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An Organized Isotropic Dispersion

Abstract: Disclosed herein is an agrochemical isotropic mutual dispersion of a hydrophilic phase and a hydrophobic phase with at least one surfactant being disposed at the interface between said hydrophilic and hydrophobic phases, wherein said hydrophilic phase comprises a herbicidally effective amount of at least one water soluble herbicidal salt dissolved in a water miscible solvent and wherein said hydrophobic phase comprises a herbicidally effective amount of a water insoluble herbicide dissolved in a solvent system comprising a non-polar organic solvent. Also present are methods for preparation of such agrochemical isotropic mutual dispersion in accordance with the present invention.

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Patent Information

Application #
Filing Date
15 July 2011
Publication Number
03/2013
Publication Type
INA
Invention Field
PHYSICS
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2021-04-23
Renewal Date

Applicants

UNITED PHOSPHORUS LIMITED
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST),MUMBAI-400 052, STATE OF MAHARASHTRA,INDIA.

Inventors

1. SHROFF, JAIDEV RAJNIKANT
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST),MUMBAI-400 052,STATE OF MAHARASHTRA,INDIA.
2. SHROFF , VIKRAM RAJNIKANT
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST),MUMBAI-400 052,STATE OF MAHARASHTRA,INDIA
3. SHIRSAT , RAJAN RAMAKANT
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST),MUMBAI-400 052,STATE OF MAHARASHTRA,INDIA

Specification

FORM2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention- AN ORGANIZED ISOTROPIC DISPERSION.
2. Applicant(s)
(a) NAME : UNITED PHOSPHORUS LIMITED
(b) NATIONALITY : An Indian Company
(c) ADDRESS : Uniphos House, Madhu Park, 11th Road, Khar (West),
Mumbai -400 052, Stateof Maharashtra, India
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

Field of the Invention
The present invention relates to a storage stable agrochemical composition comprising an organized isotropic dispersion of at least two immiscible liquids. More particularly, the present invention relates to a high loaded stable agrochemical composition comprising an organized aqueous phase mutually dispersed in a solvent-surfactant system.
Background of the Invention
The challenge involved in developing commercially acceptable products containing agriculturally active compounds continues to increase due to the rapid emergence of more complex customer and regulatory requirements. These agricultural compositions must exhibit excellent chemical stability and must also maintain a high level of physical stability under a severe range of storage and use conditions. Handling of a liquid product in bulk storage facilities represents a special challenge because the product can be subject to high shear forces at both high and low temperatures. This emerging area of performance is critical to customer satisfaction and commercial success with a product since poor compatibility in the final use mixture can cause blockage of sprayer screens and nozzles, preventing proper application of the product. At the same time the demand on the agrochemical composition performance has been increasing, the number of auxiliary chemicals approved for use in agrochemical compositions by the various regulatory authorities has been decreasing due to more stringent standards for the toxicological and ecological effect of these materials.
The agrochemical compositions are generally prepared using one or more adjuvants sometimes in specific combinations to provide optimum biological activity. Much has been published on the selection of adjuvants and specific combinations of adjuvants that have been designed to achieve particular effects with individual and classes of agrochemicals. Sometimes higher the concentration of the active agrochemical and its associated adjuvants, greater is the probability

that the stability of the formulation may be disturbed and one or more component separates out, for example as a discrete phase. In general, the separation of a discrete phase from an agrochemical is highly undesirable, particularly when the formulation is sold in bulk containers. In these circumstances it is virtually impossible to re-homogenize the formulation and to achieve even distribution of the components on dilution and spraying. Furthermore, the formulation especially when in the form of a dispersion of two or more immiscible fluids, must be stable in respect of storage for prolonged periods in both hot and cold environments. This problem is aggravated in formulations especially comprising two different pesticides, which are insoluble in a common liquid phase. These all factors present formidable problems to the formulator.
The use of herbicide combinations is a widespread and documented practice in the agricultural community. Herbicidal combinations offer significant advantages over individual applications including improved and extended weed control, reduced herbicide rates and application costs, shorter contact times for improved results in flowing water, less stringent use restrictions, improved selectivity, improved spectrum of weeds controlled, reduced cost and reduced residue problems. However, identifying appropriate herbicide application rates and combinations is essential to achieve synergistic weed control.
United States Patent No. 4713109 teaches a 2-propynyl ester of the compound 2-(4- (3-Chloro-5-fluoro-2-pyridyloxy)-phenoxy-propionic acid, which is commonly known as clodinafop-propargyl, a compound possessing demonstrated herbicidal activity against grassy weeds in winter cereals specially in wheat and barley as well as pulses. It is a member of the oxy-phenoxy acid ester class of herbicides. It is known that clodinafop-propargyl interacts with and inhibits the acetyl co-enzyme A carboxylase, which is essential for the production of lipids or fatty acids needed for plant growth. The selectivity of this herbicide is based on the difference in the speed of herbicide breakdown in the crop versus the weeds. Clodinafop-propargyl converts from the ester form to the active acid and then to biologically inactive compounds. Grass weeds such as wild oats and wild millet

