EA041447B1 - ZC COMPOSITION FOR WEEDS CONTROL - Google Patents

Description

Field of invention

The invention relates to herbicidal compositions. More specifically, the present invention relates to ZC formulations containing pendimethalin.

Information about the main application

This application is a supplementary patent application to Indian Patent Application No. 2251/MUM/2011 filed August 10, 2011 and PCT Application No. PCT/IB2011/002280 published under No. WO 2013021229 A1, or a successor in part to the application for US Patent Application No. 14/238009, the contents of all of which are incorporated herein by reference in their entirety.

Background of the invention and the state of the art

The type of herbicide formulation is very important for effective weed control. Various types of herbicidal formulations are designed to increase the effectiveness of the herbicide, whereby the active ingredient is delivered to the weed with maximum efficiency, minimum wastage and long-lasting residual effect.

The combination of two active ingredients sometimes results in incompatibility. Physical and biological incompatibilities often occur, such as insufficient stability of the combined formulation, degradation of the active ingredient, or antagonism of the active ingredients. Incompatibilities can cause the mixture to precipitate or thicken or flocculate, rendering the herbicide mixture and container unusable. This will also lead to inefficient spraying of the pesticide resulting in low efficiency. As a consequence, it is important that developers obtain stable formulations that allow two incompatible actives to be combined in one formulation, providing a favorable activity profile, high stability and, in some cases, improved synergy, thereby allowing lower application rates compared to applying separate actives. connections. For this reason, there is a need in the art for a formulation that is stable, especially when two incompatible active compounds are combined, allowing for a wide range of control while at the same time reducing the application rate.

Herbicide combinations are used to effectively and economically control weeds. These combinations provide advantages such as a broad spectrum of herbicidal activity, synergistic effect, prevention of degradation of one herbicide due to the presence of a second herbicide, and reduced herbicide dosages.

These herbicide combinations can be made by mixing the individual herbicides in a tank at the rate required just prior to application. However, adjusting the application rates of individual herbicides in tank-mix combinations is a problem for many farmers, who often tend to over-dose herbicides, resulting in undesirable effects on field crops. As a result, it is more preferable to prepare formulations containing herbicidal combinations during manufacture. These formulations and their preparation face difficulties due to mutual degradation and incompatibility of herbicides when they are and stored in the same formulation for an extended period of time. Obtaining a stable composition containing a combination of two or more active ingredients is often a difficult task for a skilled developer.

ZC formulations are a combination of a capsule suspension and a suspension concentrate, whereby the formulation contains a stable aqueous suspension of microcapsules and solid fine particles (in aqueous phase), each containing at least one active ingredient.

Pendimethalin is a herbicide based on dinitroaniline. It is a selective herbicide that controls certain broadleaf weeds and grassy weed species in crop and non-crop areas. It is applied to soil at the pre-planting, pre-emergence and post-emergence stages using ground or aerial equipment. It is an active substance with a low melting point and negligible vapor pressure, which is known to cause color problems in plants as well as any other object that comes into contact with it.

Application No. PCT/IB2011/002280 discloses a capsule suspension containing microcapsules in an organic phase, and the aqueous phase optionally contains a second herbicide. The microcapsules encapsulate pendimethalin. The aqueous phase contains an alkali or alkaline earth metal salt of an organic acid.

This application describes that the second herbicide can either be microencapsulated together with pendimethalin, or can be unencapsulated, or can be microencapsulated separately and mixed with microencapsulated pendimethalin. The second herbicide is advantageously a clomazone or a volatile herbicide such as 2,4-D esters, MCPA esters, triclopyr or picloram. This application does not provide any additional combination partner for the encapsulated pendimethalin.

- 1 041447

Pendimethalin is known to be incompatible with some classes of herbicides due to its physical characteristics, resulting in unstable formulations. Also, no other known aqueous formulations are known that are applicable to pendimethalin. For this reason, there is a need in the art for stable, water-compatible pendimethalin formulations that:

a) delivering pendimethalin non-staining formulations with a co-herbicide;

b) provide a physically stable formulation of pendimethalin with a co-herbicide;

c) providing a formulation of pendimethalin with a co-herbicide having a long lasting herbicidal effect;

d) provide an environmentally friendly aqueous formulation of pendimethalin with a co-herbicide;

e) provide a formulation of pendimethalin in which incompatibility with other active ingredients has been overcome.

Therefore, the present invention is intended to solve the problem of incompatibility and stability by using ZC formulations, in particular for active substances such as pendimethalin, when combined with herbicides which are otherwise known to be incompatible with pendimethalin.

An embodiment of the present invention can reduce one or more of the problems mentioned above.

Brief description of the invention

A ZC weed control composition comprising:

a) microencapsulated pendimethalin, wherein the microencapsulated pendimethalin comprises a suspension of pendimethalin microcapsules in an aqueous phase, said microcapsules containing a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, said polyurea polymer wall comprising from 1 to 20% of the total weight of the suspension wherein said aqueous phase contains at least one salt of an alkali or alkaline earth metal and 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 at least one 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; And

b) a suspension concentrate of a co-herbicide, wherein the suspension concentrate comprises particles of a co-herbicide selected from the group consisting of sulfonylurea herbicides, triazinon herbicides, imidazolinone herbicides, triazine herbicides, organophosphate herbicides and herbicides based on amide, where the specified suspension concentrate of the herbicide used together exhibits improved physico-chemical stability in the presence of the specified microencapsulated pendimethalin.

Detailed description of the invention

In this work, it was found that encapsulated pendimethalin stabilizes the physicochemical properties of the suspension concentrate of the first herbicide provided according to the present invention, which is otherwise known to be incompatible with pendimethalin.

Therefore, in one aspect of the present invention, a ZC composition is provided comprising:

(a) microencapsulated pendimethalin; and (b) a suspension concentrate of the co-herbicide.

Thus, in one aspect of the present invention, there is provided a suspension comprising particles of a first herbicide selected from the group consisting of sulfonylurea herbicides, triazinon herbicides, imidazolinone herbicides, triazine herbicides, anilide herbicides, sulfonamide, organophosphate herbicides, amide herbicides or alkanamide herbicides, in combination with a suspension of pendimethalin microcapsules in an aqueous phase, said microcapsules containing a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, said polymer wall from polyurea is from about 1 to about 20% of the total weight of the suspension, while the specified aqueous phase contains at least one salt of an alkali or alkaline earth metal and an organic acid selected from the group consisting of acetic acid lots, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid, succinic acid, valeric acid, malonic acid, glutaric acid, adipic acid and phthalic acid, where indicated

- 2 041447 at least one salt of an alkali or alkaline earth metal and 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.

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

Therefore, in embodiments of the present invention, a composition comprising ZC formulations comprising encapsulated pendimethalin and at least one co-herbicide may be provided.

The present inventors have surprisingly found that pendimethalin, when combined with active substances that are incompatible with pendimethalin when formulated as conventional formulations such as EC, WDG, etc., can be combined to form stable formulations when combined as ZC -composition. Thus, it has been found that the combination of a suspension concentrate of such herbicides with encapsulated pendimethalin stabilizes the physicochemical properties of the resulting ZC formulation, giving a result that has not previously been achieved satisfactorily with such herbicides.

Pendimethalin has two crystal forms, triclinic pendimethalin I (P1) is an orange thermodynamically stable form, while monoclinic pendimethalin II (P21/c) is a bright yellow metastable form. The latter is usually formed initially upon cooling of molten pendimethalin, while the orange form is formed by a polymorphic phase transition that occurs slowly when the yellow form is stored for long periods at temperatures below its melting point.

