liquid. Suitable acetamide herbicides and auxin coherbicides were previously indicated. For example, preferred acetamide herbicides include acetochlor, alachlor, metolachlor, S-metolachlor, dimethenamid, dimethenamid-P, butolachlor, and combinations thereof. Preferred auxin coherbicides include 2,4-D, 2,4-DB, dichloroprop, MCPA, MCPB, aminopyralide, clopyralide, fluroxypyr, triclopyr, diclopyr, mecoprop, dicamba, picloram, and quinclorac, and mixtures thereof. In several embodiments, the auxin coherbicide comprises dicamba.In some embodiments, the auxin coherbicide comprises 2,4-D.

[0099] Suitable alkaline salts of the auxin coherbicide include agronomically acceptable alkaline salts. For example, alkaline salts may include sodium and / or potassium. In several embodiments, the alkaline salt comprises sodium (e.g., sodium dicamba). In some forms of 1258154 of 80 realization, the alkaline salt comprises potassium (e.g., potassium dicamba).

[0100] In general, the concentration of acetamide herbicide in the aqueous concentrated herbicide composition based on the active ingredient is at least approximately 15% by weight, at least approximately 20% by weight, at least approximately 25% by weight, at least approximately % by weight, at least approximately 30% by weight, or at least approximately 35% by weight. For example, the concentration of acetamide herbicide based on the active ingredient may be between approximately 15% by weight and approximately 60% by weight, between approximately 15% by weight and approximately 50% by weight, between approximately 15% by weight and approximately 40% by weight, between approximately 20% by weight and approximately 60% by weight, between approximately 20% by weight and approximately 50% by weight, between approximately 20% by weight and approximately 40% by weight.between approximately 20% and approximately 35% by weight, between approximately 20% and approximately 30% by weight, between approximately 25% and approximately 60% by weight, between approximately 25% and approximately 50% by weight, between approximately 25% and approximately 40% by weight, between approximately 25% and approximately 35% by weight, between approximately 30% and approximately 60% by weight, between approximately 30% and approximately 50% by weight, between approximately 30% and approximately 40% by weight, or between approximately 30% and approximately 35% by weight. 1258154 of 80

[0101] Furthermore, the concentration of the auxin coherbicide in the composition on an acid equivalent basis is at least approximately 1% by weight, at least approximately 5% by weight, or at least 10% by weight. For example, the concentration of the auxin coherbicide in the composition on an acid equivalent basis may be between approximately 1% by weight and approximately 30% by weight, between approximately 1% by weight and approximately 25% by weight, between approximately 1% by weight and approximately 20% by weight, between approximately one 1% by weight and approximately 15% by weight, between approximately one 1% by weight and approximately 10% by weight, between approximately one 5% by weight and approximately 30% by weight, between approximately one 5% by weight and approximately 25% by weight, between approximately one 5% by weight and approximately 20% by weight, between approximately 5% by weight and approximately 15% by weight, between approximately one 5% by weight and approximately 10% by weight, between approximately one 10% by weight and approximately 30% by weight, between approximately 10% by weight and approximately 25% by weight, between approximately one 10% by weight and approximately 20% by weight or between approximately 10% by weight and approximately 15% by weight.

[0102] Furthermore, the weight ratio of acetamide herbicide to auxin herbicide (acid equivalent basis) in the concentrated aqueous herbicide composition may be between approximately 1:1.5 and approximately 20:1, between approximately 1:1.5 and approximately 15:1, between approximately 1:1.5 and approximately 10:1, between approximately 1:1.5 and approximately 8:1, between approximately 1:1.5 and approximately 1258154 of 80 5:1, between approximately 1:1.5 and approximately 3:1, between approximately 1:15 and approximately 15:1, between approximately 1:10 and approximately 10:1, between approximately 1:8 and approximately 8:1, between approximately 1:5 and approximately 5:1, between approximately 1:1 and approximately 20:1, between approximately 1:1 and approximately 15:1, between approximately 1:1 and approximately 10:1, between approximately 1:1 and approximately 8:1, between approximately 1:1 and approximately 5:1 or between approximately 1:1 and approximately 3:1.

[0103] The aqueous concentrated herbicide composition may include other features as described herein. For example, the aqueous concentrated herbicide composition may include the various features described above with respect to microencapsulation, liquid pesticide mixtures, and the release modulator agent.

[0104] As indicated, the concentrated aqueous herbicide composition may include additional coherbicides (i.e., one or more coherbicides in addition to the auxin coherbicide and the acetamide herbicide) as mentioned herein, also typically dissolved or dispersed in the liquid medium comprising the dispersed microencapsulated acetamide herbicide. Examples of the classes of additional coherbicides include photosystem II inhibitors, ACCase inhibitors, an acetolactate synthase or acetohydroxy acid synthase inhibitor, PPO inhibitors, carotenoid biosynthesis inhibitors, and others. Specific examples of preferred additional coherbicides include glyphosate, glufosinate, flumioxazine, fomesafen, lactophene, sulfentrazone, oxyfluorphen, saflufenacil, metribuzin, thiencarbazone, mesotrione, atrazine, flumetsulam, isoxaflutol, and fluometuron, salts and esters of 1258154 of 80 the same, racemic mixtures and resolved isomers thereof and mixtures thereof. In some embodiments, the additional coherbicide comprises fomesafene and / or a salt of fomesafene, such as sodium fomesafene. In certain embodiments, the additional coherbicide comprises metribuzin. In other embodiments, the liquid pesticide mixtures include a triple combination of microencapsulated acetochlor, sodium dicamba and fomesafene and / or a salt of fomesafene, such as sodium fomesafene, or metribuzin.

[0105] Application mixtures

[0106] Liquid pesticide mixtures (e.g., aqueous concentrated herbicide compositions) can be diluted with water as needed to form application mixtures. For example, when the microencapsulated pesticide comprises an acetamide herbicide, then the liquid pesticide mixtures are useful as controlled-release herbicides. Accordingly, the present invention is also directed to a method for applying an application mixture, which is a dilution of the concentrated composition, to control plant growth. The acetamide herbicide loading in the application mixture is typically no more than about 5% by weight or between about 0.1% and about 5% by weight based on the active ingredient, such as 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.1% by weight based on the active ingredient.

