A composition for weed control.

Description

A COMPOSITION FOR WEED CONTROL Divided from BR 11 2018 013786 3, deposited on 05 / 07 / 2018. FIELD OF THE INVENTION

[0001] The present invention relates to herbicidal compositions. More specifically, the present invention relates to ZC formulations comprising pendimethalin. ORIGINAL ORDER DETAILS:

[0002] This application is a certificate of addition to the Indian Application 2251 / MUM / 2011 filed on August 10, 2011, and to PCT Application No. PCT / IB2011 / 002280 published as WO2013021229 A1 or a continuation in part of US Patent Application 14 / 238,009, the contents of which are incorporated in full into this application by reference. BACKGROUND OF THE INVENTION AND PRIOR ART:

[0003] The type of herbicide formulation plays an important role in the effectiveness of weed control. Various types of herbicide formulations aim to increase herbicide efficacy, such that the active ingredient is delivered to the weed with maximum effectiveness, minimum waste, and prolonged residual effect.

[0004] A combination of two active ingredients sometimes leads to incompatibility. Physical and biological incompatibility is not uncommon, for example, insufficient stability of a combined formulation, decomposition of an active ingredient, or antagonism of the active ingredients. Incompatibility can lead to the mixture forming a precipitate, gel, or flakes that stabilize, rendering the herbicide mixture and container useless. This will also result in inefficient pesticide spraying, resulting in low efficacy. Therefore, it is important for formulators to prepare stable formulations that allow two incompatible actives to be combined into a single formulation, giving a favorable active profile, high stability, and in some cases, greater synergy, thus allowing a reduced application rate compared to the individual application of the active compounds.Therefore, there is a need in the state of the art for a formulation that is stable, especially when two incompatible active compounds are combined, providing a broader spectrum of control while reducing the application rate. Petition 870200048176, dated 04 / 16 / 2020, pp. 80 / 127 2 / 43

[0005] Herbicide combinations are used for the effective and economical control of weeds. These combinations offer advantages such as a broad spectrum of herbicide action, a synergistic effect, prevention of the degradation of one herbicide due to the presence of the second herbicide, and a reduction in herbicide dosages.

[0006] These herbicide combinations can be prepared by tank mixing the individual herbicides at the desired rates immediately before application. However, regulating the rates of individual herbicides in tank-mix combinations is a problem for many farmers, who often tend to overdos the herbicides, leading to undesirable effects on field crops. Therefore, it is preferable to prepare formulations comprising herbicide combinations at the time of manufacture. These formulations and their preparation suffer from the complication of mutual degradation and incompatibility of herbicides when presented and stored in the same formulation for an extended period of time. It is often a challenge for a qualified formulator to prepare a stable composition comprising a combination of two or more active ingredients.

[0007] ZC formulations are a combination of capsule suspension (CS) and concentrated suspension (SC) such that the formulation contains a stable aqueous suspension of microcapsules and fine solid particles (in aqueous phase), each of which contains at least one active ingredient.

[0008] Pendimethalin is a dinitroaniline herbicide. It is a selective herbicide that controls certain broadleaf weeds and grassy weed species in cultivated and uncultivated areas. It is a soil-applied herbicide in pre-planting, pre-emergence, and post-emergence applications using ground and aerial equipment. It is a low-melting-point active ingredient with negligible vapor pressure, which is notorious for its problem of staining / staining plants, as well as all other products and goods with which it comes into contact.

[0009] Application PCT / IB2011 / 002280 discloses a capsule suspension comprising microcapsules in an organic phase and an aqueous phase which optionally comprises a second herbicide. The microcapsules encapsulate pendimethalin. The aqueous phase includes an alkali or alkaline earth metal salt of an organic acid. Petition 870280048246, dated 06 / 04 / 2018, pp. 89 / 179 3 / 43

[0010] This application describes that the second herbicide may be co-microencapsulated with pendimethalin or may be non-encapsulated or may be microencapsulated separately and mixed with the microencapsulated pendimethalin. The second herbicide is predominantly clomazone or a volatile herbicide such as 2,4-D esters, MCPA esters, triclopyr or picloram. This application provides for any other combination partner for the encapsulated pendimethalin.

[0011] Pendimethalin is known to be incompatible with several classes of herbicides due to its physical characteristics that lead to unstable formulations. Other known water-based formulations are also known not to work well with pendimethalin. There is, therefore, a need in the art for stable and compatible water-based pendimethalin formulations that; a. provide pendimethalin formulations that do not cause discoloration / staining with a co-active herbicide. b. provide a physically stable pendimethalin formulation with a co-active herbicide. c. provide a pendimethalin formulation with a co-active that has a prolonged herbicidal effect. d. provide an environmentally friendly, water-based pendimethalin formulation with a co-active herbicide. e. provide a pendimethalin formulation that overcomes incompatibility with other active ingredients.

[0012] The present invention therefore aims to solve the problem of incompatibility and stability with the use of ZC formulations, specifically for active ingredients such as pendimethalin when combined with herbicides that are otherwise known to be incompatible with pendimethalin.

[0013] An example of an embodiment of the present invention may improve one or more of the problems mentioned above: BRIEF DESCRIPTION OF THE INVENTION

[0014] A suspension comprising; particles of a first herbicide selected from the group consisting of Petition 870280048246, dated 06 / 04 / 2018, page 80 / 179 4 / 43 sulfonylurea herbicides, triazinone herbicides, imidazolinone herbicides, triazine herbicides, anilide herbicides, sulfonamide herbicides, organophosphate herbicides, amide herbicides or alkanimid herbicides; combined with a suspension of pendimethalin microcapsules in an aqueous phase, said microcapsules comprising a herbicidally effective amount of pendimethalin encapsulated in a polyurea polymer wall, wherein said polyurea polymer wall constitutes from about 1% to about 20% by total weight of the suspension, said aqueous phase comprising at least one alkali or alkaline-earth metal salt of an organic acid selected from the group consisting of acetic acid, propyl acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, wherein said at least one alkali or alkaline-earth metal salt of an organic acid is present in an amount ranging from about 2% to about 55% by weight of the suspension;and whereby the aforementioned first herbicide exhibits improved physicochemical stability in the presence of the aforementioned encapsulated pendimethalin. DETAILED DESCRIPTION OF THE INVENTION

[0015] It has now been discovered that encapsulated pendimethalin physically and chemically stabilizes a concentrated suspension of the first herbicide contemplated according to the present invention, which is otherwise known to be incompatible with pendimethalin.

[0016] Therefore, in one aspect, the present invention provides a ZC composition comprising: (a) microencapsulated pendimethalin; and (b) a concentrated suspension of a co-herbicide.

[0017] Thus, in one aspect, the present invention provides a suspension comprising: particles of a first herbicide selected from the group consisting of sulfonylurea herbicides, triazinone herbicides, imidazolinone herbicides, triazine herbicides, anilide herbicides, sulfonamide herbicides, organophosphate herbicides, amide herbicides or alkanimid herbicides; combined with a suspension of pendimethalin microcapsules in a single phase Petition 870280048246, dated 06 / 04 / 2018, page 81 / 179 5 / 43 aqueous, said microcapsules comprising a herbicidally effective amount of pendimethalin encapsulated in a polyurea polymer wall, wherein said polyurea polymer wall constitutes from about 1% to about 20% by weight of the total suspension, said aqueous phase comprising at least one alkali or alkaline-earth metal salt of an organic acid selected from the group consisting of acetic acid, propyl acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, wherein said at least one alkali or alkaline-earth metal salt of an organic acid is present in an amount ranging from about 2% to about 55% by weight of the suspension; and wherein said first herbicide exhibits improved physicochemical stability in the presence of said encapsulated pendimethalin.

[0018] In one embodiment, the preferred suspension is a ZC formulation.

[0019] Thus, embodiments of the present invention may provide a composition comprising ZC formulations comprising encapsulated pendimethalin and at least one co-herbicide.

[0020] The present inventors have surprisingly discovered that pendimethalin, when combined with actives that are incompatible with pendimethalin when formulated as conventional formulations, such as EC, WDG, etc., can be combined to form stable formulations when combined in a ZC formulation. Therefore, it was found that the combination of a concentrated suspension of these herbicides with encapsulated pendimethalin physically and chemically stabilized the resulting ZC formulation, a result that had not been satisfactorily achieved until now for these herbicides.

[0021] Pendimetallin has two crystallomorphic forms, triclinic pendimethalin I (P1-), a thermodynamically stable orange form, and monoclinic pendimethalin II (P21 / c), a metastable bright yellow form. The latter is typically produced first after cooling molten pendimethalin, while the orange form is formed by a polymorphic phase transition that occurs slowly after long-term storage of the yellow form at temperatures Petition 870280048246, dated 06 / 04 / 2018, page 82 / 179 6 / 43 below its melting point. The polymorphic phase transition always leads to an increase in particle size. This results in the loss of formulation properties such as suspendability, retention in wet sieving, etc., and also gives rise to a unique problem with the use of pendimethalin, namely, discoloration / staining.