A polymorphic phase transition always leads to an increase in particle size. This results in the loss of formulation properties such as suspendability, retention on a wet sieve, etc., as well as a particular problem associated with the use of pendimethalin, i.e. staining.

It is known that pendimethalin is characterized by incompatibility when combined with certain active compounds. During storage of such compositions, problems of incompatibility of the active compound, coloring of objects, crystallomorphic transition, increase in particle size, loss of physicochemical properties of the composition, etc. are encountered. Mixing the formulation in the tank also results in flocculation, and separation of the pesticide results in formulation inefficiency or crop damage.

For example, pendimethalin 456 CS, when mixed with 75% metribuzin DF as a tank mix, has been found to cause flocculation, rendering the mix unusable. This has been noted with the formulation of pendimethalin 456 CS, Prowl H ₂ O, a formulation to which an inorganic salt is added prior to encapsulation. The inorganic salt was found to increase the hardness of the water, leading to flocculation in the presence of 75% metribuzin DF.

Thus, in one embodiment, a ZC formulation is provided comprising a suspension concentrate comprising particles of a first herbicide selected from the group consisting of sulfonylurea herbicides, triazinone herbicides, imidazolinone herbicides, triazine herbicides, anilide, sulfonamide-based herbicides, organophosphate herbicides, amide-based herbicides or alkanamide-based herbicides, in combination with a capsule suspension containing pendimethalin microcapsules in an aqueous phase, said microcapsules containing a herbicidally effective amount of pendimethalin encapsulated within a polymeric wall from polyurea, while the specified polymer wall of polyurea is from about 1 to about 20% of the total weight of the suspension, while the specified aqueous phase contains at least one salt of an alkali or alkaline earth metal and an organic acid lots 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, where at least one an 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.

The ZC formulation containing encapsulated pendimethalin with the first herbicide significantly improves the stability of the first herbicide, which would otherwise degrade when surrounded by other herbicides in the formulated product. The pendimethalin capsule suspension component used in the formulation is believed to contain a salt system which provides a suitable environment for the active substances to be degraded. Non-staining stable capsule suspension increases the shelf life of pendimethalin, and also to a greater extent reduces

- 3 041447 staining compared to commercially available pendimethalin formulations.

The first herbicides of the present invention are herbicides known to be degradable or known to be incompatible with pendimethalin, but show marked efficacy when stabilized in the ZC formulation of the present invention.

Many sulfonylurea herbicides are not known to be compatible with other active compounds. Known WP formulations of sulfonylurea herbicides, such as pyrazosulfuron-ethyl with pendimethalin, are known to suffer degradation and loss of physicochemical properties, while ZC formulation provides excellent stability of the active substance, which will be demonstrated in the examples below. The ZC product is stable and maintains physical and chemical properties in thermal stability test, freeze/thaw test and real time storage.

Thermal stability studies show the stability of the product at elevated temperatures and also give an indication of the shelf life of the product. Freeze/thaw stability indicates that a product can withstand cycles from low to room temperature. Real-time storage at ambient temperature gives information about the shelf life of the product.

Thus, in one embodiment, the first herbicide may be selected without limitation from classes of herbicides selected from sulfonylurea herbicides, triazinon herbicides, imidazolinone herbicides, triazine herbicides, anilide herbicides, quinolinecarboxylic acid herbicides. , benzoylcyclohexanedione herbicides, sulfonamide herbicides, benzofuranylalkylsulfonate herbicides, organophosphate herbicides, chloroacetanilide herbicides, nitrophenyl ether herbicides, sulfonamide herbicides, amide herbicides or alkaneamide herbicides and their mixtures.

In one embodiment, the sulfonylurea herbicide can be selected without limitation from amidosulfuron, azimsulfuron, bensulfuron or bensulfuron-methyl, chlorimuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, mesosulfuron, metazosulfuron, methysulfuron, methysulfuron, никосульфурона, ортосульфамурона, оксасульфурона, примисульфурона, пропирисульфурона, пиразосульфурона или пиразосульфурон-этила, римсульфурона, сульфометурона, сульфосульфурона, трифлоксисульфурона, хлорсульфурона, циносульфурона, этаметсульфурона, йодосульфурона, иофенсульфурона, метсульфурона или метсульфурон-метила, просульфурона, тифенсульфурона, триасульфурона, трибенурона, трифлусульфурона, tritosulfuron.

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

In one embodiment, the triazinon herbicide can be selected without limitation from ametridione, amibusin, etiosin, hexazinon, isomethiosin, metamitron, metribusin, or trifludimoxazine.

In another embodiment, the triazinon herbicide is metribuzin.

In one embodiment, the imidazolinone herbicide can be selected without limitation from imazametabenz, imazamox, imazapic, imazapyr, imazakhin, imazethapyr.

In another embodiment, the imidazolinone herbicide is imazapic. In yet another embodiment, the imidazolinone herbicide is imazapic acid.

In one embodiment, the triazine herbicide can be selected without limitation from dipropetrin, trihydroxytriazine, atrazine, chlorazine, cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine, propazine, sebutylazine, simazine, terbutylazine, trietazine, indaziflam, triaziflam, atratone, methomethone, promethone, sekbumeton, simeton, terbumeton, ametrine, aziprothrin, cyanathrine, desmetrin, dimethamethrin, metoprothrin, prometrin, simetrin, terbutrin.

In one embodiment, the triazine herbicide is atrazine.

In one embodiment, the amide herbicide can be selected without limitation from allidochlor, amicarbazone, beflubutamide, benzadox, benzipram, bromobutide, cafenstrol, diethanolamine (CDEA) cocamide, ciprazole, dimethenamid, dimethenamid-P, diphenamide, epronase, ethnipromide, phentrazamide, flucarbazone, flupoxam, fomesafen, halosafen, huancaolin, isocarbamide, isoxaben, napropamide, napropamide-M, petoxamide, propizamide, quinonamide, tebutam, thiafenacyl.

In one embodiment, the amide herbicide is preferably an alkanamide herbicide selected from napropamide or napropamide-M.

In one embodiment, the anilide herbicide can be selected without limitation from chloranocryl, cisanilide, clomeprop, cypromide, diflufenican, erlujixiancaoan, etobenzanide, fenasulam, flufenacet, flufenican, ipfencarbazone, mefenacet, mefluidide, methamifop,

- 4 041447 monalid, naproanilide, pentanochlor, picolinafen, propanil, sulfentrazone, triafamone.

In one embodiment, the anilide herbicide is diflufenican or flufenacet.

In one embodiment, the chloroacetanilide herbicide can be selected without limitation from acetochlor, alachlor, butachlor, butenachlor, delachlor, dietatyl, dimethachlor, ethachlor, etaprochlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prinachlor, terbuchlor, tenylchlor, xylachlor.

In one embodiment, the chloroacetanilide herbicide is metolachlor or S-metolachlor.

In one embodiment, quinolinecarboxylic acid herbicides can be selected without limitation from quinclorac, quinmerac.

In one embodiment, the benzoylcyclohexanedione herbicides can be selected without limitation from fenquinotrione, ketospiradox, mesotrione, sulcotrione, tefuryltrione, tembotrione.

In one embodiment, benzofuranylalkylsulfonate herbicides can be selected without limitation from benfuresate, ethofumesate.

In one embodiment, the dinitroaniline herbicide can be selected without limitation from benfluralin, butralin, chlornidine, dinitramine, dipropalin, ethalfluralin, fluchloralin, isopropalin, metalpropalin, nitralin, oryzalin, prodiamine, profluralin, trifluralin.