[0107] The application mixture may be applied to a field according to practices known to those skilled in the art. In some embodiments, the application mixture is applied to the soil before sowing the crop plants or after sowing but before emergence. 1258154 of 80 crop plants. Since the release characteristics of the encapsulated acetamide herbicide particles are adjustable, the timing of the release can be controlled (or the release increased), thereby achieving both commercially acceptable weed control and a commercially acceptable crop damage index.

[0108] The effective amount of encapsulated acetamide herbicide and optional co-herbicide to be applied to an agricultural field depends on the herbicide identity, the release rate of the capsules or microcapsules, the crop being treated, and environmental conditions, especially soil type and moisture. In general, application rates for acetamide herbicides, such as acetochlor, are in the range of approximately 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 kilograms of herbicide per hectare, or ranges thereof, such as 0.5 to 10 kilograms per hectare, 0.5 to 10 kilograms per hectare, 0.5 to 5 kilograms per hectare, or 1 to 5 kilograms per hectare. In some forms of implementation, an application rate of sorghum, rice, and wheat of between approximately 0.85 and approximately 1 kilogram per hectare is preferred.

[0109] In general, the application rates of optional co-herbicides such as, for example, dicamba, are in the order of approximately 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4 or 5 kilograms of herbicide per hectare, or ranges thereof, such as between 0.1 and 5 kilograms per hectare, between 0.5 and 2.5 kilograms per hectare or between 0.5 and 2 kilograms per hectare.

[0110] Application mixtures of aqueous herbicide concentrates are preferably applied in an agricultural field within a framework of 1258154 of 80 selected time of crop plant development. In various embodiments of the present invention, the application mixture prepared with an aqueous herbicide concentrate is applied after crop plant emergence. For the purposes of the present invention, post-emergence of crop plants includes initial emergence from the soil, i.e., at the time of breakout. In some embodiments, the application mixture is applied to a field 1-40 days before crop plant sowing and / or pre-emergence (i.e., from crop plant sowing until, but not including, emergence or cracking) in order to provide control of newly emerging monocots and small-seeded dicot species without significant crop damage.In various embodiments, the application mixture prepared from an aqueous herbicide concentrate of the present invention is applied to the weeds prior to emergence.

[0111] The application mixtures of the aqueous herbicide concentrates of the present invention are useful for controlling a wide variety of weeds, i.e., plants considered a nuisance or competition to commercially important crops such as corn, soybeans, cotton, broad beans, green beans, and potatoes, etc. In some embodiments, the application mixtures are applied before weed emergence (i.e., a pre-emergence application). Examples of weeds that can be controlled according to the method of the present invention include, but are not limited to, prairie foxtail (Alopecurus pratensis) and other weed species of the genus Alopecurus, barnyardgrass (Echinochloa crus-galli) and other weed species of the genus 1258154 of 80 Echinochloa, slow grasses of the genus Digitaria, white clover (Trifolium repens), chenopods (Chenopodium berlandieri), amaranth (Amaranthus retroflexus) and other weed species of the genus Amaranthus, common purslane (Portulaca oleracea) and other weed species of the genus Portulaca, Chenopodium album and other Chenopodium spp., Setaria lutescens and other Setaria spp., Solanum nigrum and other Solanum spp., Lolium multiflorum and other Lolium spp., Brachiaria platyphylla and other Brachiaria spp., Sorghum halepense and other Sorghum spp., Conyza canadensis and other Conyza spp., and Eleusine indica. In some embodiments, the weeds comprise one or more glyphosate-resistant species, 2,4-D-resistant species, dicamba-resistant species, and / or ALS-inhibitor herbicide-resistant species.In some embodiments, the glyphosate-resistant weed species is selected from the group consisting of Amaranthus palmeri, Amaranthus rudis, Ambrosia artemisiifolia, Ambrosia trifida, Conyza bonariensis, Conyza canadensis, Digitaria insularis, Echinochloa colona, ​​Eleusine indica, Euphorbia heterophylla, Lolium multiflorum, Lolium rigidum, Plantago lanceolata, Sorghum halepense, and Urochloa panicoides.

[0112] Some crop plants, such as soybeans and cotton, are less susceptible to the action of acetamide herbicides and other coherbicides, such as dicamba, than weeds. According to the present invention and based on experimental evidence to date, it is believed that the controlled acetamide release rate of encapsulated acetamide herbicides, in combination with crop plants that exhibit lower susceptibility to acetamide, allows for commercially effective weed control and commercially acceptable crop damage rates when applied 1258154 of 80 encapsulated acetamide herbicides to a field either before planting or pre-emergence to the crop plant. This allows the use of acetamide seedling growth inhibitor herbicides, or optionally acetamide seedling growth inhibitor herbicides in combination with a coherbicide, such as dicamba, in pre-planting and pre-emergence applications to crop plants.

[0113] In some embodiments of the present invention, the crop plants include, for example, corn, soybeans, cotton, broad beans, green beans, and potatoes. The crop plants include hybrid, inbred, and transgenic or genetically modified plants that have specific characteristics or combinations of characteristics, including, but not limited to, herbicide tolerance (for example, resistance to glyphosate, glufosinate, dicamba, sethoxydim, PPO inhibitors, etc.), Bacillus thuringiensis (Bt), high oil content, high lysine content, high starch content, nutrient density, and drought resistance. In some embodiments, the crop plants are tolerant to organophosphate herbicides, acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitor herbicides, auxin herbicides and / or acetyl CoA carboxylase (ACCase) inhibitor herbicides.In other embodiments, the crop plants are resistant to glyphosate, dicamba, 2,4-D, MCPA, quizalofop, glufosinate, and / or diclofop-methyl. In other embodiments, the crop plant is resistant to glyphosate and / or dicamba. In some embodiments of the present invention, the crop plants are resistant to glyphosate and / or glufosinate. In some other embodiments, the crop plants are tolerant to glyphosate, glufosinate, and dicamba. In these and other embodiments of. 1258154 of 80 realization, the crop plants are tolerant to PPO inhibitors.