cannot effectively break down clodinafop-propargyl, so they are controlled as a lethal dose accumulates at the meristematic growing points. This is a post emergence, selective systemic grass herbicide and is known to control grasses such as green foxtail, barnyard grass, persian darnel and volunteer canary seed in wheat crops. It is also known that clodinafop-propargyl is ineffective against several broadleaved weeds, which fuels a need to combine it with other known herbicides- However, a major problem with clodinafop-propargyl is that it undergoes hydrolysis in the presence of an aqueous medium in acidic environment rendering it incapable of being formulated as stable formulation along with a water soluble herbicide to form a stable soluble liquid formulation.
Nevertheless, herbicide combinations offer advantages of improved weed control, a greater spectrum of weeds controlled, reduced cost and reduced residue problems. It is desirable to provide a suitable combination partner which will synergistically potentiate clodinafop-propargyl in view of its peculiar disadvantages discussed above and including water-sensitivity.
US Patent 4285723 discloses, selective diphenyl ether herbicides including
fomesafen, 5-(2-chloro-a,a,a-trifiuoro-tolyloxy)-N-mesyl-2-
nitrobenzenecarboximidate, and its agrochemically acceptable salts. Fomesafen sodium is a selective early post emergent herbicide used to control broad leaved weeds in soybean. Fomesafen sodium is known to produce phytotoxicity to desired crop. Fomesafen sodium is formulated as Microemulsion (ME) and Soluble Liquid (SL) formulation. It is registered and marketed under the brand name of Flexstar and Reflex and its existing formulations also suffer from the disadvantage of phytotoxicity. Therefore, there is a further need in the art to provide a formulation of fomesafen sodium with clodinafop propargyl that causes no phytotoxicity.
PCT Publication No. WO 2010 143205 discloses fomesafen sodium as a preferred combination partner for clodinafop-propargyl. However, the exemplified formulations of fomesafen sodium with clodinafop-propargyl utilize a high

amount of a polar organic solvent (even about 70%), which is undesirable. There are a number of reported disadvantages of using an increased amount of organic solvent such as increased flammability of the formulation and other solvent-exposure associated health hazards such as toxicity to the nervous system, reproductive damage and dermatitis as well as stringent environmental issues. There is thus a need in the art for a formulation comprising clodinafop propargyl in combination with fomesafen sodium wherein the formulation is more eco-friendly in comprising a reduced amount of an organic solvent without compromising the physico-chemical stability profile of the formulation.
US Patent No. 6369001 provides a liquid concentrate herbicidal microemulsion composition comprising water; a water-soluble herbicide and an oil-soluble cyclohexenone or aryloxyphenoxypropionate graminicide. This patent discloses many examples of water soluble herbicide such as acifluorfen and fomesafen and oil soluble cyclohexenone such as Clodinafop-propargyl. However, it does not teach the selective combinations of fomesafen sodium and Clodinafop propargyl. Further, this patent does not address and solve the specific degradation problem of Clodinafop- propargyl, particularly in an aqueous environment. It was found that liquid concentrates or water based formulations comprising clodinafop- propargyl and fomesafen sodium have poor stability and aggravate the problem of degradation of clodinafop-propargyl.
Therefore, there is a long felt need in the art to provide a stable formulation comprising clodinafop propargyl and fomesafen sodium that solves the problems of degradation of clodinafop propargyl in aqueous medium and solves the existing problem of phytotoxicity induced by these active ingredients. The present invention provides such a storage stable dispersion that is dilutable to a microemulsion or emulsifiable concentrate formulation of clodinafop-propargyl and fomesafen sodium that causes no phytotoxicity and prevents clodinafop-propargyl from contacting the aqueous medium despite the presence of a hydrophilic phase (containing water) within the same dispersion.