In one embodiment, the sulfonamide herbicides can be selected without limitation from asulam, carbasulam, fenasulam, oryzalin, penoxulam, pyroxulam.

In one embodiment, the sulfonamide herbicide is oryzalin.

In one embodiment, the nitrophenyl ether herbicides can be selected without limitation from acifluorfen and its salts, aclonifen, bifenox, chlomethoxifen, chlornitrofen, ethnipromide, fluorodifen, fluoroglycofen, fluoronitrophen, fomesafen, fucaomi, furyloxifene, halosafen, lactofen, nitrofen, , oxyfluorfen.

In one embodiment, the organophosphate herbicides can be selected without limitation from amiprofos-methyl, amiprofos, anilofos, bensulide, bilanaphos, butamiphos, claciphos, fosamine, glufosinate and all its salts and esters, glufosinate-P, glyphosate and all its salts and esters, huangcaolin, piperophos, shuangjiaancaolin.

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

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

Therefore, in this embodiment of the present invention, there is provided a ZC composition comprising:

(a) microencapsulated pendimethalin; and (b) a suspension concentrate of a co-herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide M, fluphenacet, oryzalin, glufosinate, glyphosate, and their agrochemically acceptable salts, and derivatives.

In another embodiment, the present invention provides a suspension containing particles of a first herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic-acid, atrazine, napropamide, napropamide-M, fluphenacet, oryzalin, glufosinate, glyphosate and their agrochemically acceptable salts. and derivatives, in combination with a suspension of pendimethalin microcapsules in an aqueous phase, wherein said microcapsules contain a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, wherein said polyurea polymer wall is from about 1 to about 20% of the total weight of the suspension, wherein said aqueous phase contains at least one salt of an alkali or alkaline earth metal and 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 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.

In another embodiment of the present invention, a ZC formulation is provided comprising

- 5 041447 suspension concentrate containing particles of the first herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic-acid, atrazine, napropamide, napropamide-M, fluphenacet, oryzalin, glufosinate, glyphosate and their agrochemically acceptable salts and derivatives, in combination with a capsule suspension containing pendimethalin microcapsules in an aqueous phase, wherein said microcapsules contain a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, wherein said polyurea polymer wall is from about 1 to about 20% of the total weight of the suspension, wherein said aqueous phase contains at least one salt of an alkali or alkaline earth metal and 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 acidacid, 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 contain another herbicide that is different from the first herbicide. This additional herbicide, as a rule, can be encapsulated together with pendimethalin within microcapsules. The choice of this additional herbicide is not particularly limited, and any herbicide that is compatible with pendimethalin can be selected.

The ZC formulations according to the present invention are prepared in such a way that pendimethalin is first microencapsulated and the resulting microcapsule dispersion, optionally after partial or complete removal of the liquid phase, is mixed with the suspension of the first herbicide.

In the embodiment where the first herbicide is a liquid, it is usually absorbed/adsorbed onto a particulate support. The particulate support with the liquid herbicide absorbed/adsorbed therein is then typically used to form a suspension for combination with the encapsulated pendimethalin.

In one aspect, a pendimethalin capsule suspension can be prepared by encapsulating pendimethalin within a polymer wall, said polymer wall being formed in situ by an interfacial polymerization reaction occurring between a first phase dispersed in a second phase, wherein at least one of said first and second phases is characterized by in that it contains a predetermined amount of at least one salt of an alkali or alkaline earth metal and an organic acid; And

The suspension concentrate of the present invention can be obtained by mixing surfactants, excipients, water and the first herbicide.

A capsule suspension containing pendimethalin can be obtained using the method described in the previously mentioned main applications.

The method includes:

(a) forming an aqueous solution containing at least one surfactant and a predetermined amount of at least one salt of an alkali or alkaline earth metal and an organic acid;

(b) forming an organic phase by melting a herbicidally effective amount of the pendimethalin active ingredient and adding a predetermined amount of the first wall-forming component to said organic phase;

(c) dispersing said organic phase in said aqueous solution to form an emulsion; and (d) adding a second wall-forming component to said emulsion, whereby said second wall-forming component reacts with said first wall-forming component contained in said emulsion to form a polymeric wall encapsulating at least said herbicidally effective amount of pendimethalin active ingredient.

Suspension concentrate containing selected first herbicides according to the present invention can be obtained as follows:

(a) forming a slurry containing water, surfactants and additional excipients with the first herbicide or mixtures thereof; and (b) grinding the slurry to the desired particle size at ambient temperature.

The microcapsules and suspension concentrate can then be mixed together to form a stable ZC formulation.

In alternative embodiments, the polymeric capsule wall of the present invention may be any known shell wall material, but is preferably selected from polyurea, polyurethane, polyamide, polycarbonate, polysulfonamide shell wall, or crosslinked or non-crosslinked combinations thereof. Preferably, the polymeric wall of the capsule is a polyurea wall.

The polymeric wall of the capsule of the present invention is formed by interfacial polymerization by bringing said first wall-forming component into contact with a second wall-forming component, as is generally known in the art.

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

Preferred polyisocyanates as the first wall-forming component can be selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethylene-4,4'-diisocyanate, polymethylene polyphenylene isocyanate, 2,4,4'-diphenyl ether triisocyanate, 3,3'-dimethyl- 4,4'-diphenyl diisocyanate, 3,3'-dimethoxy4,4'-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4'4-triphenylmethane triisocyanate. A preferred polyisocyanate for the first wall-forming component is polymethylene polyphenylisocyanate.

Preferred polyamines as the second wall-forming component can be selected from ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4,9-dioxadodecane-1,12-diamine, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4'diaminodiphenylmethane or their acid addition salts. The preferred polyamine according to the present invention is diethylenetriamine.

The first wall-forming component is from about 0.1 to about 20% by weight of the organic phase of the present invention. The second wall-forming component is preferably present in an amount of from about 0.3 to 7.5% by weight relative to the total weight of the composition.

In a further preferred embodiment, the preferred polyurea polymer shell wall may be formed by a self-condensation reaction of the wall-forming polyisocyanate component. In this embodiment, the method of obtaining the composition of the capsule suspension according to the present invention includes the formation of a physical dispersion of the organic phase in the aqueous phase. In this embodiment, the organic phase contains an organic isocyanate intermediate such as those described above, in addition to the active ingredient pendimethalin.

In one embodiment, the surfactants may be selected from ethylene oxide/propylene oxide condensates; alkylaryl and arylaryl ethoxylates and their derivatives; lignosulfonates; cresol- and naphthalene-formaldehyde condensates and sulfonates; polycarboxylates and their derivatives; and their mixtures.

In one embodiment, adjuvants may be selected from defoamers, antifreeze agents, suspending agents, preservatives, and thickening agents.

In one embodiment, antifoam agents can be selected from silicone emulsions such as SAG-1572, long chain alcohols, fatty acids, organofluorines, and mixtures thereof.

In one embodiment, the suspension containing the first herbicide, from which its suspension concentrate is obtained, can be ground to a particle size D ₉₀ of 8-10 microns.