[0114] Particularly preferred crop species are cotton and soybeans. In embodiments where the crop is cotton, it is preferred to apply the application mixture at planting time until before crop emergence, before planting (e.g., 1-4 weeks before planting), and / or after crop emergence (e.g., using a protected sprayer to keep the application mixture out of the crop). In embodiments where the crop is soybeans, it is preferred to apply the application mixture at planting time until before crop emergence, before planting (e.g., 1-4 weeks before planting), and / or after crop emergence.

[0115] Having described the invention in detail, it will be evident that it is possible to make modifications and variations without departing from the scope of the invention, which is defined in the attached claims. EXAMPLES

[0116] The following non-exhaustive examples are provided to illustrate the present invention in further detail. Example 1

[0117] An aqueous concentrated herbicide composition was prepared according to the protocol described in this example.

[0118] A microencapsulated acetochlor dispersion was prepared as follows. The internal phase was prepared with the components and amounts shown in Table 1-1. The percentages indicate the approximate weight percent of each component in the composition 1258154 of 80 final aqueous concentrated herbicide. TABLE 1-1: Internal Phase Components Active ingredient % by weight of active component % by weight in the final concentrated composition % by weight of active ingredients in the final concentrated composition Acetochlor 96.0 44.79 43.0 ISOPAR M (solvent, C11-C16 isoalkanes) 100 2.32 2.32 DESMODUR N 3215 (aliphatic isocyanate based on hexamethylene diisocyanate) 100 3.26 3.26

[0119] To prepare the inner phase of the acetochlor microcapsules, acetochlor was loaded into the mixing vessel. Next, ISOPAR M solvent was loaded into the mixing vessel, followed by DESMODUR N 3215 polyisocyanates. The solution was stirred to obtain a clear, homogeneous solution. The solution can be sealed within the mixing vessel and stored until needed. Before use, the mixture was heated to 50 °C in an oven.

[0120] The external aqueous phase was prepared containing the components and quantities shown in Table 1-2. TABLE 1-2: External phase components Active ingredient % by weight of active ingredients % by weight in final concentrated composition % by weight of active ingredients in final concentrated composition Glycerin 100 8.41 8.41 SOKALAN CP9 (maleic acid-olefin copolymer) 25 2.56 0.64 Ammonium caseinate 100 0.05 0.05 Citric acid 50 0.15 0.05 Urea 50 5.0 2.5 1258154 of 80 Water 100 33.41 33.41 Triethylenetetramine (TETA) 50 1.655 0.83

[0121] To prepare the external phase, water and the remaining external phase component other than TETA were loaded into a mixing vessel. The solution was stirred to obtain a clear, homogeneous solution. The solution can be sealed within the mixing vessel and stored until needed. Before use, the mixture was heated to 50°C in an oven.

[0122] The interfacial polymerization medium was prepared by first loading the external phase (without TETA) into the vessel of a Waring mixer preheated to 50 °C. The commercial Waring mixer (Waring Products Division, Dynamics Corporation of America, New Hartford, Conn., Mixer 700) was powered by a variable autotransformer from 0 to 120 volts. The mixing speed of the mixer was modified by controlling the mixer's power. The internal phase was added to the external phase over a 16-second interval, and mixing continued to obtain an emulsion.

[0123] To initiate polymerization and encapsulation of the internal phase, TETA was added to the emulsion over a period of approximately 5 seconds. The mixer speed was then reduced to a speed sufficient to produce a vortex for approximately five to fifteen minutes. The emulsion was then transferred to a heated plate and stirred. The reaction vessel was covered and maintained at approximately 50°C for about two hours, as this has been found to be sufficient time to achieve an essentially complete reaction of the isocyanate.

[0124] The capsule slurry is then allowed to cool to near room temperature. The acetochlor microcapsules are then mixed with a stabilizer whose ingredients are listed in the following table. 1258154 of 80 1-3 to form an aqueous dispersion of acetochlor microcapsules. The components listed in Table 1-3, with the exception of the buffer solution, are premixed beforehand using a high-speed mixer (Waring or Cowles mixer). The resulting stabilizer premix is ​​then added to the capsule slurry to stabilize the microcapsule dispersion. Finally, the buffer solution is added, and the mixture is stirred for at least 15 minutes until visual homogeneity is achieved. TABLE 1-3: Stabilizer Components Active ingredient % by weight of active ingredients % by weight in the concentrated composition % by weight of active ingredients in the concentrated composition KELZAN CC (xanthan gum) 100 0.06 0.06 Urea 50 5 2.5 INVALON DAM (naphthalene sulfonate condensate) 40 6.76 2.70 AGNIQUE DFM-111S (silicone-based defoamer) 100 0.001 0.001 PROXEL GXL (1,2-benzisothiazolin-3-one solution) 100 0.06 0.06 Caustic soda (NaOH) 20 0.02 0.004 Disodium phosphate 100 0.201 0.201

[0125] This acetochlor microcapsule dispersion was prepared to have an excess of amine molar equivalents to isocyanate molar equivalents and herbicide-to-coating-wall component ratios. TETA has an approximate equivalent weight of 36.6 g / mol. DESMODUR N3215 has an approximate equivalent weight of 181 g / mol. The average particle size of the acetochlor microcapsules was approximately 10 microns. 1258154 of 80 TABLE 1-4: Final composition 1 of microencapsulated acetochlor Active ingredient % by weight of active ingredients % by weight in the concentrated composition % by weight of active ingredients in the concentrated composition Acetochlor 96.0 44.79 43.0 ISOPAR M (solvent, C11-C16 isoalkanes) 100 2.32 2.32 DESMODUR N 3215 (aliphatic isocyanate based on hexamethylene diisocyanate) 100 3.26 3.26 Glycerin 100 8.41 8.41 SOKALAN CP9 25 2.56 0.64 Ammonium caseinate 100 0.05 0.05 Citric acid 50 0.15 0.05 Urea 50 10.0 5.0 Water 100 33.41 33.41 Triethylenetetramine (TETA) 50 1.655 0.83 KELZAN CC (xanthan gum) 100 0.06 0.06 INVALON DAM (naphthalene sulfonate condensate) 40 6.76 2.70 AGNIQUE DFM-111S (silicone-based defoamer) 100 0.001 0.001 PROXEL GXL (1,2-benzisothiazolin-3-one solution) 100 0.06 0.06 Caustic soda 20 0.02 0.004 Disodium phosphate 100 0.201 0.201 Example 2