Accordingly, in another embodiment, the present invention provides an emulsifiable concentrate formulation or a microemulsion formulation comprising the mutual dispersion such as herein described.
It has also been observed that a high loading of the active ingredients in a formulation always results into an unstable product on storage. Thus, there is a further need in the art for a formulation that is able to accommodate a high concentration of herbicidal active ingredients without compromising on the storage stability of the product.
It is also advantageous according to an embodiment of the present invention to prepare a formulation which is thermodynamically stable and an isotropic dispersion of one liquid into at least another immiscible liquid. These formulations are conventionally also prepared as microemulsion formulations or microemulsifiable concentrate formulations, which are formed spontaneously on simple mixing. Without wishing to be bound by theory, it is believed that these formulations are stabilized by an adsorbed surfactant film at the liquid-liquid interface.
However, it is known to be difficult to prepare a stable microemulsion or a stable emulsifiable concentrate of a water soluble herbicide. The resultant microemulsion of a water soluble herbicide is also required to meet the requirements of the end user for effective weed control including good crop safety.
Thus all these challenges have now surprisingly been met by an invention set out immediately below.
Object of the Invention:
An object of the present invention is a storage stable formulation comprising an organized isotropic dispersion of at least two immisicible liquids, each comprising a herbicidal active ingredient.

Another object of the present invention is a high loaded stable agrochemical composition comprising an organized aqueous phase comprising a water soluble herbicide dispersed in an external second herbicide-solvent-surfactant system.
Another object of the present invention is a herbicidal composition that exhibits superior chemical stability and maintains a high level of physical stability under a severe range of storage and use conditions.
Another object of the present invention is a liquid herbicidal formulation comprising clodinafop-propargyl along with a suitable combination partner wherein clodinafop-propargyl does not undergo hydrolysis even in the presence of an aqueous system.
Another object of the present invention is a liquid herbicidal formulation offering improved weed control, a greater spectrum of weeds controlled, reduced cost and reduced residue problems.
Another object of the present invention is a liquid herbicidal formulation comprising clodinafop-propargyl in combination with fomesafen sodium wherein the formulation is more eco-friendly in comprising a reduced amount of an organic solvent without compromising the physico-chemical stability profile of the formulation.
Another object of the present invention is a liquid herbicidal formulation comprising clodinafop-propargyl in combination with fomesafen sodium wherein the formulation exhibits reduced phytotoxicity in comparison to the conventional soluble liquid formulation comprising fomesafen sodium.
Another object of the present invention is in providing a formulation that is able to accommodate a high concentration of herbicidal active ingredients without compromising on the storage stability of the product.

These and other object of the present invention would be apparent from the description of the invention set out hereinafter.
Summary of the Invention
Accordingly, in one aspect, the present invention provides an agrochemical isotropic mutual dispersion of a hydrophilic phase and a hydrophobic phase with at least one surfactant being disposed at the interface between said hydrophilic and hydrophobic phases, wherein said hydrophilic phase comprises a herbicidally effective amount of at least one water soluble herbicidal salt dissolved in a water miscible solvent and wherein said hydrophobic phase comprises a herbicidally effective amount of a water insoluble herbicide dissolved in a solvent system comprising a non-polar organic solvent.
In another aspect, the present invention provides an agrochemical isotropic mutual dispersion of an aqueous phase and an organic phase with at least one surfactant being disposed at the interface between said aqueous and organic phases, wherein said aqueous phase comprises a herbicidally effective amount of fomesafen sodium dissolved in water and wherein said organic phase comprises clodinafop-propargyl dissolved in a solvent system comprising a non-polar organic solvent.
In yet another aspect, the present invention provides a process for the preparation of an agrochemical isotropic dispersion of at least two immiscible liquids, said process comprising:
(a) dissolving a herbicidally effective amount of at least one water soluble herbicide in water and adding at least one surfactant and a co-solvent to obtain a hydrophilic phase;
(b) mixing a herbicidally effective amount of at least one water insoluble herbicide in an organic solvent to obtain a hydrophobic phase; and
(c) adding a predetermined quantity of said hydrophilic phase to a predetermined quantity of said hydrophobic phase.