[0022] Pendimethalin is known to suffer from incompatibilities when combined with certain active compounds. These formulations face problems of active compound incompatibility, product staining, crystallomorphic transition, particle size growth, loss of physicochemical properties of the formulation on the shelf, etc. Tank mixing also leads to flocculation, and pesticide separation leads to lack of formulation efficacy or crop damage.

[0023] For example, it was found that mixing pendimethalin 456 CS tank with metribuzin 75% DF leads to flocculation, rendering the mixture useless. This was observed when the pendimethalin 456 CS formulation used was Prowl H2O, a formulation that includes an inorganic salt before encapsulation. The inorganic salt was found to increase water hardness, which led to flocculation in the presence of metribuzin 75% DF.

[0024] Thus, in one embodiment, the present invention provides a ZC formulation comprising: a concentrated suspension comprising particles of a first herbicide selected from the group consisting of sulfonylurea herbicides, triazinone herbicides, imidazolinone herbicides, triazine herbicides, anilide herbicides, sulfonamide herbicides, organophosphate herbicides, amide herbicides or alkanimid herbicides; combined with a capsule suspension comprising pendimethalin microcapsules in an aqueous phase, said microcapsules comprising a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, wherein said polyurea polymer wall constitutes from about 1% to about 20% by total weight of the suspension, said aqueous phase comprising at least one alkali or alkaline earth metal salt of an organic acid selected from the group consisting of acetic acid, propyl acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, wherein said at least one salt of Petition 870280048246, dated 06 / 04 / 2018, p. 83 / 179 7 / 43 an alkali or alkaline-earth metal of an organic acid is present in an amount ranging from about 2% to about 55% by weight of the capsule suspension; and wherein said first herbicide exhibits improved physicochemical stability in the presence of said encapsulated pendimethalin.

[0025] The ZC formulation comprising pendimethalin encapsulated with a first herbicide considerably improved the stability of the first herbicide, which was otherwise susceptible to degradation in the environment of the other herbicides in the formulated product. It is believed that the pendimethalin capsule suspension component used in the formulation contains a salinized system that provides a suitable environment for the susceptible actives. The stable, non-stained capsule suspension improves the shelf life of pendimethalin and reduces staining to a greater degree compared to commercially available pendimethalin formulations.

[0026] The first herbicides of the present invention are those that are known to be susceptible to degradation or to be known to be incompatible with pendimethalin, but show remarkable efficacy when stabilized in the ZC formulation of the present invention.

[0027] Many sulfonylurea herbicides are known to be incompatible with other active compounds. Known wettable powder (WP) formulations of sulfonylurea herbicides, such as pyrazosulfuron-ethyl with pendimethalin, are known to be susceptible to degradation and loss of physicochemical properties, whereas the ZC formulation provides excellent activity stability, as will be demonstrated in the examples below. The ZC product is stable and maintains its physicochemical properties in thermal stability testing, freeze / thaw testing, and real-time storage.

[0028] Heat stability studies indicate a product's stability at higher temperatures and also give an idea of ​​the product's shelf life. Freeze / thaw stability indicates whether the product can withstand low temperature and room temperature cycles. Real-time storage and room temperature indicate the product's shelf life. Petition 870280048246, dated 06 / 04 / 2018, page 84 / 179 8 / 43

[0029] Thus, in one embodiment, the first herbicide may be selected from, but not limited to, classes of herbicides selected from sulfonylurea herbicides, triazinone herbicides, imidazolinone herbicides, triazine herbicides, anilide herbicides, quinolinecarboxylic acid herbicides, quinolinocarboxylic acid herbicides, benzoylcyclohexanedione herbicides, sulfonamide herbicides, benzofuranyl alkylsulfonate herbicides, organophosphorus herbicides, chloroacetanilide herbicides, nitrophenyl ether herbicides, sulfonamide herbicides, amide herbicides or alkanamide herbicides and mixtures thereof.

[0030] In one embodiment, the herbicide sulfonylurea may be selected from, but not limited to; amidosulfuron, azimsulfuron, bensulfuron or methyl bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, mesosulfuron, metazosulfuron, methiopirisulfuron, monosulfuron, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, propirisulfuron, pyrazosulfuron or ethyl pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, trifloxysulfuron, chlorsulfuron, cinosulfuron, etametsulfuron, iodosulfuron, iofensulfuron, metsulfuron or methyl metsulfuron, prosulfuron, tifensulfuron, triasulfuron, tribenuron, triflusulfuron, tritosulfuron.

[0031] In another embodiment, the sulfonylurea herbicide is pyrazosulfuron or an agrochemically acceptable derivative thereof such as pyrazosulfuron-ethyl.

[0032] In one embodiment, the herbicide triazinone may be selected from, but not limited to, ametridione, amibuzin, etiozin, hexazinone, isometiozin, metamitron, metribuzin or trifludimoxazim.

[0033] In another example of embodiment, the herbicide triazinone is metribuzin.

[0034] In one embodiment, the herbicide imidazolinone may be selected from, but not limited to, imazametabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr.

[0035] In another embodiment, the herbicide imidazolinone is imazapic. In another embodiment, the herbicide imidazolinone is imazapic acid.

[0036] In one embodiment, the herbicide triazine may be selected from, but not limited to; dipropetrin, trihydroxytriazine, atrazine, chlorazine, cyanazine, Petition 870280048246, dated 06 / 04 / 2018, page 86 / 179 9 / 43 cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine, propazine, sebuthylazine, simazine, terbuthylazine triethazine, indaziflam, triaziflam, atraton, metometom, prometom, secbumetom, simetom, terbumetom, ametrine, aziprothrine, cyanatrine, desmethrin, dimethethrin, metoprothrin, promethrin, symethrin, terbutrin.

[0037] In another example of embodiment, the herbicide triazine is atrazine.

[0038] In one embodiment, the amide herbicide may be selected from, but not limited to, alidochlor, amicarbazone, beflubutamide, benzadox, benzipram, bromobutide, cafenstrol, CDEA, ciprazole, dimethenamide, dimethenamide-P, diphenamide, epronaz, ethnipromide, fentrazamide, flucarbazone, flupoxam, fomesafen, halosafen, huangcaoling, isocarbamide, isoxaben, napropamide, napropamide-M, petoxamide, propizamide, quinonamide, tebutam, thiafenacil.

[0039] In one embodiment, the amide herbicide is preferably an alkanimid herbicide selected from Napropamide or Napropamide-M.

[0040] In one embodiment, the herbicide anilide may be selected from, but not limited to, chloranocril, cisanilide, clomeprop, cypromide, diflufenicam, erlujxikancaoan, etobenzanide, fenasulam, flufenacet, flufenicam, ipfencarbazone, mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor, picolinafen, propanil, sulfentrazone, triafamon.

[0041] In one embodiment, the herbicide anilide is diflufenicam or flufenacet.

[0042] In one embodiment, the herbicide chloroacetanilide may be selected from, but not limited to, acetochlor, alachlor, butachlor, butenachlor, delachlor, dietatil, dimetachlor, etachlor, etaprochlor, metazachlor, metolaclor, S-metolaclor, pretilaclor, propachlor, propisochlor, prinachlor, terbuchlor, tenilchlor, xylaclor.

[0043] In one embodiment, the herbicide chloroacetanilide is metolachlor or Smetolachlor.

[0044] In one embodiment, quinolinocarboxylic acid herbicides may be selected from, but are not limited to, quinclorac, quinmerac.

[0045] In one embodiment, benzoylcyclohexanedione herbicides may be selected from, but are not limited to, phenquinotrione, ketospiradox, mesotrione, sulcotrione, tefuryltrione, tembotrione. Petition 870280048246, dated 06 / 04 / 2018, page 86 / 179 10 / 43

[0046] In one embodiment, benzofuranyl sulfonate herbicides may be selected, but are not limited to; benfuresate, etofumesate.

[0047] In one embodiment, the herbicide dinitroaniline may be selected from, but is not limited to, benfluralin, butralin, chlornidine, dinitramine, dipropaline, etalfluralin, fluchloralin, isopropaline, metallopralin, nitralin, oryzalin, prodiamine, profluralin, trifluralin.

[0048] In one embodiment, sulfonamide herbicides may be selected from, but are not limited to, asulam, carbasulam, fenasulam, oryzalin, penoxsulam, piroxsulam.

[0049] In one embodiment, the sulfonamide herbicide is orizine.