[0126] A series of premixed herbicide concentrates containing microencapsulated acetochlor and selected dicamba salts were prepared. The dicamba salt concentrates were prepared by mixing water with the respective dicamba salt provided in Tables 2-1, 2-2, and 2-3 below. 1258154 of 80 As stated herein, dicamba salts comprise: DGA = diglycolamine salt; MEA = monoethanolamine salt; Na = sodium salt; and K = potassium salt. TABLE 2-1: Dicamba DGA Formulation Active ingredient % by weight of active component (AE) % by weight of active component (IA) % by weight of active component Dicamba 38.5 56.90 Water 43.10 TABLE 2-2: Dicamba MEA Formulation Active ingredient % by weight of active component (AE) % by weight of active component (IA) % by weight of active component Dicamba 38.5 49.32 Water 50.68 TABLE 2-3: Sodium Dicamba Formulation Active ingredient % by weight of active component (AE) % by weight of active component (IA) % by weight of active component Dicamba 34.5 38.1 Water 61.90

[0127] To prepare the premixed concentrates, the microencapsulated acetochlor composition prepared according to Example 1 was mixed with the dicamba salt concentrates at the concentrations shown in Table 2-4. Water was added as needed to adjust the concentration of each herbicide.

[0128] In order to estimate the potential damage to crops from microencapsulated acetochlor, the acetochlor release rate profile was measured in the laboratory using a SOTAX AT-7 stirring dissolution test apparatus (SOTAX Corporation; Horsham, PA 19044). A slurry was prepared A 1258154 aqueous solution containing 1 wt% of the microencapsulated herbicide active ingredient acetochlor was prepared by combining the concentrated compositions with deionized water and mixing at 150 RPM and 25 °C. An aliquot of each solution was taken after 24 hours. Each aliquot was filtered through a syringe filter (TARGET 0.2 μm cellulose acetate, ThermoFisher Scientific) to remove all capsules. The resulting solution was then analyzed for acetochlor by HPLC. The release rate test results are shown in Table 2-4. TABLE 2-4: Release rate of solutions prepared from a concentrate containing acetochlor and dicamba Formulation No. Acetochlor (% of ai) Dicamba (% of ae) Dicamba salt Weight ratio of acetochlor / dicamba Acetochlor release rate in 24 hours (ppm) Control 33.0 0 -- -- 108.6- 176.1 110-B-1 26.24 11.7 DGA 2.25:1:0 300.4 110-B-2 26.61 11.8 MEA 2.25:1:0 303.5 110-B-3 23.01 10.2 Na 2.25:1:0 226.2 110-B-4 25.02 11.1 K 2.25:1:0 251.4

[0129] These results show that the acetochlor release rate increases by as much as approximately three times when the solution is prepared from a concentrate containing microencapsulated acetochlor and various dicamba salts. The results also show that the acetochlor release rate is unexpectedly affected by the type of dicamba salt used. When an alkali metal (sodium and potassium) dicamba salt was used, the acetochlor release rate increased relative to 1258154 of 80 control, but to a significantly lesser degree compared to the release rates when a dicamba amine salt was used.

[0130] Additional premixed concentrates were prepared in the same manner, except that a release-modulating agent comprising a polyvalent metal salt (calcium chloride, calcium acetate, or copper sulfate) was first added to the microencapsulated acetochlor composition before mixing it with the dicamba salt concentrate. A representative procedure for preparing the premixed concentrates of microencapsulated acetochlor, dicamba, and the release-modulating agent is described below.

[0131] In a beaker, 61.40 g of 43% microencapsulated acetochlor prepared according to Example 1 were poured into a 200 mL beaker. A portion of a polyvalent metal salt (e.g., 0.94 g of calcium chloride) was then slowly added to the beaker while the suspension was continuously stirred using a magnetic stirrer. The suspension was stirred for at least 30 minutes to ensure thorough dissolution of the polyvalent metal salt (e.g., calcium chloride). A portion of the dicamba salt concentrate (e.g., 30.39 g of dicamba DGA (38.5% ae)) was then added to the beaker, followed by water (e.g., 7.27 g). The mixture was stirred for an additional 10 minutes.

[0132] The previously described release rate test was repeated. The results are provided in Table 2-5. The results show that the addition of a polyvalent metal salt to the premixed concentrates significantly reduced the release rate of acetochlor. 1258154 of 80 The use of calcium (e.g., calcium chloride) was effective in reducing the release rate of acetochlor by as much as four times. TABLE 2-5: Release rate of solutions prepared from a concentrate containing acetochlor, dicamba, and a salt of a polyvalent metal No. Formulation Acetochlor (% ai) Dicamb a (% ae) Dicamb a salt Salt of a polyvalent metal Salt of a polyvalent metal (% by weight) Weight ratio of acetochlor / di camba / metal salt Release rate of acetochlor in 24 hours (ppm) 7110-B-5 22.04 9.8 DGA CaCl2 1.18 2.25:1:0.12 118.8 7110-B-6 24.87 11.1 MEA CaCl2 1.33 2.25:1:0.12 98.6 7110-B-7 21.75 9.7 Na CaCl2 1.16 2.25:1:0.12 75.0 7110-B-8 23.79 10.6 K CaCl2 1.27 2.25:1:0.12 77.6 576-A-1 25.18 11.19 DGA CaCl2 1.2 2.25:1:0.11 109.5 576-A-4 25.3 11.24 DGA CaCl2 1.05 2.25:1:0.09 118.4 126-A-3 25.87 11.5 DGA Calcium acetate 1.38 2.25:1:0.12 128.3 126-A-7 25.95 11.53 DGA Calcium acetate 1.73 2.25:1:0.15 110.3 126-A-1 25.72 11.43 DGA Calcium acetate 2.29 2.25:1:0.2 97.3 110-B-9 21.97 9.8 DGA CuSO4 1.66 2.25:1:0.17 197.1 110-B-10 19.55 8.7 Na CuSO4 1.48 2.25:1:0.17 136.2 Example 3