Thus, in another aspect of the present invention, there is provided a method for preparing a ZC composition, said method comprising:

(a) forming an aqueous solution containing at least one surfactant and a predetermined amount of at least one salt of an alkali or alkaline earth metal and an organic acid;

(b) forming an organic phase by melting a herbicidally effective amount of pendimethalin active ingredient and adding a predetermined amount of a wall-forming polyisocyanate component;

(c) dispersing said organic phase in said aqueous solution to form an emulsion in which an interface is formed between the discrete droplets of the organic phase and the aqueous phase; and (d) maintaining said emulsion for a sufficient period of time to ensure that the polyisocyanate self-polymerization reaction is actually completed, whereby said liquid droplets in the organic phase are converted into capsules containing polyurea shells containing the active ingredient pendimethalin;

(e) the formation of a slurry containing a dispersant, water, surfactants

- 7 041447 substances and auxiliaries for obtaining a suspension and adding the first herbicide to the suspension;

(f) grinding the slurry to the desired particle size and mixing the resulting dispersion with the dispersion of the capsule suspension or mixing the dried microcapsules with the suspension; and (g) combining the microencapsulated portion of the formulation with the suspension.

In one embodiment, an emulsion of said organic phase in said aqueous solution may preferably be heated to a temperature of 20 to about 100°C, preferably to about 35-85°C to promote self-condensation of the polyisopianate prepolymer.

However, whether self-condensation of the first wall-forming component is preferred or whether condensation between the first and second wall-forming components is preferred, the relative amounts of organic and aqueous phases are not critical to the method of the present invention. Typically, the organic phase may comprise no more than about 75% by volume of the total emulsion, and the emulsion contains discrete drops of an organic solution dispersed in an aqueous solution.

It has been found that the droplet size in the emulsion is not critical to the composition and method of the present invention, and can be from 0.5 to about 4000 microns, which can be further adapted using a high shear device to preferably from about 1 to about 100 µm. In addition, the self-condensation in situ polymerization reaction has been found to be self-terminating and is typically allowed to continue to completion. The reaction, as a rule, continues to completion within a period of time from several minutes to several hours. In a preferred embodiment, the reactions are generally allowed to proceed for about 2-3 hours.

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

The alkali or alkaline earth metal salt of an organic acid used herein is 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.

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

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

The aqueous solution contains at least one surfactant. Preferably, the surfactant may be selected from the group consisting of ethoxylated lignosulfonic acid salts, lignosulfonic acid salts, oxidized lignins, lignin salts, styrene-maleic anhydride copolymer salts, polyvinyl alcohol, partial ester salts of styrene-maleic anhydride copolymers, partial salts polyacrylic acid; and partial salts of polyacrylic acid terpolymers.

Preferably the surfactant is calcium or sodium lignosulfonate.

Preferably, the surfactant is present in an amount of from about 0.2 to about 5% by weight of the composition.

The aqueous solution of the present invention comprises an alkali or alkaline earth metal salt of an organic acid, or mixtures thereof, in an amount of from about 2% to about 55% by weight of the composition.

The term herbicidally effective amount of pendimethalin or first herbicide (hereinafter referred to as co-herbicide) is that amount of pendimethalin or co-herbicide, respectively, which, when applied in that amount, will provide the desired weed control. The exact amount depends on many factors, including, for example, the crop, the weeds being controlled, and environmental conditions. The choice of the proper amount of active agent to be used, however, is within the skill of the art and is not considered to be particularly limiting.

The microcapsules of the present invention contain from about 5% to about 60% pendimethalin. The suspension concentrate of the present invention contains from 5% to about 60% of the co-herbicide.

In a preferred embodiment, the wall of the polymer shell according to the present invention is from about 1% by weight to about 20% by weight of the composition.

In another preferred embodiment, the wall of the polymer shell is approximately 2.5% of the total weight of the composition.

The microcapsules of the present invention are preferably characterized by a particle size of from about 2 to 50 microns.

In one embodiment, the slurry can be ground to a particle size D ₉₀ of 8-10 microns.

Preferably, the composition of the present invention contains an antifoam agent in an amount of from about 0.01 to about 5% by weight of the composition. Such suitable defoamers are generally known in the art and are not particularly limiting.

Preferably, the composition of the present invention contains surfactants in the form of salts of lignosulfonic acids, most preferably sodium or calcium salts.

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

The composition of the capsule suspension according to the present invention can be further neutralized, preferably with an organic acid, to stabilize the pH in the desired range. Accordingly, the compositions of 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.

Another advantage of adding a neutralizing acid is that the added acid combines with unreacted amines to form an ammonium salt, which greatly reduces the amount of externally added salt required to achieve a perceptible stain-free property. The addition of a neutralizing acid is particularly advantageous in that it reduces the level of inorganic salt compared to prior art formulations, which has been reported to exacerbate the problem of phytotoxicity in the various plants tested. In this embodiment of the present invention, substantially more amines in excess can be used to further reduce the amount of externally added salt by forming more salt in situ upon reaction with the neutralizing acid.

In a preferred embodiment, the compositions of the present invention may further contain a biocide in an amount of from about 0.01 to about 3% by weight of the composition.

In one aspect of the present invention, a ZC composition is provided comprising encapsulated pendimethalin and a co-administered herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, fluphenacet, oryzalin, glufosinate, glyphosate, and their agrochemically acceptable salts and derivatives, in the form of a suspension concentrate.

In one aspect of the present invention, there is provided a ZC composition comprising encapsulated pendimethalin and a suspension concentrate comprising at least two co-herbicides, wherein at least one of these co-herbicides is selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic α-acid, atrazine, napropamide, napropamide-M, fluphenacet, oryzalin, glufosinate, glyphosate and their agrochemically acceptable salts and derivatives.

In another aspect of the present invention, a process for preparing a ZC formulation is also provided, said process comprising:

(a) forming an aqueous solution containing at least one surfactant and a predetermined amount of at least one salt of an alkali or alkaline earth metal and an organic acid, and optionally heating said aqueous solution;

(b) forming an organic phase by melting a herbicidally effective amount of the pendimethalin active ingredient and adding a predetermined amount of the first wall-forming component to said organic phase;

(c) dispersing said organic phase in said aqueous solution to form an emulsion, and optionally heating said emulsion formed;

(d) adding a second wall-forming component to said emulsion, whereby said second wall-forming component reacts with said first wall-forming component contained in said emulsion to form a polymeric wall encapsulating at least said herbicidally effective amount of pendimethalin active ingredient;

(e) forming a slurry containing water, at least one herbicide, surfactants and excipients applied together;

(f) grinding the slurry to the desired particle size to form a stable suspension of the applied

- 9 041447 co-herbicide;

(g) combining the microencapsulated portion (d) of the formulation with the suspension.

Preferably, said step of forming an aqueous solution comprises heating water to an elevated temperature, preferably about 60° C., and adding said surfactant and said alkali or alkaline earth metal organic acid salt. In a preferred embodiment, an antifoam agent is also added to the aqueous solution.

In another preferred embodiment, said first wall-forming component is preferably added to said molten pendimethalin with stirring.

In yet another preferred embodiment, said step of dispersing said organic phase in said aqueous solution to form an emulsion is carried out to the desired particle size.

In another preferred embodiment, after adding the second wall-forming component to the emulsion, the reaction is allowed to continue for a predetermined time, preferably one hour, with stirring, while the reaction mixture is maintained at an elevated temperature.

The reaction mixture is then neutralized with an organic acid. Neutralization is preferably carried out until the pH of the composition is from about 6.5 to about 7.5.

The xanthan gum is then preferably added with stirring.

In a preferred embodiment, a biocide is added to obtain the desired composition.

In a preferred embodiment, the process of the present invention is carried out at an elevated temperature to keep the pendimethalin active ingredient molten and to increase the rate of polymer wall formation. In this embodiment, the method of the present invention is preferably carried out at a temperature of from about 35 to about 85°C, and more preferably is carried out at a temperature of from about 50 to 65°C.