[0050] In one embodiment, nitrophenyl ether herbicides may be selected from, but not limited to, acifluorfen and salts thereof, aclonifem, bifenox, clomethoxyfen, chlornitrofem, ethnipromide, fluorodifen, fluoroglycofem, fluoronitrofem, fomesafen, fucaomi, furiloxyfen, halosafen, lactofen, nitrofem, nitrofluorfen, oxyfluorfen.

[0051] In one embodiment, organophosphate herbicides may be selected from, but are not limited to, amiprofos-methyl, amiprofos, anilofos, bensulide, bilanafos, butamifos, clacifos, fosamine, glufosinate and all its salts and esters, glufosinate-P, glyphosate and all its salts and esters, huangcaolin, piperofos, shuangjiaancaolin.

[0052] In one embodiment, the organophosphate herbicide is glufosinate or a salt or derivative thereof, and glyphosate or a salt or derivative thereof.

[0053] Therefore, in a preferred embodiment, the first herbicide is selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, flufenaceto, oryzalin, glufosinate, glyphosate and agrochemically acceptable salts and their derivatives.

[0054] Therefore, in this embodiment, the present invention provides a ZC composition comprising: (a) microencapsulated pendimethalin; and (b) a concentrated suspension of a co-herbicide selected from the group Petition 870280048246, dated 06 / 04 / 2018, page 87 / 179 11 / 43 consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, flufenaceto, oryzalin, glufosinate, glyphosate and agrochemically acceptable salts and their derivatives.

[0055] In another embodiment, the present invention provides a suspension comprising: particles of a first herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamideM, flufenaceto, oryzalin, glufosinate, glyphosate and agrochemically acceptable salts and their derivatives; combined with a suspension of pendimethalin microcapsules in an aqueous phase, said microcapsules comprising a herbicidally effective amount of pendimethalin encapsulated in a polyurea polymer wall, wherein said polyurea polymer wall constitutes from about 1% to about 20% by total weight of the suspension, said aqueous phase comprising at least one alkali or alkaline-earth metal salt of an organic acid selected from the group consisting of acetic acid, propyl acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, wherein said at least one alkali or alkaline-earth metal salt of an organic acid is present in an amount ranging from about 2% to about 55% by weight of the suspension;and whereby the aforementioned first herbicide exhibits improved physicochemical stability in the presence of the aforementioned encapsulated pendimethalin.

[0056] In another embodiment, the present invention provides a ZC formulation comprising: a concentrated suspension comprising particles of a first herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, flufenaceto, oryzalin, glufosinate, glyphosate and agrochemically acceptable salts and their derivatives; combined with a capsule suspension comprising pendimethalin microcapsules in an aqueous phase, said microcapsules comprising a Petition 870280048246, dated 06 / 04 / 2018, page 88 / 179 12 / 43 herbicidally effective quantity of pendimethalin encapsulated within a polyurea polymer wall, wherein said polyurea polymer wall constitutes from about 1% to about 20% by total weight of the suspension, said aqueous phase comprising at least one alkali or alkaline-earth metal salt of an organic acid selected from the group consisting of acetic acid, propyl acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, wherein said at least one alkali or alkaline-earth metal salt of an organic acid is present in an amount ranging from about 2% to about 55% by weight of the capsule suspension; and wherein said first herbicide exhibits improved physicochemical stability in the presence of said encapsulated pendimethalin. In one embodiment, the encapsulated pendimethalin component may comprise another herbicide that is different from the first herbicide. This additional herbicide may typically be co-encapsulated with pendimethalin within the microcapsules. The choice of this additional herbicide is not particularly limiting, and the herbicide may be selected from any herbicide that is compatible with pendimethalin.

[0057] The ZC formulations according to the present invention are prepared in such a way that the microencapsulation of pendimethalin is carried out first and the dispersion of the resulting microcapsule, if appropriate after partial or complete removal of the liquid phase, is mixed with a suspension of the first herbicide.

[0058] In an embodiment where the first herbicide is a liquid, it is normally absorbed / adsorbed onto a particulate solid support. The solid support particles, having the absorbed / adsorbed herbicide liquid on them, are subsequently used in a conventional manner to prepare a suspension to be combined with encapsulated pendimethalin.

[0059] In one aspect, the pendimethalin capsule suspension can be prepared by encapsulating pendimethalin within a polymeric wall, said polymeric wall being formed in situ by an interfacial polymerization reaction occurring between a first phase dispersed in a second phase, at least one of said first phases being a second phase. Petition 870280048246, dated 06 / 04 / 2018, pp. 89 / 179 13 / 43 and the second phase is characterized by comprising a predefined quantity of at least one alkali or alkaline-earth metal salt of an organic acid.

[0060] The concentrated suspension of the present invention can be prepared by mixing surfactants, co-formulants, water and the first herbicide.

[0061] The capsule suspension comprising pendimethalin can be prepared by a process as described in the original applications mentioned above.

[0062] The process includes: (a) to form an aqueous solution comprising at least one surfactant and a predefined amount of at least one alkali or alkaline earth metal salt of an organic acid; (b) forming an organic phase by melting a herbicidally effective amount of the active ingredient pendimethalin and adding a predetermined amount of a first wall-forming component to said organic phase; (c) dispersing said organic phase in said aqueous solution to obtain an emulsion; and (d) adding a second wall-forming component to said emulsion such that said second wall-forming component reacts with said first wall-forming component comprised within said emulsion to form a polymeric wall, encapsulating at least said herbicidally effective substance of the active ingredient pendimethalin.

[0063] The concentrated suspension comprising the first selected herbicides according to the present invention can be prepared as follows: (a) forming a paste (semi-fluid suspension) comprising water, surfactant and additional co-formulants with the first herbicide or mixtures thereof; and (b) grinding the paste (semi-fluid suspension) to a desired particle size at room temperature.

[0064] The microcapsules and the concentrated suspension can then be mixed to form a stable ZC formulation.

[0065] In alternative embodiments, the polymeric wall of the capsule of Petition 870280048246, dated 06 / 04 / 2018, pp. 90 / 179 14 / 43 The present invention may be any known casing wall material, but is preferably selected from polyurea, polyurethane, polyamide, polycarbonate, polysulfonamide casing wall or crosslinked or non-crosslinked combinations. Preferably, the polymeric wall of the capsule is a polyurea wall.

[0066] The polymeric wall of the capsule of the present invention is formed using interfacial polymerization by contact of said first wall-forming component with a second wall-forming component, as is conventionally known in the state of the art.

[0067] The first wall-forming component is preferably selected from a polyisocyanate, a polyacid chloride, a polyoroformate, and a polysulfonyl chloride. The second wall-forming component is preferably selected from a polyamine and a polyol. Preferably, a polyisocyanate reacts with a polyamine to form a polyurea capsule wall of the present invention.

[0068] Os poli-siocianatos preferidos como primeiro elemento formador de parede podem ser selecionados a partir de di-siocianato de tetrametileno, di-siocianato de pentametileno, di-siocianato de hexametileno, di-siocianato de tolueno, 4,4'-di-siocianato de difenilmethane, isocyanato de polifenileno polimetileno, tri-isocianato de éter 2,4,4'difenílico, 3, Di-siocianato de 3'-dimetil-4,4'-difenila, di-siocianato de 3,3'-dimetoxi-4,4'difenila, di-siocianato de 1,5-naftileno e tri-siocianato de 4,4'4-trifenilmethane. A preferred primary polyisocyanate wall-forming component is polymethylethylene polyphenylisocyanate.

[0069] Preferred polyamines as secondary wall-forming components may be selected from ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4,9-dioxadodecane-1,1,2-diamine, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4'-diaminodiphenylmethane or the acid addition salts thereof. The preferred polyamine according to the present invention is diethylenetriamine.

[0070] The first wall-forming component comprises from about 0.1% to about Petition 870280048246, dated 06 / 04 / 2018, page 91 / 179 15 / 43 of 20% by weight of the organic phase of the present invention. The second wall-forming component is preferably present in an amount of about 0.3% to 7.5% by weight relative to the total weight of the formulation.

[0071] In another preferred embodiment, the preferred polyurea polymeric shell wall can be formed by a self-condensation reaction of a polyisocyanate wall-forming component. In this embodiment, the process for preparing the capsule suspension formulation according to the present invention comprises establishing a physical dispersion of an organic phase in the aqueous phase. In this embodiment, the organic phase comprises the organic isocyanate intermediate, as described above, together with the active ingredient pendimethalin.

[0072] In one embodiment, surfactants may be selected from ethylene / propylene acid condensates; alkyl, aryl- and aryl, aryl ethoxylates and their derivatives; lignosulfonates; cresol- and naphthaleneformaldehyde condensates and sulfonates; polycarboxylates and derivatives thereof; and mixtures thereof.

[0073] In one embodiment, coformulants can be selected from antifoaming agents, antifreeze agents, suspending agents, preservatives, and thickening agents.