[0133] A series of herbicide concentrates containing microencapsulated acetochlor and sodium dicamba were prepared by blending a microencapsulated acetochlor composition prepared according to Example 1, wherein sodium dicamba is at the concentrations specified in Table 3-1. Calcium chloride was also added to the herbicide concentrates in varying amounts as a modulating agent of 1258154 of 80 the release before mixing with sodium dicamba. The release rate test of Example 2 was repeated with these concentrates. These results are also provided in Table 3-1. TABLE 3-1: Samples to detect the association of acetochlor release rate with calcium ion content in premixed formulations Formulation No. Acetochlor (% of ai) Dicamba Na (% of ae) CaCl2 (% wt) Ca2+ / Acetochlor (% w / w) Molar ratio of TETA / Ca 2+ Acetochlor release rate in 24 hours (ppm) 260-B-6 24.7 30.1 0.00 0 — 231.3 260-B-1 24.6 28.48 0.12 0.0018 11.97 230.2 260-B-2 24.6 27.36 0.25 0.0037 5.75 226.8 260-B-3 24.4 28.85 0.52 0.0077 2.74 209.9 260-B-4 24.3 27.6 0.74 0.011 1.92 151.2 260-B-5 24.4 31.88 1.15 0.017 1.24 126.8 Example 4

[0134] A series of premixed herbicide concentrates containing microencapsulated acetochlor and selected dicamba salts were prepared by mixing a microencapsulated acetochlor composition prepared according to Example 1 with dicamba salts at the concentrations specified in Tables 4-1 and 4-2. One or more polyvalent metal salts (calcium chloride, calcium acetate, or copper sulfate) were added to each concentrate during preparation as release modulators. In addition, sodium acetate was added alone or in combination with 1258154 of 80 EDTA was added to the selected concentrates. The release rate test from Example 2 was repeated with these concentrates. These results are also provided in Tables 4-1 and 4-2. TABLE 4-1: No. Formulation Acetochlor (% of ia) Dicamba (% of ea) Dicamba salt CaCl2 (% by weight) CuSO4 (% by weight) Sodium acetate (% by weight) EDTA (% by weight) Acetochlor / Dicamba / CaCl2 (% w / w) Release rate of acetoclor in 24 hours Control 1 33 0 — — — — — — 124 Control 2 36 0 — — — — — — 116 Control 3 43 0 — — — — — — 118 110-C-5 26.4 11.7 DGA 2.4 0 2.2 0 2.25:1:08:00-10-C-0. 26.4 11.8 DGA 2.4 0 3.5 0 2.25:1:0, 08 141.2 110-C-9 26.4 11.8 DGA 1.8 0 0 0 2.25:1:0, 06 203.9 110-C- 101 1.4 DGA 1.8 0 2.2 0 2.25:1:0, 06 203.3 110-C-11 26.4 11.7 DGA 1.8 0 4.4 0 2.25:1:0, 06 203.9 110-C-12 26.4 11.8 DGA 0.20.2 2.25:1:0, 1 179.9 110-C-13 26.4 11.7 DGA 2.4 0 2.2 0.5 2.25:1:0, 08 135.1 110-C-14 26.4 11.7 DGA 1.8 2.0.2.0:2:5 06 240.1 110-D-1 26.4 11.7 DGA 3.0 0 0 0 2.25:1:0, 1 110.8 110-D-2 26.4 11.7 DGA 2.4 0 2.2 0 2.25:1:0-13-3-13. 26.4 11.7 DGA 2.4 0 2.2 0.5 2.25:1:0, 08 133.0 110-D-4 26.4 11.7 DGA 2.4 0 4.4 0 2.25:1:0, 08 115.7 10-D-5 1.4 1.67 DGA 2.4 0 4.4 0.5 2.25:1:0, 08 131.0 110-D-6 26.4 11.9 DGA 3.0 0 4.4 0 2.25:1:0, 1 103.2 11.09-GA 11:4 0.5 2.25:1:0, 1 112.7 110-D-8 26.4 11.9 DGA 1.8 0 4.4 0 2.25:1:0, 06 128.2, 1258154 of 80 110-D-9 26.4 11.9 DGA 1.8 0 2.2 0.5 2.25:1:0, 06 157 110-E-1 26.4 11.7 Na 0.9 0.3 0 0 2.25:1:0, 110, 08 8 11.8 0.9 0 0 0 2.25:1:0, 08 84.02 110-E-3 26.4 11.7 0.9 0 2.2 0 2.25:1:0, 08 85.94 110-E-4 0 1.26 2.25:1:0, 06 89.83 110-E-5 26.4 11.8 DGA 3.0 0 4.4 0.5 2.25:1:0, 1 125.9 110-E-6 26.4 11.7 DGA 4.2.4 0 118.6 TABLE 4-2: Formula No. Acetochlor (ai%) Dicamba (ea) Dicamba salt Calcium acetate (wt%) CuS O4 (wt% ) Sodium acetate (wt% ) ED TA (wt%) Acetochlor / Dicamba / Veacloch / Calcium p%acet SO acetochlor release in 24 hours (ppm) Control 33 0 — — — — -- -- 124 Control 43 0 -- -- -- -- -- -- 116 758-A-2 25.7 10.3 MEA 2.1 0 0 0 2.25-25:1.0-4.0:0 24.8 10.0 MEA 1.0 0.25 0 0 2.25:1.0:0.025:0.1 139 758-L-5 24.0 9.7 MEA 1.0 0.39 2.99 0 2.25-L3.0-0.61 84 9.7 MEA 1.0 0.39 3.00 1.0 2.25:1.0:0.04:0.1 141 471-N-2 21.8 8.8 Na 1.0 0.26 0 0 2.25:1.0:0.025:0.1 102 758-M-7 25.9 10.4 Na 1.0 0.00 3.22 0 2.25:1.0:0.0:0.1 125 1258154 of 80 758-M-9 24.6 9.9 Na 1.0 0.25 3.06 0 2.25:1.0:0.025:0.1 97 758-M- 11 24.6 9.9 Na Example 5.