Thus, in one embodiment, the present invention also provides a process for preparing a capsule suspension formulation, said process comprising:

(a) forming an aqueous solution containing at least one surfactant and a predetermined amount of at least one salt of an alkali or alkaline earth metal and an organic acid, and optionally heating said aqueous solution;

(b) forming an organic phase by melting a herbicidally effective amount of pendimethalin active ingredient and an additional herbicide 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 form an emulsion, and optionally heating said emulsion formed; and (d) adding a second wall-forming component to said emulsion, whereby said second wall-forming component reacts with said first wall-forming component contained in said emulsion to form a polymeric wall encapsulating at least said herbicidally effective amount of pendimethalin active ingredient, and any additional herbicide;

(e) forming a slurry containing water, the herbicide applied together, surfactants and excipients;

(f) grinding the slurry to the desired particle size to form a stable slurry of the co-herbicide;

(g) combining the microencapsulated portion (d) of the formulation with the suspension.

In one embodiment, the ZC formulation of the present invention comprises a mixture of the pendimethalin component and the co-herbicide slurry 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.

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

The present invention further relates to a method for controlling weeds at the locus by applying to the locus of weeds a herbicidally effective amount of a ZC formulation comprising microencapsulated pendimethalin and a co-herbicide.

Preferably, the present invention provides a method for controlling unwanted plant species which comprises applying to the foliage of plants, or to soil or water containing seeds or their other reproductive organs, a herbicidally effective amount of a ZC formulation comprising microencapsulated pendimethalin and a co-applied herbicide present as suspension concentrate.

Alternatively, the present invention provides a method for controlling undesirable plant species, which includes application to plant foliage or to soil

- 10 041447 or water containing seeds or their other reproductive organs, herbicidally effective amount

A ZC formulation containing pendimethalin microencapsulated together with an additional herbicide and the first herbicide present as a suspension concentrate in said formulation.

In one embodiment, the composition of the present invention may be packaged as a kit of constituents. In one embodiment, the set of constituents may contain various components of the composition of the present invention, which can be mixed according to the instructions before spraying.

Accordingly, in one aspect of the present invention, a herbicidal product of individually packaged components for controlling weeds in situ can be provided, comprising the components of the present invention and a manual for use. The Instructions for Use includes instructions for using the components of the ZC compound.

In one embodiment, the instructions for use include instructions for applying the ZC formulation to the locus, or to the foliage of the plants, or to the soil or water containing the seeds or other plant propagation organs.

In another embodiment, the instruction manual includes instructions for mixing the encapsulated pendimethalin component with the suspension concentrate component of the first herbicide in a predetermined ratio. In an embodiment, the instruction manual directs 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.

In an embodiment, the combination set is packaged in a bag or carton. In another embodiment, the instruction manual may be printed on said bag or carton, or may be printed in a booklet that may be included in the bag or carton.

The herbicidal composition and method of the present invention may provide some specific advantages over compositions known in the art. The novel combination of microencapsulated pendimethalin and the first herbicide in a ZC formulation allows for stable formulations that cover a wide range of weeds. ZC formulations significantly improve stability and allow the combination of incompatible active substances. The new ZC formulation also has the added benefit of being a non-staining pendimethalin formulation.

The present invention will now be described with reference to the following specific examples. It should be noted that the example(s) below are illustrative and not limiting of the present invention, and those skilled in the art will be able to develop many alternative embodiments without departing from the scope of the present invention.

Examples

Example 1 ZC composition of pendimethalin and sulfonylurea.

Composition of pendimethalin capsule suspension.

No. p / p Ingredients % w/w 1 Pendimethalin technical 40 at 97% purity, tech. 40.41 2 PMPI 1.01 3 Water 38.21 4 Borresperse Na 2.50 5 Na acetate (anhydrous) 15.30 6 Defoamer 0.10 7 EDA 0.23 8 DETA 0.26 9 Acetic acid 0.35 10 2% gel Rhodopol-23 1.50 AND Proxel GXL 0.13 12 Total 100.00

The above composition was obtained by operating in accordance with the encapsulation method of the present invention as follows.

An aqueous solution was obtained by heating water to 60°C, while adding sodium lignosulfonate and subsequently sodium acetate, then the defoamer with stirring. Sufficient water was stored separately to produce amine and gum. At this time, the organic phase was obtained by melting technical pendimethalin by heating it to 60°C and then adding polymethylene polyphenylisocyanate (PMPI) with stirring. The aqueous and organic phases were maintained at 60° C. throughout the reaction. The organic phase was emulsified in an aqueous solution

- 11 041447 to the desired particle size. DETA/EDA was added to the resulting emulsion. The reaction was allowed to proceed for 1 hour while maintaining 60° C. with stirring. The reaction mixture was allowed to cool to ambient temperature for 15 minutes before being neutralized with acetic acid. The composition was neutralized to pH 8.0 under reduced temperature conditions or to pH 7 under warmer conditions. The neutralized formulation was filtered through a 60 mesh sieve. A slurry of xanthan gum-water was prepared separately and added to the above formulation with stirring for at least 15 minutes. The biocide was added last and the final product was filtered through a 60 mesh sieve. Particle size was measured using Horiba LA-910 or CILAS 1064.

Suspension concentrate of sulfonylurea._____________________________________________

No. p / p 1 Composition component Sulfonylurea 51 at 98% purity, tech. Pyrazosulfuron-ethyl 52.04 Bensulfuron- Sulfosul- methyl 52.04 furon 52.04 2 Borresperse Na 06.00 06.00 06.00 3 Defoamer (SAG-1572) 00.10 00.10 00.10 4 Water (QS) 41.86 41.86 41.86 Total 100.00 100.00 100.00

The above composition was obtained, acting in accordance with the method, as follows.

An aqueous solution was prepared using water, sodium lignosulfonate and a defoamer. The sulfonylurea herbicide was added to the mixture and homogenized. The homogenized solution was crushed to particle size D ₉₀ 8-10 μm in a ball mill to form a suspension.

The microencapsulated pendimethalin was added to the sulfonylurea suspension concentrate to form the final ZC formulation. The resulting composition was subjected to stability tests.

Example 2 Data on the physicochemical properties of the ZC composition of pendimethalin + sulfonylurea.

No. p / p Properties Pyrazosulfuron-ethyl Bensulfuron-methyl Sulfosulfuron Ambient temperature 14 days AHS at 54°C Ambient temperature 14 days AHS at 54°C Ambient temperature 14 days AHS at 54°C 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 458.5 457.2 452.01 450.60 459.38 457.38 3 The content of the active ingredient sulfonylurea, g/l I,7 11.36 (destruction 2.9%) 27.53 26.99 (destruction 1.96%) 33.43 32.67 (destruction 2.27%)

- 12 041447

4 Suspension, % 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 a sieve during wet screening, % w/w 0.02 0.02 0.05 0.12 0.03 0.09 7 pH 1% of water composition 7.43 7.36 7.82 7.69 7.85 7.80 8 Fluidity: residue after washing, % 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

Conclusion.

1) All three formulations showed good physicochemical stability, suspension, dispersion spontaneity, pH range, wet screen retention, particle size in AHS at 54°C.

2) All three formulations showed improved active ingredient stability in AHS.

Example 3 Stability of the ZC formulation of pendimethalin + PSE at low temperature.