[0074] In one embodiment, antifoaming agents may be selected from silicone emulsions, such as SAG-1572, long-chain alcohols, fatty acids, organofluorine compounds, and mixtures thereof.

[0075] In one embodiment, the paste (semi-fluid suspension) comprising the first herbicide, from which its concentrated suspension is prepared, can be subjected to grinding to a particle size with a D90 of 8-10 micrometers.

[0076] Thus, in another aspect, the present invention provides a process for the preparation of a ZC formulation, wherein said process comprises: (a) the formation of an aqueous solution comprising at least one surfactant and a predefined amount of at least one alkali or alkaline-earth metal salt of an organic acid; (b) the formation of an organic phase by the fusion of a quantity Petition 870280048246, dated 06 / 04 / 2018, page 92 / 179 16 / 43 herbicidally effective active ingredient pendimethalin and the addition of a predetermined amount of a first wall-forming component polyisocyanate; (c) dispersing said organic phase in said aqueous solution to obtain an emulsion in order to form an interface between the discrete droplets of organic phase and the aqueous phase; and (d) maintaining said emulsion for a period of time sufficient to permit substantial completion of the polyisocyanate autopolymerization reaction, such that said liquid droplets in the organic phase are converted into capsules comprising polyurea shells containing the active ingredient pendimethalin; (e) the formation of a paste comprising dispersant, water, surfactants and co-formulants to obtain the paste; and the addition of the first herbicide to the paste; (f) grinding the paste to a desired particle size; and mixing the resulting dispersion with the capsule suspension dispersion or the mixture of microcapsules drained from the suspension; and (g) combining the microencapsulated portion of the formulation with the suspension.

[0077] In one embodiment, the emulsion of said organic phase in said aqueous solution may preferably be heated to a temperature between 20 °C and about 100 °C, preferably to about 35-85 °C to accelerate the autocondensation of the polyisocyanate prepolymer.

[0078] However, regardless of whether self-condensation of the first wall-forming component or condensation between a first and a second wall-forming component is preferred, the relative amounts of the organic and aqueous phases are not critical to the process of the present invention. Typically, the organic phase may comprise up to about 75% by volume of the total emulsion and the emulsion comprises discrete droplets of an organic solution dispersed in the aqueous solution.

[0079] The droplet size in the emulsion was not found to be critical for the formulation and process of the present invention, but can be found between 0.5 Petition 870280048246, dated 06 / 04 / 2018, page 93 / 179 17 / 43 micrometer to about 4000 micrometers, which can be further adapted using a high shear device to preferably a size of about 1 micrometer to about 100 micrometers. It has also been found that the in situ self-condensation polymerization reaction is self-limiting and the reaction is generally maintained to completion. The reaction usually runs to completion within a period of a few minutes to a few hours. In a preferred embodiment, the reaction is typically allowed to run for about 2 to 3 hours.

[0080] However, the preferred polyurea polymer shell can be formed by a self-condensation reaction of a preferred polyisocyanate using other preferred methods. In a preferred embodiment, the formation of the polyurea capsule shell around the dispersed organic droplets can be achieved by (a) dispersing the organic phase droplets in the continuous aqueous phase to form an emulsion followed by heating the resulting emulsion; or (b) heating the continuous aqueous phase and dispersing the organic phase droplets in the heated continuous aqueous phase to form the emulsion, thus effecting the desired self-condensation reaction at the interface between the organic droplets and the aqueous phase.

[0081] The alkali or alkaline-earth metal salt of an organic acid as used in the present invention preferably selected from an alkali or alkaline-earth metal salt of a weak organic acid selected from acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid.

[0082] The preferred alkali metal is selected from sodium and potassium. In a more preferred embodiment, the preferred alkali metal is sodium.

[0083] In another preferred embodiment, the alkali or alkaline earth metal salt of an organic acid is selected from sodium acetate or disodium succinate.

[0084] The aqueous solution comprises at least one surfactant. Preferably, the surfactant may be selected from the group comprising ethoxylated lignosulfonic acid salts, lignosulfonic acid salts, oxidized lignins, lignin salts, styrene-maleic anhydride copolymer salts, polyvinyl alcohol, partial salts of Petition 870280048246, dated 06 / 04 / 2018, page 94 / 179 18 / 43 styrene-maleic anhydride copolymer esters, partial salts of polyacrylic acid and partial salts of polyacrylic acid terpolymers.

[0085] Preferably, the surfactant is calcium or sodium lignosulfonate.

[0086] Preferably, the surfactant is present in an amount of about 0.2% to about 5% by weight of the formulation.

[0087] The aqueous solution of the present invention includes an alkali or alkaline earth metal salt of an organic acid or mixtures thereof in an amount of about 2% to about 55% by weight of the formulation.

[0088] The term “herbicidally effective amount of pendimethalin or the first herbicide (hereinafter “co-herbicide”)” is the amount of pendimethalin or co-herbicide, respectively, which when applied in such quantity will provide the necessary control of weeds. The specific amount depends on many factors, including, for example, the crop, the weeds to be controlled, and environmental conditions. However, the selection of the appropriate amount of active agent to be applied is within the expertise of a person skilled in the art and is not considered particularly limiting.

[0089] The microcapsules of the present invention comprise from about 5% to about 60% pendimethalin. The concentrated suspension of the present invention comprises from 5% to about 60% of the co-herbicide.

[0090] In a preferred embodiment, the polymeric casing wall according to the present invention constitutes from about 1% by weight to about 20% by weight of the formulation. In another preferred embodiment, the polymeric casing wall constitutes about 2.5% by total weight of the formulation.

[0091] The microcapsules of the present invention preferably have a particle size of about 2 micrometers to 50 micrometers.

[0092] In one embodiment, the paste (semi-fluid suspension) can be subjected to grinding to a particle size with a D90 of 8-10 micrometers.

[0093] Preferably, the formulation of the present invention comprises an antifoaming agent in an amount of about 0.01% to about 5% by weight of the formulation. Such suitable antifoaming agents are conventionally known in the state. Petition 870280048246, dated 06 / 04 / 2018, page 96 / 179 19 / 43 of the technique and are not limiting the scope of the invention.

[0094] Preferably, the formulation of the present invention comprises surfactants in the form of lignosulfonate salts, most preferably sodium or calcium salts.

[0095] The microcapsules of the present invention may also include a rheology modifier. The preferred rheology modifier includes xanthan gum and clay, which may be present in an amount of about 0.01% to about 3% by weight of the formulation.

[0096] The capsule suspension formulation according to the present invention may be further neutralized, preferably with an organic acid, to regulate the pH within the desired range. Consequently, the formulations according to the present invention further comprise from about 0.1% to about 10% of a neutralizing acid, which may be an organic acid. Preferably, the neutralizing acid is acetic acid.

[0097] Another advantage of adding a neutralizing acid is that the added acid combines with the unreacted amines to form an ammonium salt, which substantially reduces the amount of external salt addition needed to obtain a property that does not cause appreciable discoloration / staining. The addition of a neutralizing acid is particularly beneficial in reducing the level of inorganic salt in prior art formulations, which has been reported to exacerbate the phytotoxicity problem in several plants tested. In this embodiment of the present invention, a significantly large amount of excess amines can be used to further reduce the external addition of a salt by generating in situ a greater amount of salt after reaction with the neutralizing acid.

[0098] In a preferred embodiment, the formulations according to the present invention may further comprise a biocide in an amount of about 0.01% to about 3% by weight of the formulation.

[0099] In one aspect, the present invention provides a ZC composition comprising encapsulated pendimethalin and a co-herbicide selected from the group consisting of pyrazolosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, flufenacet, oryzalin, glufosinate, glyphosate and agrochemically acceptable salts and derivatives thereof, in a concentrated suspension. Petition 870280048246, dated 06 / 04 / 2018, pp. 98 / 179 20 / 43

[0100] In one aspect, the present invention provides a ZC composition comprising encapsulated pendimethalin and a concentrated suspension comprising at least two co-herbicides, wherein at least one of the co-herbicides is selected from the group consisting of pyrazolosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, flufenacet, oryzalin, glufosinate, glyphosate and agrochemically acceptable salts and derivatives thereof, in a concentrated suspension.

[0101] In another aspect, the present invention also provides a process for the preparation of a ZC formulation, wherein said process comprises: (a) the formation of an aqueous solution comprising at least one surfactant and a predefined amount of at least one alkali or alkaline earth metal salt of an organic acid and, optionally, heating said aqueous solution; (b) the formation of an organic phase by fusing a herbicidally effective amount of the active ingredient pendimethalin and adding a predetermined amount of a first wall-forming component to said organic phase; (c) dispersing said organic phase in said aqueous solution to obtain an emulsion and, optionally, heating said emulsion formed; (d) the addition of a second wall-forming component to said emulsion such that said second wall-forming component reacts with said first wall-forming component comprised within said emulsion to form the polymeric wall, encapsulating at least said herbicidally effective substance of the active ingredient pendimethalin. (e) the formation of a paste comprising water, at least one co-herbicide, surfactants and co-formulants; (f) grinding the paste to a desired particle size to form a stable co-herbicide suspension; (g) the combination of the microencapsulated part (d) of the formulation with the suspension.