[0135] A series of premixed herbicide concentrates containing microencapsulated acetochlor and selected dicamba salts were prepared by blending a microencapsulated acetochlor composition prepared according to Example 1, where the dicamba salts are at the concentrations specified in Table 5-1. One or more polyvalent metal salts (calcium acetate or copper sulfate) were added to each concentrate during preparation as a release modulator. In addition, sodium acetate was added alone or in combination with EDTA to the selected concentrates. The release rate test of Example 2 was repeated with these concentrates. These results are also provided in Table 5-1. TABLE 5-1: No. Formulation Acetochlor (% of water) Dicamba (% of ea) Dicamba salt Calcium acetate (% by weight) CuS O4 (% by weight) Sodium acetate (% by weight) EDT A (% by weight ) Rate of release of acetochlor in 28-755 hours 24.06 10.70 MEA 1.07 0.54 0 0 124 758-L-2 24.90 11.18 MEA 1.32 0 2.88 0 136 758-L-4 24.34 10.82 MEA 1.20.29 1.83 183 758-P-2 24.32 10.79 MEA 1.3 0.27 2.81 0.44 122 758-P-12 22.44 10.02 Na 0.99 0 0.9 0.6 114 758-P-9 22.19 9.8 Na 0.029 0.89 0.6 107 1258154 of 80 758-J-10 24.88 11.06 Na 1.1 0.27 0.93 0 100 758-J-11 25.00 11.18 Na 1.11 0.28 0.99 1.18 114 Example 6

[0136] A series of premixed herbicide concentrates containing microencapsulated acetochlor and selected dicamba salts were prepared by blending a microencapsulated acetochlor composition prepared according to Example 1, wherein the dicamba salts are at the concentrations specified in Table 6-1. A polyvalent metal salt (calcium chloride) was added to each concentrate during preparation as a release modulator. The release rate test of Example 2 was repeated with these concentrates. These results are also provided in Table 6-1. TABLE 6-1: Formulation No. Acetochlor (% ai) Dicamba (% ae) Dicamba salt Calcium chloride (% wt) Acetochlor release rate in 24 hours (ppm) Control 34 - - - 104 260-A-1 26.4 11.7 DGA - 317 260-A-2 26.4 11.7 Na - 252 110-L-2 26.4 11.7 DGA 0.94 147 110-P-9 26.4 11.7 Na 0.94 110

[0137] Application mixtures were prepared from these concentrates and applied to soybeans and cotton to determine crop damage using the following procedure.

[0138] Spray solutions were diluted to appropriate application rates using a Packard MultiProbe 204DT. Each treatment was replicated 4 times. 1258154 of 80 times. The herbicide mixtures were applied using a TJET 9501 flat nozzle with the pressure set to 24 psi (165 kPa). The spray nozzle was positioned approximately 16 inches above the top of the plant material. Each application was made with a spray volume of 10 gallons per acre (GPA).

[0139] Treatments were carried out when plants had reached the desired size, height, or leaf stage. For crop safety studies, soybeans were treated between the 2-3 leaf stage and when plants were approximately 15-20 cm tall, and cotton was treated between the 3-4 leaf stage and when plants were approximately 20-30 cm tall. For weed efficacy treatments, ABUTH plants were treated at the 5-6 leaf stage. Application rates for crop safety were selected to mimic real-world 1X and 2X treatment scenarios or overlapping conditions. Application rates for weed efficacy were selected to achieve percentage control ratings ranging from 50% control at the lower rate to 90% control at the higher rate.Doses within this control range provide the best possible comparisons of efficacy between formulations, allowing for the separation of the relative performance of test samples. The dosage structure used for a given test depends on the environmental conditions at the time of spraying (time of year), the plant species being treated (highly susceptible or difficult to kill), and the age (or size) of the plants being treated.

[0140] Figures 1-2 show the results of damage to soybean and cotton crops, respectively. 1258154 of 80

[0141] The release rate test and crop safety tests on soybeans and cotton were repeated for the formulations described in Table 6-2. The results of the crop safety tests for soybeans and cotton are shown in Table 6-3. Crop damage is reported as a percentage average calculated using the least squares method. Crop damage is compared to applications of the commercial products HARNESS (available from Monsanto Co.) and CLARITY (available from BASF) at the rates specified in Table 6-3. HARNESS contains the herbicide acetochlor in an emulsifiable concentrate. CLARITY contains the diglycolamine salt of dicamba. The premix formulation WARRANT was prepared by blending the commercial concentrate WARRANT (available from Monsanto Co.) with a sodium dicamba concentrate. TABLE 6-2: Formulation No. Acetochlor (% ai) Dicamba (% ae) Dicamba salt Calcium chloride (% wt) Acetochlor release rate in 24 hours (ppm) Control 33 - - - 105.8 WARRANT Premix 26.4 11.7 Na 0.8 116.0 260-A-1 26.4 11.7 DGA - 315.4 260-A-2 26.4 11.7 Na - 251.5 110-L-2 26.4 11.7 DGA 0.9 146 110-P-9 26.4 11.7 Na 0.8 109.3 TABLE 6-3: No. Formulation Dose of Damage in application soybean cotton (g / ha) (%) (%) 1258154 of 80 HARNESS 1260 11.3 7.1 HARNESS 2520 26.3 16.9 CLARITY 560 0.0 0.1 CLARITY 1120 0.0 1.6 Premix WARRANT 1260 0.5 0.8 Premix WARRANT 2520 3.8 0.7 260-A-1 1260 3.3 3.5 260-A-1 2520 10.8 6.3 260-A-2 1260 4.1 1.0 260-A-2 2520 5.3 2.1 110-L-2 1260 1.2 0.4 110-L-2 2520 1.6 2.8 110-P-9 1260 2.5 0.2 110-P-9 2520 2.4 2.4

[0142] The results show that formulations containing calcium chloride (Formulations No. 110-L-2, 110-P-9, and the WARRANT premix) showed lower acetochlor release rates at 24 hours and generally less crop damage when compared to similar formulations not containing calcium chloride (Formulations No. 260A-1 and 260-A-2).