No. p / p Properties Before freeze/thaw test After freeze/thaw test 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 458.5 458.3 3 The content of the active ingredient pyrazosulfuron-ethyl, g / l I,7 11.65 4 The content of the active ingredient of free pendimethalin,% w/w 0.13 0.16 5 Suspension, % w/w 98.3 98.56 6 Retention on a sieve during wet screening, % w/w 0.02 0.03 7 pH 1% of water composition 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

Conclusion.

The content of free pendimethalin in the formulation was very low and both the stability of the capsules and the stability of the suspension at low temperature were excellent.

- 13 041447

Example 4 Real Time Storage Stability Data of ZC Formulation of Pendimethalin + Pyrazosulfuronethyl

No. p / p Properties Zero day 6 months 12 months 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 451.6 450.04 449.90 3 The content of the active ingredient pyrazosulfuronethyl, g/l 11.46 11.22 (destruction 2.09%) 11.15 (destruction 2.7%) 4 Suspension, % w/w 99.52 99.0 98.5 5 Spontaneity of dispersion, % w/w 100.93 100.5 99.85 6 Retention on a sieve during wet screening, % w/w 0.04 0.04 0.04 7 pH as indicated 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

Conclusion.

The composition was stable over a period of 12 months. Very little degradation was shown for pyrazosulfuron-ethyl and pendimethalin.

Example 5 Preparation of the ZC composition of pendimethalin + triazinon.

A capsule suspension of pendimethalin was prepared as described in Example 1. A metribuzin suspension concentrate was prepared according to the following composition.________________________

No. p / p Composition component % 1 Metribuzin technical 52 at 95% purity, tech. 54.74 2 Borresperse Na 7.50 4 Defoamer 0.10 6 Water 37.66 Total 100.00

The above composition was obtained in accordance with the following method.

An aqueous solution was prepared using water, sodium lignosulfonate and a defoamer. Metribuzin was added to the mixture and homogenized. The homogenized solution was crushed to particle size D ₉₀ 8-10 μm in a ball mill to form a suspension.

The microencapsulated pendimethalin was added to the metribuzin suspension concentrate to form the final ZC formulation. The resulting composition was subjected to stability tests.

Example 6 Data on the physicochemical properties of the ZC composition of pendimethalin + metribuzin.

No. p / p Properties Ambient temperature 14 days AHS at 54°C 1 Appearance Orange-yellow capsule suspension Liquid, orange-yellow capsule suspension 2 Active content pendimethalin ingredient 389.31 388.8

- 14 041447

3 Active content metribuzin ingredient 68.07 67.72 4 Suspension, % w/w 104.3 102.31 5 Spontaneity of dispersion, % w/w 105.3 103.26 6 Retention on the sieve during wet screening, % w/w 0.02 0.03 7 pH as indicated 7.15 7.29 8 Fluidity: residue after washing, % 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

Conclusion.

1) The formulation showed good stability of physico-chemical properties, suspension, spontaneity of dispersion, pH range, wet screen retention, particle size in AHS at 54°C.

2) The formulation showed improved active ingredient stability in AHS.

Example 6.1. Stability of the ZC composition of pendimethalin + metribuzin at low temperature.

No. p / p Properties Before testing with freeze/thaw After testing with freeze/thaw 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 389.31 389.19 3 The content of the active ingredient metribuzin, g/l 68.07 67.95 4 Suspension, % w/w 104.3 103.6 5 Retention on a sieve during wet screening, % w/w 0.02 0.03 6 pH as indicated 7.15 7.21 7 Particle size D-50 7.38 7.41 D-4.3 10.0 Yu,1 D-90 14.9 15.1

Conclusion.

The content of free pendimethalin in the formulation was very low and both the stability of the capsules and the stability of the suspension at low temperature were excellent.

Example 7 Real Time Storage Stability Data of Pendimethalin + Metribuzin ZC Formulation. _______________________________________________________________

No. p / p Properties Zero day 6 months 12 months 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 389.31 388.72 388.14 3 The content of the active ingredient metribuzin, g/l 68.07 66.78 66.43 4 Suspension, % w/w 104.3 99.68 99

- 15 041447

5 Spontaneity of dispersion, % w/w 105.3 100.12 101.0 6 Retention on a sieve during wet screening, % w/w 0.02 0.02 0.02 7 pH 1% aqueous dispersion 7.15 6.91 6.80 9 Particle size D-50 7.38 6.05 5.03 D-4.3 10.0 8.8 8.64 D-90 14.9 15.8 17.9

Conclusion.

1) The composition showed the stability of physical and chemical properties such as suspension, dispersion spontaneity, pH range, wet screen retention, particle size, etc. in AHS at 54°C and real-time storage over a period of 12 months.

2) Both pendimethalin and metribuzin showed good stability in AHS and real time storage.

Example 8 Pendimethalin + triazine herbicidal combination.

A capsule suspension of pendimethalin was prepared as described in Example 1. An atrazine suspension concentrate was prepared according to the following composition.____________________________

No. p / p Composition component % 1 Pendimethalin 18.1% at 40% pure CS 45.25 2 Atrazine 18.1% at 50% slurry purity 36.2 3 2% gel Rhodopol-23 2.50 4 R-100M 2.00 5 Proxel GXL 0.10 6 Water 13.95 Total 100.00

The above composition was obtained in accordance with the following method.

An aqueous solution was prepared using water, sodium lignosulfonate and a defoamer. Atrazine was added to the mixture and homogenized. The homogenized solution was crushed to particle size D ₉₀ 8-10 μm in a ball mill to form a suspension.

The microencapsulated pendimethalin was added to the atrazine suspension concentrate to form the final ZC formulation. The resulting composition was subjected to stability tests.

Example 9 Data on the physicochemical properties of the ZC composition of pendimethalin + atrazine.

No. p / p Properties Ambient temperature 14 days AHS 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 206.99 205.98 3 The content of the active ingredient atrazine, g/l 206.69 205.50 4 Suspension, % w/w 103.91 102.69 5 Spontaneity of dispersion, % w/w 100.83 100.11 6 Retention on a sieve during wet screening, % w/w 0.01 0.03 7 pH as indicated 7.31 7.48 8 Fluidity: residue after washing, % 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

Conclusion regarding the ZC composition of pendimethalin with atrazine.

1) The formulation showed good stability of physical and chemical properties such as suspension, dispersion spontaneity, pH range, wet screen retention, particle size, etc. in AHS at 54°C and real-time storage.

2) The formulation showed excellent stability in AHS.

- 16041447

Example 10 Low Temperature Stability

No. p / p Properties Before freeze/thaw test After freeze/thaw test 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 206.99 206.27 3 The content of the active ingredient atrazine, g/l 206.69 206.50 4 Suspension, % w/w 103.91 101.73 5 Retention on a sieve during wet screening, % w/w 0.01 0.05 6 pH as indicated 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

Conclusion.

The composition was found to be stable in the freeze/thaw cycle and retain its physico-chemical properties as a sample at ambient temperature.

Example 11 ZC formulation of pendimethalin + alkanamide herbicide.

A capsule suspension of pendimethalin was prepared as described in Example 1. A suspension concentrate of D-napropamide was prepared according to the following composition._____________________

No. p / p Composition component % 1 D-napropamide 52 at 98% pure 53.06 2 Borresperse ΝΑ 7.00 3 Defoamer (SAG-1572) 0.50 4 Water (QS) 39.44 Total 100.00

The above composition was obtained in accordance with the following method.

An aqueous solution was prepared using water, sodium lignosulfonate and a defoamer. D-napropamide was added to the mixture and homogenized. The homogenized solution was crushed to particle size D ₉₀ 8-10 μm in a ball mill to form a suspension.