[0102] Preferably, the said step of forming an aqueous solution comprises heating the water to an elevated temperature, preferably around 60 °C and Petition 870280048246, dated 06 / 04 / 2018, p. 97 / 179 21 / 43 addition of said surfactant and said alkaline or alkaline-earth salt of an organic acid. In a preferred embodiment, an antifoaming agent is also added to the aqueous solution.

[0103] In another preferred embodiment, said first wall-forming component is preferably added to molten pendimethalin under stirring.

[0104] In yet another preferred embodiment, said dispersion step of said organic phase in said aqueous solution to obtain an emulsion is carried out to a desired particle size.

[0105] In another preferred embodiment, after the addition of the second wall-forming component to the emulsion, the reaction is allowed to continue for a predetermined time, preferably one hour under stirring, while the reaction mass is maintained at an elevated temperature.

[0106] Subsequently, the reaction mixture is neutralized with an organic acid. Neutralization is preferably carried out to achieve a formulation pH of about 6.5 to about 7.5.

[0107] Subsequently, xanthan gum is preferably added under agitation.

[0108] In a preferred embodiment, a biocide is added to obtain the target formulation.

[0109] In a preferred embodiment, the process of the present invention is carried out at an elevated temperature to maintain the active ingredient pendimethalin in a molten state and to increase the rate of polymer wall formation. In this embodiment, the process of the present invention is preferably carried out at a temperature of about 35 °C to about 85 °C, and is more preferably conducted at a temperature of about 50 °C to 65 °C.

[0110] Thus, in one embodiment, the present invention also provides a process for preparing a capsule suspension formulation, said process comprising: (a) the formation of an aqueous solution comprising at least one surfactant and a predefined amount of at least one alkali or alkaline earth metal salt of an organic acid and, optionally, heating the solution. 22 / 43 referred aqueous solution; (b) the formation of an organic phase by fusing a herbicidally effective amount of the active ingredient pendimethalin and an additional herbicide and adding a predetermined amount of a first cell wall-forming component to said organic phase; (c) dispersing said organic phase in said aqueous solution to obtain an emulsion and, optionally, heating said emulsion formed; and (d) adding a second wall-forming component to said emulsion such that said second wall-forming component reacts with said first wall-forming component comprised within said emulsion to form a polymeric wall, encapsulating at least said herbicidally effective substance of the active ingredient pendimethalin and any additional herbicide; (e) the formation of a paste comprising water, a co-herbicide, surfactants and co-formulants; (f) grinding the paste to a desired particle size to form a stable co-herbicide suspension; (g) the combination of the microencapsulated portion (d) of the formulation with the suspension.

[0111] In one embodiment, the ZC formulation of the present invention comprises a mixture of the pendimethalin component and the co-herbicide suspension component in a predetermined ratio. In one embodiment, the pendimethalin component and the co-herbicide component are mixed in a ratio of about 1:90 to about 90:1, preferably in a ratio of about 1:10 to about 10:1.

[0112] In another non-limiting embodiment, the pendimethalin component and the co-herbicide component are mixed in a ratio of about 1:2 to about 1:3.

[0113] The invention further relates to a mode for controlling weeds in a location by applying to the weed location a herbicidally effective amount of a ZC formulation comprising microencapsulated pendimethalin and a co-herbicide.

[0114] Preferably, the present invention provides a method for controlling species of ffiáçãoswií^^ wwMSKiRg. 23 / 43 undesirable plants comprising application to the foliage of plants or to soil or water containing seeds or other propagation organs of these plants, a herbicidally effective amount of a ZC formulation comprising microencapsulated pendimethalin and a co-herbicide present in a concentrated suspension.

[0115] Alternatively, the present invention provides a method for controlling undesirable plant species comprising applying to the foliage of the plants or to the soil or water containing seeds or other propagation organs of these plants, a herbicidally effective amount of a ZC formulation comprising pendimethalin, encapsulated with an additional herbicide and the first herbicide present as a concentrated suspension of said formulation.

[0116] In one embodiment, the composition of the present invention may be packaged as a parts kit. In one embodiment, a parts kit may contain several components of the formulation of the present invention that may be mixed as instructed before spraying.

[0117] Consequently, one aspect of the present invention may provide a multi-pack herbicide product for controlling weeds in a single location comprising components of the present invention and an instruction manual. The instruction manual includes instructions for administering the components of the ZC formulation.

[0118] In one embodiment, the instruction manual includes instructions for administering the ZC formulation to a location or to the foliage of plants or to soil or water containing seeds or other plant propagation organs.

[0119] In another embodiment, the instruction manual includes instructions for mixing the encapsulated pendimethalin component with the first component, which is the concentrated herbicide suspension, in a predetermined ratio. In one embodiment, the instruction manual instructs the user to mix the pendimethalin component and the first herbicide component in a ratio of about 1:10 to about 10:1, preferably in a ratio of about 1:2 to 1:3.

[0120] In one embodiment, the combination kit is packaged in a package or box. In another embodiment, the instruction manual may be printed on said package or box, or it may be printed on a leaflet that may Petition 870180048146, dated 06 / 04 / 2018, pages 100 / 117 24 / 43 to be included inside the packaging or box.

[0121] The herbicide composition and method of the present invention may offer some specific advantages over compositions known in the prior art. The novel combination of microencapsulated pendimethalin and the first herbicide in a ZC formulation allows for stable formulations that enable broad-spectrum weed coverage. ZC formulations greatly improve stability and allow for the combination of incompatible actives. The novel ZC formulation also has the added advantage of being a non-staining pendimethalin composition.

[0122] The invention will now be described with reference to the following specific examples. It should be noted that the accompanying example(s) illustrate(s) rather than limit the invention, and that those skilled in the art will be able to devise many alternative embodiments without departing from the scope of the present invention. EXAMPLES EXAMPLE 1: ZC FORMULATION OF SULFONYLUREA AND PENDIMETHALINE A) Composition of pendimethalin capsule suspension: Sr. No. Ingredients % w / w 1 Pendimethalin technical 40 @ 97% technical purity 40.41 2 PMPI 1.01 3 Water 38.21 4 Borresperse Na 2.50 5 Sodium acetate (an) 15.30 6 Antifoaming agent 0.10 7 EDA 0.23 8 DETA 0.26 9 Acetic acid 0.35 10 2% Rhodopol-23 gel 1.50 11 Proxel GXL 0.13 12 Total 100.00

[0123] The above composition was prepared following the encapsulation process described below: Petition 870180048146, dated 06 / 04 / 2018, pp. 101 / 129 25 / 43

[0124] An aqueous solution was created by heating water to 60 °C while adding sodium lignosulfonate and subsequently sodium acetate, followed by the addition of the antifoaming agent under stirring. A sufficient quantity of water was kept separate for the amine and gum preparations. Meanwhile, the organic phase was formed by melting the pendimethalin technique, heating it to 60 °C, and then adding polymethylene polyphenylisocyanate (PMPI) under stirring. The aqueous and organic phases were maintained at 60 °C throughout the reaction. The organic phase was emulsified in the aqueous solution to the desired particle size. DETA / EDA were added to the resulting emulsion. The reaction was allowed to proceed for 1 hour and maintained at 60 °C under stirring. The reaction mixture was allowed to cool to room temperature for 15 minutes before neutralizing with acetic acid. The formulation was neutralized to pH 8.0 under cold conditions or pH 7 under warmer conditions.The neutralized formulation was filtered through a 60 mesh sieve. A xanthan gum-water paste was prepared separately and added to the above formulation under stirring for at least 15 minutes. Finally, a biocide was added and the final product was filtered through a 60 mesh sieve. Particle size was measured using a Horiba LA-910 or CILAS 1064 device.

[0125] Sulfonyl-urea concentrated paste Mr. No. Formulation Component Ethyl pyrazosulfuron Methyl benzosulfuron Sulfosulfuron 1 Sulfonylurea 51 @ 98% technical purity 52.04 52.04 52.04 2 Borresperse NA 06.00 06.00 06.00 3 Antifoaming agent (SAG-1572) 00.10 00.10 00.10 4 Water (QS) 41.86 41.86 41.86 Total 100.00 100.00 100.00

[0126] The composition above was prepared following the process below:

[0127] An aqueous solution was prepared using water, sodium lignosulfonate, and an antifoaming agent. The sulfonylurea herbicide was added to the mixture and homogenized. The homogenized solution was ground to a D90 particle size of 8-10 micrometers in a Petition 870180048146, dated 06 / 04 / 2018, pages 104 / 129 26 / 43 ball mill for forming the slurry (semi-fluid suspension).