[0143] The results also show that crop damage was generally less for Formulation No. 260-A-2, which contained sodium dicamba, compared to Formulation No. 260-A-1, which contained dicamba DGA, especially at the higher application rate of 2520 g / ha. Crop damage for Formulation No. 260-A-2 was also comparable to formulations containing calcium chloride, particularly in the case of 1258154 of 80 cotton. The crop safety results for Formulation No. 260A-2 are surprising given that the release rate of acetochlor at 24 hours for this formulation was as much as 2.5 times higher than in the case of formulations containing calcium chloride. Example 7

[0144] A series of premixed herbicide concentrates containing WARRANT (microencapsulated acetochlor available from Monsanto Co., St. Louis, Missouri) and selected coherbicides were prepared by mixing the two components in water at the concentrations specified in Table 7-1. A polyvalent metal salt (calcium chloride) was added to each concentrate during formulation as a release modulator. The release rate test described in Example 2 was repeated. The results are also provided in Table 7-1. TABLE 7-1: Effect of selected coherbicides on acetochlor release and the effect of Ca2+ on the release rate No. Formulation Acetochlor (% ai) Coherbicide Coherbicide (% by weight) CaCl 2 (% by weight) Acetochlor / coh erbicda / CaCl 2 Acetochlor release rate in 24 hours (ppm) 110-A-5 30.85 Fomesafe no 15.43 0 2.25:0.5:0 412.7 110-A-6 26.88 Fomesafe no 13.44 1.43 2.25:0.5:0.12 111.7 110-A-7 25.04 Glufosinate 18.78 0 2.25:0.75:0 521.3 110-A-8 21.95 Glufosinat or 16.46 1.17 2.25:0.75:0.1 2 272.1 Example 8 1258154 of 80

[0145] A series of herbicide concentrates containing WARRANT (microencapsulated acetochlor) were prepared at the concentrations specified in Table 8-1. A salt of a polyvalent metal (calcium acetate) was added to the selected concentrates during formulation. The release rate test described in Example 2 was repeated. The results are also provided in Table 8-1. TABLE 8-1: Modulation of WARRANT release rate with calcium acetate Formulation No. Acetochlor (% ai) Calcium acetate (% wt) Acetochlor / calcium acetate (% w / w) Acetochlor release rate in 24 hours (ppm) Control 33.0 0 -- 148 758-K-1 32.9 0.24 2.25:0.025 146 758-K-2 32.8 0.48 2.25:0.05 111 758-K-3 32.7 0.94 2.25:0.1 88 758-K-4 32.3 1.84 2.25:0.2 78 Example 9

[0146] A series of application mixtures (1 wt. ai) were prepared from commercial-grade concentrates (microencapsulated acetochlor available from Monsanto Co., St. Louis, Missouri). A salt of a polyvalent metal (calcium acetate) was added to each mixture. The release rate test described in Example 2 was repeated. The results are provided in Figures 3 and 4. The results show that the release rate of acetochlor decreases with increasing concentration of the polyvalent metal ion (e.g., calcium). Example 10

[0147] A series of premixed concentrated herbicide formulations containing microencapsulated acetochlor (WARRANT) and salts were prepared 1258154 of 80 selected dicamba samples were prepared by mixing a microencapsulated acetochlor composition prepared according to Example 1, where the dicamba salts were at the concentrations specified in Table 10-1 along with additional components, including a dispersant and a stabilizer. Sodium acetate was also added as a volatility control additive. The amount of a polyvalent metal salt (calcium chloride) added to each formulation ranged from 0.0 to 0.8 wt%. The release rate test described in Example 2 was conducted with these formulations. The results are also provided in Table 10-1. TABLE 10-1: Formulation No. Acetochlor (% ai) Dicamba (% ae) Dicamba salt Calcium chloride (% wt) Sodium acetate (% wt) Acetochlor release rate in 24 hours (ppm) 100218 26.4 11.7 Na 0.8 3.3 112 100219 26.4 11.7 Na 0.4 3.3 171 100220 26.4 11.7 Na 0.0 3.3 252 100222 26.4 11.7 DGA 0.0 3.3 317 100226 26.4 11.7 Na 1.6 3.3 --

[0148] A series of field trials were conducted for crop safety in cotton (Gossypium hirsutum, GOSHI) and soybean (Glycine max, GLXMA) fields. Application timing was post-emergence, and treatments were applied using a backpack or tractor-mounted sprayer. Spray mixtures prepared from the formulations listed in Table 10-1 were applied under field conditions at application rates of 1.26 kg / ha and 2.52 kg / ha of acetochlor (ia) and 0.56 kg / ha and 1.12 kg / ha of dicamba (ea). For comparison, 1258154 of 80 conducted field tests with tank-mixed application mixtures of CLARITY with WARRANT and of CLARITY with DUAL II MAGNUM (S-metolachlor herbicide not encapsulated in an emulsifiable concentrate available from Syngenta).