The microencapsulated pendimethalin was added to the D-napropamide suspension concentrate to form the final ZC formulation. The resulting composition was subjected to stability tests.

Example 12 Data on the physicochemical properties of the ZC composition of pendimethalin + P-napropamide.

No. p / p Properties Ambient temperature 14 days AHS 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 241.01 240.8 3 The content of the active ingredient D-napropamide, g/l 221.2 221.0 4 Suspension, % w/w 98.3 99.0 5 Spontaneity of dispersion, % w/w 99.89 100.2 6 Retention on a sieve during wet screening, % w/w 0.04 0.05 7 pH 1% aqueous suspension 7.69 7.58 8 Fluidity: residue after washing, % 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

- 17041447

Conclusion regarding the ZC composition of pendimethalin with D-napropamide.

1) The composition showed excellent stability of physical and chemical properties such as suspension, dispersion spontaneity, pH range, wet screen retention, particle size, etc. in AHS at 54°C and real-time storage.

2) Both pendimethalin and D-napropamide showed excellent stability in AHS.

Example 13 Stability of the ZC formulation of pendimethalin + +D-napropamide at low temperature.

No. p / p Properties Before freeze/thaw test After freeze/thaw test 1 Appearance Orange-yellow capsule suspension Fluid, orange-yellow capsule suspension 2 The content of the active ingredient pendimethalin, g/l 241.01 240.92 3 Active content 221.2 221.45 ingredient D-propamide, g/l 4 Suspension, % w/w 98.3 98.96 5 Retention on a sieve during wet screening, % w/w 0.04 0.06 6 pH as indicated 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

Conclusion.

The composition was found to be stable in the freeze/thaw cycle and retain its physico-chemical properties as a sample at ambient temperature.

Example 14 ZC formulations of pendimethalin + imidazolinone herbicide.

A capsule suspension of pendimethalin was prepared as described in Example 1. The imidazolinone herbicides, imazapic and imazatapyr, were formulated into suspension concentrates according to the following formulation. ________________________________________________________________________

No. p / p Composition component Imazapicacid Imazatpyracid 1 Imidazolinone at 96% purity, tech. 46.4 52.08 2 Borropsperse ΝΑ 7.00 7.00 3 Defoamer (SAG-1572) 0.50 0.50 4 Water (QS) 46.1 40.42 Total 100.00 100.00

The above composition was obtained in accordance with the following method.

An aqueous solution was prepared using water, pendimethalin capsule suspension, sodium lignosulfonate and a defoamer. Imidazolinone was added to the mixture and homogenized to give the final ZC formulation.

Example 15 ZC formulation of pendimethalin + imazapic acid.

A capsule suspension of pendimethalin was prepared as described in Example 1. Imazapic was formulated into a suspension concentrate according to the following formulation.

No. p / p Composition component % 1 Pendimethalin 31.3 at 40.7% pure CS 76.90 2 Imazapic acid 8.5 at 45% pure slurry 18.88 3 Reax-100 M 2.00 4 2% gel Rhodopol-23 1.00 5 Proxel GXL 0.10 6 Water (QS) 1.12 Total 100.00

The above composition was obtained in accordance with the following method.

An aqueous solution was prepared using water, pendimethalin capsule suspension, sodium lignosulfonate, xanthan gum, biocide. The mixture was homogenized. Imazapic was added to the mixture and homogenized to obtain the final ZC formulation. The composition was found to be stable at ambient temperature.

- 18 041447

Example 16 ZC formulation of pendimethalin + organophosphate herbicide.

A capsule suspension of pendimethalin was prepared as described in Example 1. A glyphosate suspension concentrate was prepared according to the following formulation.

No. p / p Composition component % w/w 1 Glyphosate Acid 45 at 96% Purity 46.4 2 Borresperse ΝΑ 7.00 3 Defoamer (SAG-1572) 0.50 4 Water (QS) 46.1 Total 100.00

The above composition was obtained, acting in accordance with the method, as follows.

An aqueous solution was prepared using water, sodium lignosulfonate and a defoamer. Glyphosate acid was added to the mixture and homogenized. The homogenized solution was crushed to particle size D9 ₀ 8-10 μm in a ball mill to form a suspension.

The microencapsulated pendimethalin was added to the glyphosate acid suspension concentrate to form the final ZC formulation.

Example 17 ZC formulation of pendimethalin + glyphosate.

A capsule suspension of pendimethalin was prepared as described in Example 1. A glyphosate suspension concentrate was prepared according to the following formulation.

No. p / p Composition component % 1 Pendimethalin 27 at 40.7% pure CS 66.34 2 Glyphosate acid 11.75 at 45% slurry purity 26.11 3 Reax-100 M 2.00 4 2% gel Rhodopol-23 2.00 5 Proxel GXL 0.10 6 Water (QS) 3.45 Total 100.00

The above composition was obtained in accordance with the following method.

An aqueous solution was prepared using water, pendimethalin capsule suspension, sodium lignosulfonate and xanthan gum. Glyphosate was added to the mixture and homogenized to give the final ZC formulation. The composition was found to be stable at ambient temperature.

Comparative examples.

Compositions of pendimethalin were prepared using other types of formulations to compare efficacy, stability and compatibility compared to the ZC formulation.

Example 18A. WP compositions of pendimethalin + pyrazosulfuron-ethyl Composition of the WP composition of pendimethalin.

No. p / p Ingredients % w/w 1 Pendimethalin 45.5% at 96% pure CS 47.40 2 M-fill А-100 26.94 3 Metasperse 550S 8 4 Supragil WP 4.5 5 Defoamer (DC 1920) 1 5 Ammonium sulfate 10 Total 97.85

Composition of the WP-composition of pyrazosulfuron-ethyl.

No. p / p Ingredients % w/w 1 PSE 1.1% at 95% purity, tech. 1.16 2 Supragil WP 0.50 3 M-fill А-100 0.5 Total 2.15

Way.

Stage-1: pendimethalin premix.

a) Pendimethalin was melted and absorbed onto the precipitated silica by slowly adding to the stirrer at low rpm and kept overnight.

b) Mixed Metasperse 550s (modified styrene-acrylic polymer), Supragil WP

- 19 041447 (dialkylnaphthalenesulfonate sodium salt), ammonium sulfate and antifoam powder

DC1920 into the above pendimethalin+silica mixture from step a) and stirred until homogeneous.

c) The premix was ground with an Air jet mill to obtain a lump-free material.

Step-2: pyrazosulfuron-ethyl premix.

a) Pyrazosulfuron-ethyl technical, Supragil WP (sodium salt of dialkylnaphthalenesulfonate) and M-fill A-100 (precipitated silicon dioxide) were mixed and ground using an Air jet mill to obtain a particle size D ₉₈ of 30-36 microns.

Stage-3: mixing.

The pendimethalin premix from step 1 and the pyrazosulfuron premix from step 2 were mixed to form the final WP formulation.

The resulting formulation was then subjected to stability tests.

Data on the physicochemical properties of the WP-composition of pendimethalin + pyrazosulfuron-ethyl.