[0128] Microencapsulated pendimethalin was added to the concentrated sulfonylurea suspension to form the final ZC formulation. The resulting formulation was subjected to stability tests: EXAMPLE 2: PHYSICAL-CHEMICAL DATA OF ZC PENDIMETHALIN + SULFONYLUREA: S r. n ° Properties Pyrazosulfuron ethyl Bensulfuron methyl Sulfosulfuron Ambient 14 days in AHS at 54°C Ambient 14 days in AHS at 54°C Ambient 14 days in AHS at 54°C 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid 2 Pendimethalin, ia content (active ingredient) g / L 458.5 457.2 452.01 450.60 459.38 457.38 3 SU, ia content g / L 11.7 11.36 (2.9% degradation) 27.53 26.99 (1.96% degradation) 33.43 32.67 (2.27% degradation) 4 Suspensibility % w / w 100.26 100.9 98.67 98.28 99.10 98.69 5 % Spontaneity of dispersion w / w 100.16 100.29 99.14 98.98 99.26 99.14 6 % Retention on wet sieve w / w 0.02 0.02 0.05 0.12 0.03 0.09 Petition 870180048146, dated 06 / 04 / 2018, pp. 103 / 117 27 / 43 Mr. n ° Properties Ethyl pyrazosulfuron Methyl bensulfuron Sulfosulfuron Ambient 14 days in AHS at 54°C Ambient 14 days in AHS at 54°C Ambient 14 days in AHS at 54°C 7 pH 1% aqueous 7.43 7.36 7.82 7.69 7.85 7.80 8 % flowability (pourabn / ty) washing residue 0.1 0.12 0.06 0.11 0.5 0.10 9 Particle size, D-50 5.58 5.57 5.36 5.57 5.29 5.50 D-4.3 6.59 6.72 6.61 6.69 6.53 6.62 D-90 13.28 13.32 14.10 14.17 13.26 13.60

[0129] Conclusion: 1) All three formulations showed good stability of physicochemical properties, suspension capacity, dispersion spontaneity, pH range, wet sieve retention, and particle size in AHS at 54 °C. 2) All three formulations showed improved stability of the active ingredient in AHS. EXAMPLE 3: LOW TEMPERATURE STABILITY OF THE CZ OF PENDIMETHALIN + PSE Mr. No. Properties Before freeze / thaw test After freeze / thaw test 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid 2 Pendimethalin, content of ia g / L 458.5 458.3 3 Pyrazosulfuron ethyl, content of ia g / L 11.7 11.65 Petition 870180048146, dated 06 / 04 / 2018, pp. 104 / 117 28 / 43 Mr. No. Properties Before freeze / thaw test After freeze / thaw test 4 Free pendimethalin, % ai, w / w 0.13 0.16 5 Suspensibility % w / w 98.3 98.56 6 % Wet sieve retention w / w 0.02 0.03 7 pH 1% aqueous 7.43 7.36 8 Particle size D-50 5.58 5.59 D-4.3 6.59 6.61 D-90 13.28 13.40

[0130] Conclusions: The free pendimethalin content in the formulation was very low, and both the capsule stability and the low-temperature suspension stability were excellent. EXAMPLE 4: REAL-TIME STABILITY DATA FOR ZC OF PENDIMETHALINE + ETHYL PYRAZOSULFURON Mr. No. Properties Day zero 6 months 12 months 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid Yellow-orange capsule suspension, fluid 2 Pendimethalin, ia content g / L 451.6 450.04 449.90 3 Ethyl pyrazosulfuron, ia content g / L 11.46 11.22 (2.09% degradation) 11.15 (2.7% degradation) 4 Suspensibility % w / w 99.52 99.0 98.5 5 % spontaneity of dispersion w / w 100.93 100.5 99.85 6 % retention on wet sieve w / w 0.04 0.04 0.04 Petition 870180048146, dated 06 / 04 / 2018, pp. 107 / 117 29 / 43 Sr No. Properties Day zero 6 months 12 months 7 pH 7.33 7.30 7.45 9 Particle size D-50 6.17 6.15 6.16 D-4.3 9.78 9.76 9.86 D-90 20.89 21.2 21.1

[0131] Conclusion: The formulation was stable for a period of 12 months. Ethyl pyrazosulfuron and pendimethalin showed very little degradation. EXAMPLE 5: PREPARATION OF THE PENDIMETHALIN + TRIAZINONE ZC COMPOSITION:

[0132] The pendimethalin capsule suspension was prepared as described in example 1. The metribuzin concentrate suspension was prepared according to the following formulation: Mr. No. Formulation Component % 1 Metribuzin technical 52 @ 95% purity, technical 54.74 2 Borresperse Na 7.50 4 Antifoaming agent 0.10 6 Water 37.66 Total 100.00

[0133] The composition above was prepared using the following process:

[0134] An aqueous solution was prepared using water, sodium lignosulfonate and an antifoaming agent. Metribuzin was added to the mixture and homogenized. The homogenized solution was ground to a D90 particle size of 8-10 micrometers in a ball mill to form the slurry (semi-fluid suspension).

[0135] Microencapsulated pendimethalin was added to the concentrated metribuzin suspension to form the final ZC formulation. The resulting formulation was subjected to stability tests: EXAMPLE 6: PHYSICO-CHEMICAL DATA OF THE ZC OF PENDIMETHALINE + METRIBUZINE Sr n° Properties Environment 14 days in AHS 54 °C 1 Appearance Yellow capsule suspension Yellow capsule suspension Petition 870180048146, dated 06 / 04 / 2018, pages 106 / 117 30 / 43 Sr No. Properties Environment 14 days in AHS 54 °C orange orange, fluid 2 Pendimethalin, ia content 389.31 388.8 3 Metribuzin, ia content 68.07 67.72 4 Suspensibility % w / w 104.3 102.31 5 Spontaneity of dispersion w / w 105.3 103.26 6 Wet sieve retention w / w 0.02 0.03 7 pH 7.15 7.29 8 Pourability % wash residue 0.05 0.05 9 Particle size D-50 7.38 7.58 D-4.3 10.0 10.2 D-90 14.9 16.50

[0136] Conclusion: 1) The formulation showed good stability of physicochemical properties, suspension capacity, dispersion spontaneity, pH range, retention on a wet sieve, and particle size in AHS at 54 °C. 2) The formulation showed improved stability of the AI ​​(active ingredient) in AHS. EXAMPLE 7: LOW TEMPERATURE STABILITY OF THE CZ OF PENDIMETHALIN + METRIBUZINE Mr. No. Properties Before freeze / thaw test After freeze / thaw test 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid 2 Pendimethalin, content of 1a g / L 389.31 389.19 Petition 870180048146, dated 06 / 04 / 2018, pages 107 / 117 31 / 43 Mr. No. Properties Before freeze / thaw test After freeze / thaw test 3 Metribuzin, ia content g / L 68.07 67.95 4 % suspendability w / w 104.3 103.6 5 % retention on wet sieve w / w 0.02 0.03 6 pH 7.15 7.21 7 Particle size D-50 7.38 7.41 D-4.3 10.0 10.1 D-90 14.9 15.1

[0137] Conclusions: Free pendimethalin in the formulation was very low, and both capsule stability and low-temperature suspension stability were excellent. EXAMPLE 8: REAL-TIME STABILITY DATA FOR PENDIMETHALINE ZC + METRIBUZINA Mr. No. Properties Day zero 6 months 12 months 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid Yellow-orange capsule suspension, fluid 2 Pendimethalin, ia content g / L 389.31 388.72 388.14 3 Metribuzin, ia content g / L 68.07 66.78 66.43 4 % suspendability w / w 104.3 99.68 99 5 % dispersion spontaneity w / w 105.3 100.12 101.0 6 % retention on wet sieve w / w 0.02 0.02 0.02 7 pH 1% aqueous dispersion 7.15 6.91 6.80 9 D-50 size 7.38 6.05 5.03 Petition 870180048146, dated 06 / 04 / 2018, pp. 108 / 129 32 / 43 Mr. No. Properties Day zero 6 months 12 months particle. D-4.3 10.0 8.8 8.64 D-90 14.9 15.8 17.9

[0138] Conclusion: 1) The formulation demonstrated stability of physicochemical properties such as suspendability, dispersion spontaneity, pH range, wet sieve retention, particle size, etc. in AHS at 54 °C and real-time storage for a period of 12 months. 2) Both pendimethalin and metribuzin exhibited good stability in AHS and real-time storage. EXAMPLE 9: COMBINATION OF PENDIMETHALIN + TRIAZINE HERBICIDE

[0139] Pendimethalin capsule suspension was prepared as described in Example 1. Atrazine concentrate suspension was prepared according to the following formulation: Formulation Component No. % 1 Pendimethalin 18.1% @ 40% purity, CS 45.25 2 Atrazine 18.1% @ 50% purity, paste 36.2 3 2% Rhodopol-23 gel 2.50 4 R-100 M 2.00 5 Proxel GXL 0.10 6 Water 13.95 Total 100.00

[0140] The composition above was prepared using the following process:

[0141] An aqueous solution was prepared using water, sodium lignosulfonate and an antifoaming agent. Atrazine was added to the mixture and homogenized. The homogenized solution was ground to a D90 particle size of 8-10 micrometers in a ball mill to form the slurry (semi-fluid suspension).