[0149] Crop damage was assessed three days post-treatment. The results of the crop safety field tests are shown in Table 10-2. Results are reported relative to crop damage produced using an application mixture of CLARITY with WARRANT. A crop damage rating that is > 0 but < 1 indicates that the crop damage is indistinguishable from the crop damage produced using an application mixture of CLARITY with WARRANT. A crop damage rating that is > 1 indicates that the crop damage is significantly less detrimental compared to the crop damage produced using the application mixture of CLARITY with WARRANT. A crop damage rating that is > 0 indicates that the crop damage is significantly more detrimental compared to the crop damage produced using the application mixture of CLARITY with WARRANT. TABLE 10-2: Formulation No. Necrosis with 1X dose at 3 days post-treatment compared to necrosis with CLARITY + WARRANT All data n GO SHI n GLXMA n CLARITY + DUAL II MAGNUM -9.3 68 -5.8 36 -13.3 32 100218 0.5 68 0.9 36 0.0 32 100219 0.2 68 0.4 36 0.0 32 100220 0.3 68 1.0 36 -0.5 32 100222 -0.7 68 -1.3 36 0.0 32 TABLE 10-3: 1258154 of 80 Necrosis with 2X dose at 3 days post-treatment compared to necrosis with CLARITY + WARRANT Formulation All data n GOSHI n GLXMA n CLARITY + DUAL II MAGNUM -16.1 68 -6.5 36 -26.9 32 100218 2.4 68 4.4 36 0.2 32 100219 1.1 68 1.8 36 0.2 32 100220 1.6 68 2.8 36 0.3 32 100222 -0.8 68 -1.4 36 -0.1 32

[0150] The results show that the tank mix application mixture of CLARITY (dicamba diglycolamine salt) and DUAL II MAGNUM (non-encapsulated S-metolachlor) was significantly more harmful to cotton and soybeans compared to the control (tank mix application mixture containing CLARITY and WARRANT). Formulation 100222 was also harmful to cotton and soybeans, but to a much lesser degree compared to the tank mix application mixture of CLARITY and DUAL II MAGNUM. Formulations 100218 and 100219, which contain a polyvalent metal cation (calcium chloride) to modulate acetochlor release, were significantly less harmful compared to the control.Furthermore, although formulation 100220 exhibited a high 24-hour acetochlor release rate of 252 ppm, this formulation unexpectedly provided acceptable crop safety, especially at the highest application rate. Example 11

[0002] Volatility tests were conducted with spray solutions prepared from the concentrates described in Example 10. Spray solutions of CLARITY and a mixture of CLARITY and WARRANT (i.e., spray solutions not containing the volatility control additive) 1258154 of the 80 samples were also subjected to volatility testing for comparison. The protocol for volatility testing is described below.

[0100] The humididomes (24.25 L) were obtained from Hummert International (Part No. 14-3850-2 for the humididomes and 11-3050-1 for the 1020 flat tray) and modified by cutting a 2.2 cm diameter hole at one end approximately 5 cm from the top to allow the insertion of a glass air sampling tube (22 mm OD) containing a polyurethane foam (PUF) filter. The sampling tube was secured with a VITON O-ring on each side of the humididome wall. The external air sampling tube of the humididome was fitted with tubing connected to a vacuum distributor immediately before sampling.

[0101] The flat tray beneath the humididome was filled with 1 liter of dry or moist 50 / 50 sieved soil (50% Redi-Earth and 50% US 10 Field Soil) to a depth of approximately 1 cm. Spray solutions of each formulation were prepared to contain 1.2% dicamba ae, which is equivalent to an application rate of 1.0 lb / A ae at a rate of 10 gallons per acre (GPA), and then sprayed onto the soil in each humididome. Four separate humididome boxes were sprayed to obtain four replicate measurements for each formulation.

[0102] The flat tray bottom containing the soil-based dicamba formulation was covered with the humididome lid, and the lid was secured with fasteners. The assembled humididomes were placed in a temperature- and humidity-controlled environment and connected to a vacuum distributor via the air sampling line. The humididome chambers were set at 35°C and 40% relative humidity (RH). Air was removed through the humididome and from the 1258154 of 80 PUF was introduced at a rate of 2 liters per minute (LPM) for 24 hours, at which point air sampling was stopped. The humidifiers were then removed from the controlled environment, and the PUF filter was removed. The PUF filter was extracted with 20 mL of methanol, and the solution was analyzed for dicamba concentration using known LC-MS methods.

[0103] Table 11-1 provides the average concentration of dicamba in air for the formulations evaluated. The results show that sodium acetate was effective in reducing the volatility of dicamba by a factor of ten compared to a CLARITY spray solution and a CLARITY and WARRANT spray solution. TABLE 11-1: Formulation Concentration of dicamba in air (ng / l) CLARITY 0.057 CLARITY + WARRANT 0.061 100218 0.005 100220 0.006 100226 0.006

[0104] When elements of the present invention or one or more preferred embodiments thereof are introduced, the determinatives “a”, “an”, “the” and “said” shall denote that there is one or more of the elements. The terms “comprising”, “including” and “having” shall be construed inclusively, so that there may be additional elements other than those enumerated.

[0105] Taking into account the above, it can be observed that the various objectives of the invention are achieved and that other advantageous results are obtained.

[0106] Since it is possible to make various changes in the 1258154 of 80 compositions and the preceding methods without departing from the scope of the invention, all the content presented in the preceding description and represented in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. 1258154 of 80 MIGUEL NORBERTO ARMANDO - 20109002225 Digitally signed by PORTALTRAM ITES - INPI Date: 2021.01.21 14:44:39-03:00 Reason: Digitally Signed by the INPI Location: Buenos Aires, Argentina 1258154

Claims

1. An aqueous concentrated herbicidal composition, characterized in that it comprises: (a) at least one microencapsulated particulate acetamide herbicide dispersed in a liquid aqueous medium comprising a water-immiscible core material comprising the acetamide herbicide and a polyurea coating wall containing the core material,wherein the concentration of the acetamide herbicide in the composition based on the active ingredient is at least 10% by weight and wherein the polyurea coating wall is formed in a polymerization medium by a polymerization reaction between a polyisocyanate component comprising a polyisocyanate or a mixture of polyisocyanates and a polyamine component comprising a polyamine or a mixture of polyamines to form the polyurea and wherein the ratio of amine molar equivalents contained in the polyamine component to isocyanate molar equivalents contained in the polyisocyanate component is at least 1.01:1; and (b) a release-modulating agent comprising a polyvalent metal cation,wherein the molecular weight of the release-modulating agent is not greater than 1000 g / mol; and wherein the mole ratio of the polyvalent metal cation to the molar equivalents of amine contained in the polyamine component is between 0.05:1 and 1.5:

1. 14 Claims follow,