No. p / p Properties Ambient temperature 6 weeks AHS at 45°C Data acquired with 7 months real-time storage 1 Appearance Yellow powder with high flowability Yellow-orange powder in the form of small soft lumps Yellow-orange powder 2 The content of the active ingredient pendimethalin,% w/w 45.87 45.75 45.67 3 The content of the active ingredient pyrazosulfuronethyl,% w/w 1.05 1.002 (destruction 4.5%) 0.92 (destruction 12%) 4 Suspension, % w/w gravimetric results 84.39 68 58 5 Wetting time in seconds 40 20 thirty 6 Retention on a sieve during wet screening, % w/w 0.07 0.30 1.62 7 pH 1% aqueous suspension 6.89 6.71 6.80

Conclusion.

1. The formulation showed a reduction in suspension in AHS and real-time storage.

2. The degradation of pyrazosulfuron-ethyl was found to be 12% with only 7 months of real time storage, which is a very high value compared to the stable formulations of Example 1.

3. The formulation showed an increase in wet screen retention in AHS and a strong increase in wet screen retention of up to 1.68% with only 7 months of real time storage.

Example 18B. WP-compositions of pendimethalin + metribuzin.

8.2.1. Composition of the WP-composition of pendimethalin.

No. p / p Ingredients % w/w 1 Pendimethalin 38.7% at 97% pure 39.90 2 M-fill А-100 22 3 Metasperse 550S 7 4 Supragil WP 4.5 5 Defoamer DC 1920 1 5 Ammonium sulfate 15.05 Total 89.45

- 20 041447

8.2.2. Composition of the WP-composition of metribuzin.

No. p / p Ingredients % w/w 1 Metribuzin 6.7% at 95% purity, tech. 7.05 2 Supragil WP 0.50 3 M-fill A-100 2.00 4 Metasperse 55OS 1.00 Total 10.55

Way.

Stage-1: pendimethalin premix.

a) M-fill A-100 (precipitated silica), Metasperse 550s (modified styrene-acrylic polymer) and Supragil WP (modified styrene-acrylic polymer) were added to the mixer and the melted pendimethalin tech. by slowly adding at low rpm.

b) Ammonium sulfate and DC1920 antifoam powder were then added and mixed until homogeneous. The material was kept overnight.

Stage-2: metribuzin premix.

c) Metribuzin tech., Metasperse 550 S (modified styrene-acrylic polymer), Supragil WP (modified styrene-acrylic polymer) and M-fill A-100 (precipitated silica) were pre-mixed and ground using an Air jet mill to obtain a size particles D ₉₈ 30-36 microns.

Stage-3: mixing.

The pendimethalin premix from step 1 and the metribuzin premix from step 2 were mixed to form the final WP formulation.

The resulting formulation was then subjected to stability tests.

Data on the physicochemical properties of the WP-composition of pendimethalin + metribuzin.

No. p / p Properties Ambient temperature 6 weeks AHS at 45°C 1 Appearance Yellow powder with high flowability Yellow-orange powder in the form of small soft lumps 2 The content of the active ingredient pendimethalin,% w/w 38.57 38.53 3 The content of the active ingredient metribuzin,% w/w 6.75 6.72 4 Suspension, % w/w 88.48 40.29 5 Wetting time in seconds 17 thirty 6 Retention on a sieve during wet screening, % w/w 0.12 0.48 7 pH 1% aqueous suspension 7.27 7.01

Conclusion regarding the WP composition of pendimethalin with metribuzin.

1. The formulation showed reduced suspension in AHS and real-time storage for 6 weeks.

2. The formulation showed improved wet screen retention in AHS.

3. It was a soft lump in AHS, which is undesirable.

As used herein, the term ZC will be used to refer to formulations of capsule suspensions and suspension concentrates, each of which may contain a single herbicide or a combination of herbicides, such as those described herein. Therefore, ZC is an aqueous suspension of microcapsules and solid particles, each containing one or more herbicidal active ingredients according to the present invention. The capsule suspension component typically contains encapsulated pendimethalin, optionally together with another herbicide. The suspension concentrate component typically includes another herbicide or combination of herbicides.

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Claims (4)

CLAIM 1. ZC-composition for weed control, containing: a) microencapsulated pendimethalin, wherein the microencapsulated pendimethalin comprises a suspension of pendimethalin microcapsules in an aqueous phase, said microcapsules containing a herbicidally effective amount of pendimethalin encapsulated within a polyurea polymer wall, said polyurea polymer wall comprising 1 to 20% of the total weight of the suspension wherein said aqueous phase contains at least one salt of an alkali or alkaline earth metal and 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 at least one 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; And b) a suspension concentrate of a co-herbicide, the suspension concentrate comprising particles of a co-herbicide selected from the group consisting of sulfonylurea herbicides, triazinone herbicides, imidazolinone herbicides, triazine herbicides, organophosphate herbicides, herbicides based on an amide and a herbicide based on benzoylcyclohexanedione selected from the group consisting of fenquinotrione, ketospiradox, mesotrione, sulcotrione, tefuryltrione and tembotrione. 2. ZC-composition according to claim 1, where the suspension concentrate contains a herbicide, which is: (a) a sulfonylurea herbicide selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron or bensulfuron-methyl, chlorimuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupirsulfuron, foramsulfuron, halosulfuron, imazosulfuron, mesosulfuron, никосульфурона, ортосульфамурона, оксасульфурона, примисульфурона, пропирисульфурона, пиразосульфурона или пиразосульфурон-этила, римсульфурона, сульфометурона, сульфосульфурона, трифлоксисульфурона, хлорсульфурона, циносульфурона, этаметсульфурона, йодосульфурона, иофенсульфурона, метсульфурона или метсульфурон-метила, просульфурона, тифенсульфурона, триасульфурона, трибенурона, трифлусульфурона и tritosulfuron; or (b) a triazinon herbicide selected from the group consisting of ametridione, amibusin, etiosin, hexazinon, isomethiosin, metamitron, metribuzin, and trifludimoxazine; or (c) an imidazolinone herbicide selected from the group consisting of imazametabenz, imazamox, imazapic acid, imazapyr, imazakhin and imazethapyr; or (d) a triazine herbicide selected from the group consisting of dipropetrin, trihydroxytriazine, atrazine, chlorazine, cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglynasine, propazine, sebutylazine, simazine, terbutylazine, trietazine, indaziflam, triaziflam , atratone, methomethone, promethone, sekbumeton, simeton, terbumeton, ametrin, aziprothrin, cyanathrine, desmetrin, dimethamethrin, metoprotrin, prometrin, simetrin and terbutrin; or (e) an amide based herbicide selected from the group consisting of allidochlor, amicarbazone, beflubutamide, benzadox, benzipram, bromobutide, cafestrol, diethanolamine cocamide, ciprazole, dimethenamid, dimethenamid-P, diphenamide, epronase, ethnipromide, phentrazamide, flucarbazone, flupoxam, fomesafen, halosafen, huancaolin, isocarbamide, isoxaben, napropamide, napropamide, petoxamide, propizamide, quinonamide, tebutam and thiafenacyl; or (f) an organophosphate herbicide selected from the group consisting of amiprofos-methyl, amiprofos, anilofos, bensulide, bilanaphos, butamiphos, claciphos, fosamine, glufosinate and all its salts and esters, glufosinate-P, glyphosate and all its salts and esters, huangcaolin, piperophos and shuangjiaancaolin. 3. The ZC composition according to any one of the preceding claims, wherein the suspension concentrate contains a herbicide selected from the group consisting of pyrazosulfuron-ethyl, metribuzin, imazapic acid, atrazine, napropamide, napropamide-M, glufosinate and glyphosate. 4. A method for controlling weeds in a locus by applying to the locus of weeds or plant foliage, or soil or water containing seeds or their other reproductive organs, a herbicidally effective amount of the ZC composition of claim 2. -22Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2