[0142] Microencapsulated pendimethalin was added to the concentrated atrazine suspension to form the final ZC formulation. The resulting formulation was subjected to tests. Petition 870180048146, dated 06 / 04 / 2018, pp. 109 / 129 33 / 43 stability: EXAMPLE 10: PHYSICO-CHEMICAL DATA OF THE ZC OF PENDIMETHALINE + ATRAZINE Mr. No. Properties Environment 14 days in AHS 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid 2 Pendimethalin, ia content g / L 206.99 205.98 3 Atrazine, ia content g / L 206.69 205.50 4 % suspendability w / w 103.91 102.69 5 % dispersion spontaneity w / w 100.83 100.11 6 % retention on wet sieve w / w 0.01 0.03 7 pH 7.31 7.48 8 % flowability (pourabn / ty) washing residue 0.03 0.08 9 Particle size D-50 3.75 3.42 D-4.3 6.67 6.07 D-90 14.4 13.6

[0143] Conclusion of the ZC formulation of Pendimethalin with Atrazine: 1) The formulation demonstrated good stability of physicochemical properties such as suspendability, dispersion spontaneity, pH range, retention on a wet sieve, particle size, etc. in AHS at 54 °C and in real-time storage. 2) The formulation demonstrated excellent stability in AHS. EXAMPLE 11: LOW TEMPERATURE STABILITY Mr. No. Properties Before freeze / thaw test After freeze / thaw test 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid Petition 870180048146, dated 06 / 04 / 2018, pp. 110 / 117 34 / 43 Mr. No. Properties Before freeze / thaw test After freeze / thaw test 2 Pendimethalin, ia content g / L 206.99 206.27 3 Atrazine, ia content g / L 206.69 206.50 4 % suspendability w / w 103.91 101.73 5 % retention on wet sieve w / w 0.01 0.05 6 pH 7.31 7.42 7 Particle size D-50 3.75 3.41 D-4.3 6.67 6.62 D-90 14.4 14.3

[0144] Conclusion:

[0145] The formulation was found to be stable in the freeze / thaw cycle and maintains its physicochemical properties as an ambient sample. EXAMPLE 12: PENDIMETHALIN ZC FORMULATION + ALCANAMIDE HERBICIDE

[0146] Pendimethalin capsule suspension was prepared as described in Example 1. D-Napropamide concentrated suspension was prepared according to the following formulation: Formulation Component No. % 1 D-Napropamide 52% @ 98 53.06 2 Borresperse NA 7.00 3 Antifoaming agent (SAG-1572) 0.50 4 Water (QS) 39.44 Total 100.00

[0147] The composition above was prepared using the following process:

[0148] An aqueous solution was made using water, sodium lignosulfonate and an antifoaming agent. D-Napropamide was added to the mixture, which was homogenized. The homogenized solution was ground to a D90 particle size of 8-10 micrometers in a ball mill to form the slurry (semi-fluid suspension).

[0149] Microencapsulated pendimethalin was added to concentrated D suspension Petition 870180048146, dated 06 / 04 / 2018, pages 113 / 117 35 / 43 napropamide to form the final ZC formulation. The resulting formulation was subjected to stability tests: EXAMPLE 13: PHYSICO-CHEMICAL DATA OF THE PENDIMETHALINE + D-NAPROPAMIDE ZC Mr. No. Properties Environment 14 days in AHS 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid 2 Pendimethalin, ia content g / L 241.01 240.8 3 D-Napropamide, ia content g / L 221.2 221.0 4 % suspendability w / w 98.3 99.0 5 % dispersion spontaneity w / w 99.89 100.2 6 % retention on wet sieve w / w 0.04 0.05 7 1% aqueous suspension 7.69 7.58 8 % flowability (pourabn / ty) washing residue 0.18 0.21 9 Particle size D-50 4.35 4.16 D-4.3 8.54 8.32 D-90 14.5 14.7 [F0150]Conclusion of the ZC formulation of Pendimethalin with D-Napropamide: 1) The formulation demonstrated excellent stability of physicochemical properties such as suspendability, dispersion spontaneity, pH range, wet sieve retention, particle size, etc. in AHS at 54 °C and in real-time storage. 2) Both pendimethalin and D-napropamide demonstrated excellent stability in AHS. EXAMPLE 14: LOW TEMPERATURE STABILITY OF PENDIMETHALIN + DNAPROPAMIDE Petition 870180048146, dated 06 / 04 / 2018, pages 111 / 117 36 / 43 Mr. No. Properties Before freeze / thaw test After freeze / thaw test 1 Appearance Yellow-orange capsule suspension Yellow-orange capsule suspension, fluid 2 Pendimethalin, ia g / L content 241.01 240.92 3 D-Napropamide, ia g / L content 221.2 221.45 4 % suspendability w / w 98.3 98.96 5 % retention on wet sieve w / w 0.04 0.06 6 pH 7.35 7.48 7 Particle size D-50 4.35 4.26 D-4.3 8.54 8.45 D-90 14.5 14.61

[0151] Conclusions:

[0152] The formulation was considered stable in the freeze / thaw cycle and maintains its physicochemical properties as an ambient sample. EXAMPLE 15: PENDIMETHALIN + IMIDAZOLINONE HERBICIDE ZC FORMULATION

[0153] The Pendimethalin capsule suspension was prepared as described in Example 1. The imidazolinone herbicides imazapic and imazatapyr were formulated in concentrated suspensions according to the following formulation: Mr. No. Formulation Component Imazapic Acid Imazatapyr Acid 1 Imidazolinone 96% purity, technical 46.4 52.08 2 Borropsperse NA 7.00 7.00 3 Antifoaming agent (SAG-1572) 0.50 0.50 4 Water (QS) 46.1 40.42 Total 100.00 100.00

[0154] The composition above was prepared using the following process:

[0155] An aqueous solution was prepared using water, pendimethalin capsule suspension, sodium lignosulfonate, and an antifoaming agent. Imidazolinone was Petition 870180048146, dated 06 / 04 / 2018, pages 113 / 117 37 / 43 added to the mixture and homogenized to obtain the final ZC formulation. EXAMPLE 16: ZC FORMULATION OF PENDIMETHALINE + IMAZAPIK

[0156] The Pendimethalin capsule suspension was prepared as described in Example 1. The herbicide imazapic was formulated as a concentrated suspension according to the following formulation; Formulation Component No. % 1 Pendimethalin 31.3 @ 40.7 % Purity CS 76.90 2 Imazapic acid 8.5 @ 45 % purity, paste 18.88 3 Reax-100 M 2.00 4 2% Rhodopol-23 gel 1.00 5 Proxel GXL 0.10 6 Water (QS) 1.12 total 100.00

[0157] The composition above was prepared using the following process:

[0158] An aqueous solution was prepared using water, pendimethalin capsule suspension, sodium lignosulfonate, xanthan gum, and biocide. The mixture was homogenized. Imazapic was added to the mixture and homogenized to obtain the final ZC formulation. The formulation was found to be stable at room temperature. EXAMPLE 17: PENDIMETHALIN + ORGANOPHOSPHATE HERBICIDE ZC FORMULATION

[0159] The pendimethalin capsule suspension was prepared as described in example 1. The glyphosate concentrate suspension was prepared according to the following formulation: Mr. No. Formulation Component % w / w 1 Glyphosate acid 45 @ 96 46.4 2 Borresperse NA 7.00 3 Antifoaming agent (SAG-1572) 0.50 4 Water (QS) 46.1 Total 100.00

[0160] The composition above was prepared following the process below:

[0161] An aqueous solution was prepared using water, sodium lignosulfonate and agent Petition 870180048146, dated 06 / 04 / 2018, pages 114 / 117 38 / 43 antifoam. Glyphosate was added to the mixture and homogenized. The homogenized solution was ground to a D90 particle size of 8-10 micrometers in a ball mill to form the slurry (semi-fluid suspension).

[0162] Microencapsulated pendimethalin was added to the concentrated glyphosate suspension to form the final ZC formulation. EXAMPLE 18: PENDIMETHALINE + GLYPHOSATE ZC FORMULATION

[0163] Pendimethalin capsule suspension was prepared as described in Example 1. Glyphosate concentrate suspension was prepared according to the following formulation: Formulation Component No. % 1 Pendimethalin 27 @ 40.7% Purity CS 66.34 2 Glyphosate acid 11.75 @ 45% purity, paste 26.11 3 Reax-100 M 2.00 4 2% Rhodopol-23 gel 2.00 5 Proxel GXL 0.10 6 Water (QS) 3.45 total 100.00

[0164] The composition above was prepared using the following process:

[0165] An aqueous solution was prepared using water, pendimethalin capsule suspension, sodium lignosulfonate, and xanthan gum. Glyphosate was added to the mixture and homogenized to obtain the final ZC formulation. The formulation was found to be stable at room temperature. COMPARATIVE EXAMPLES

[0166] Pendimethalin compositions were prepared using other formulation types to compare efficacy, stability, and compatibility with respect to formulation ZC: EXAMPLE 19A Pendimethalin + Ethyl Pyrazosulfuron WP (Wettable Powder) Formulations

[0167] Pendimethalin WP Composition Mr. No. Ingredients % w / w Petition 870180048146, dated 06 / 04 / 2018, page 117 / 117 39 / 43 Mr. No. Ingredients % w / w 1 Pendimethalin 45.5% @ 96% purity 47.40 2 M-fiii A-100 26.94 3 Metasperse 550S 8 4 Supragil WP 4.5 5 Antifoaming agent DC1920 1 5 Ammonium sulfate 10 Total 97.85

[0168] Ethyl pyrazosulfuron WP composition Mr. No. Ingredients % w / w 1 PSE 1.1% @ 95% technical purity 1.16 2 Supragil WP 0.50 3 M-fiii A-100 0.5 Total 2.15

[0169] Process: STEP 1: PENDIMETHALIN PREMIX a) Pendimethalin was melted and absorbed into precipitated silica by slow addition at low rpm to a mixing bowl and held overnight. b) Metasperse 550s (modified styrene acrylic polymer), Supragil WP (sodium salt of dialkyl naphthalenesulfonate), ammonium sulfate and Defoamer DC1920 powder antifoaming agent were mixed with the pendimethalin + silica mixture from step (a) until homogeneous. c) The premix was subjected to grinding in an air jet mill to obtain a lump-free material. STEP 2: PYRAZOSULFURON-ETHYL PREMIX a) Technical grade pyrazosulfuron-ethyl, Supragil WP (sodium salt of alkyl naphthalenesulfonate) and M-fiiii A-100 (precipitated silica) were mixed and ground in an air jet mill to obtain a D98 particle size of 30-36 micrometers. STEP 3: - MIXING Petition 870180048146, dated 06 / 04 / 2018, pages 116 / 117 40 / 43

[0170] The Pendimethalin premix from Step 1 and the Pyrazosulfuron premix from Step 2 were mixed to obtain the final WP formulation.

[0171] The resulting formulation was then subjected to stability tests: PHYSICO-CHEMICAL DATA OF THE PENDIMETHALIN WP FORMULATION + PYRAZOSULFURON-ETHYL: Sr No. Properties Environment 6 weeks in AHS at 45°C Real-time test data, 7 months 1 Appearance Loose fluid yellow powder Soft yellow-orange powder with few lumps Yellow-orange powder 2 Pendimethalin, ia content %, w / w 45.87 45.75 45.67 3 Ethyl pyrazosulfuron, ia content (%), w / w 1.05 1.002 (4.5% degradation) 0.92 (12% degradation) 4 % suspendability w / w gravimetric 84.39 68 58 5 Wetting time in seconds 40 20 30 6 % retention on wet sieve w / w 0.07 0.30 1.62 7 pH 1% aqueous suspension 6.89 6.71 6.80

[0172] Conclusion: The formulation showed a decrease in suspendability in AHS and real-time storage. It was found that the degradation of pyrazosulfuron-ethyl was 12% in just 7 months of real-time storage, which is very high when compared to the stable formulations of Example 1. The formulation showed an increase in wet sieve retention in AHS, and Petition 870180048146, dated 06 / 04 / 2018, page 117 / 117 41 / 43 intense increase in wet sieve, that is, 1.68% in just 7 months of real-time storage. EXAMPLE 19B: WP FORMULATIONS OF PENDIMETHALINE + METRIBUZINE: 8.2.1 - PENDIMETHALIN WP COMPOSITION Mr. No. Ingredients % w / w 1 Pendimethalin 38.7% @ 97% purity 39.90 2 M-fii A-100 22 3 Metasperse 550S 7 4 Supragi WP 4.5 5 Antifoaming agent DC1920 1 5 Ammonium sulfate 15.05 Total 89.45 8.2.2 - Metrobuzzer WP Composition Sr. No. Ingredients % w / w 1 Metribuzin 6.7% @ 95% technical purity 7.05 2 SupragU WP 0.50 3 M-fii A-100 2.00 4 Metasperse 550S 1.00 Total 10.55 Γ0173Ί Process: Step 1: Pendimethalin Premix a) M-ii A-100 (precipitated silica), Metasperse 550s (modified styrene acrylic polymer) and Supragi WP (modified styrene acrylic polymer) were added to the mixing vessel and absorbed the molten technical Pendimetallin by slow addition at low rpm. b) Next, ammonium sulfate and Defoamer DC1920 antifoaming agent powder were added and mixed until homogeneous. The material was stored until the following day. Step 2: Matribuzin Premix c) Metribuzin (technical grade), Metasperse 550 S (modified styrene acrylic polymer), Petition 870180048146, dated 06 / 04 / 2018, pages 118 / 117 42 / 43 Supragil WP (modified styrene acrylic polymer) and M-fill A-100 (precipitated silica) were premixed and milled in an air jet mill to obtain a D98 particle size of 30-36 micrometers. Step 3: - Mixing

[0174] The Pendimethalin premix from Step 1 and the metribuzin premix from Step 2 were mixed to obtain the final WP formulation.

[0175] The resulting formulation was then subjected to stability tests: Physicochemical data of the pendimethalin + metronidazole WP formulation Mr. No. Properties Environment 6 weeks in AHS at 45°C 1 Appearance Loose, fluid yellow powder Yellow-orange powder with few soft lumps 2 Pendimethalin, ia content (%), w / w 38.57 38.53 3 Metribuzin, ia content (%), w / w 6.75 6.72 4 % suspendability w / w 88.48 40.29 5 Wetting time in seconds 17 30 6 % retention on wet sieve w / w 0.12 0.48 7 pH 1% aqueous suspension 7.27 7.01

[0176] Conclusion of the Pendimethalin WP formulation with Metribuzin: The formulation showed decreased suspensibility in AHS and real-time storage at 6 weeks. The formulation showed increased wet sieve retention in AHS. There was a soft lump in AHS, which is undesirable.

[0177] As used in the present invention, the term ZC should be used to designate mixed formulations of capsule suspensions and concentrated suspensions, each of which may comprise a single herbicide or a combination of herbicides, Petition 870180048146, dated 06 / 04 / 2018, pages 119 / 117 43 / 43 as described in the present invention. ZC is therefore an aqueous suspension of microcapsules and solid particles, each of which may comprise one or more herbicidal active ingredients according to the present invention. The capsule suspension component typically comprises encapsulated pendimethalin, optionally in conjunction with another herbicide. The 'concentrated suspension' component typically includes another herbicide or a combination of herbicides.

Claims

1. ZC composition for weed control, characterized by comprising: a) microencapsulated pendimethalin, wherein the microencapsulated pendimethalin comprises a suspension of pendimethalin microcapsules in an aqueous phase, said microcapsules comprising a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, said polyurea polymer wall constituting from 1% to 20% by total weight of the suspension, said aqueous phase comprising an alkali or alkaline-earth metal salt of an organic acid selected from the group consisting of acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, wherein said alkali or alkaline-earth metal salt of an organic acid is present in an amount ranging from 2% to 55% by weight of the suspension;(b) concentrated suspension of a co-herbicide, wherein the concentrated suspension comprises particles of a first herbicide selected from the group consisting of metribuzin and mesotrione.

2. Composition ZC according to claim 1, characterized in that the suspension concentrate comprises at least two herbicides.

3. A method for controlling weeds in a location characterized by applying to the weed site, or to the foliage of the plants, or to the soil or water containing seeds or other propagating organs thereof, a herbicidally effective quantity of the ZC composition as defined in claims 1 and 2.

4. A multi-pack herbicide product for controlling weeds in a single location, characterized by comprising: (a) a ZC composition as defined in claims 1 and 2; and (b) an instruction manual that includes instructions for administering the ZC composition.