In yet another aspect, the present invention provides a process for the preparation of an agrochemical isotropic dispersion of at least two immiscible liquids, said process comprising:
(a) dissolving a herbicidally effective amount of fomsafen sodium in water and adding at least one surfactant and a co-solvent to obtain a hydrophilic phase;
(b) mixing a herbicidally effective amount of clodinafop-propargyl in an organic solvent to obtain a hydrophobic phase; and
(c) adding a predetermined quantity of said hydrophilic phase to a predetermined quantity of said hydrophobic phase.
In yet another aspect, the present invention provides a method of controlling an undesired weed at a location comprising applying an isotropic mutual dispersion according to the present invention at the desired location.
Brief Description of Accompanying Figures
Figure 1 illustrates the conductivity of the mutual dispersion of Example A and a salt solution at different dilution levels from 0.4% to 21%.
Figure 2 illustrates the conductivity of the micro-emulsion in accordance with the present invention and a salt solution at different dilution levels.
Detailed Description of the Invention
In an embodiment, the formulations according to the present invention comprise water as the water miscible solvent into which a herbicidally effective amount of fomesafen sodium is dissolved to form the hydrophilic phase of the present invention. A water immiscible solvent, more preferably a non-polar organic solvent, dissolves a water insoluble herbicide to form the hydrophobic phase of the present invention. It has been found that a formulation comprising the surfactant contemplated according to the present invention and the water soluble

herbicide of the invention is physicochemically stable even at a high loading of the active ingredients. There was no change in the chemical and physical stability of such formulations even after a prolonged storage.
In an embodiment, the mutual dispersion of the invention is a microemulsion, which is a mutual dispersion of the hydrophilic and hydrophobic phase globules in contact with each other. It has been found that the presence of fomesafen sodium in the hydrophilic phase maximizes the mutual dispersion of the hydrophobic and hydrophilic phases, which was considered surprising. The maximized mutual dispersion of the hydrophilic and hydrophobic phases resulted into a stable micellar solubilization of the water-insoluble herbicide within fomesafen-sodium induced micellization of the surfactant containing the water-insoluble herbicide dissolved in a non-polar organic solvent. Fomesafen sodium is present in the range of 7.5% to 50 % by total weight and clodinafop-propargyl is present in the range of 2% to 27% by total weight. Further, fomasafen sodium and clodinafop propargyl is present in the ratio of 0.35:1 and 1:0.04.
In an embodiment, the water soluble and insoluble herbicides reside within the hydrophilic and hydrophobic micro-domains respectively. In another embodiment, the water soluble herbicide is fomesafen sodium while the water insoluble herbicide is clodinafop-propargyl. In this embodiment, the residence of clodinafop-propargyl within the hydrophobic micro-domains prevented its contact with the aqueous phase thereby enhancing the chemical stability of the herbicide, when present within the formulations of the instant invention. This thermodynamic partitioning of the herbicidal water soluble salt in the aqueous phase and the micellar solubilization of the water-insoluble herbicide in the hydrophobic phase was surprising. The formulations according to the present invention may be presented as an herbicidal concentrate such as an emulsifiable concentrate (EC) or as a microemulsion (ME) such that it is normally diluted with a suitable volume of water or an oil before application, for example by spraying on to foliage of plants.

The present invention thus provides an agrochemical isotropic mutual dispersion of a hydrophilic phase and a hydrophobic phase with at least one surfactant being disposed at the interface between said hydrophilic and hydrophobic phases, wherein said hydrophilic phase comprises a herbicidally effective amount of at least one water soluble herbicidal salt dissolved in a water miscible solvent and wherein said hydrophobic phase comprises a herbicidally effective amount of a water insoluble herbicide dissolved in a solvent system comprising a non-polar organic solvent. In an embodiment, the solvent system comprises a co-solvent such as herein described in addition to said non-polar organic solvent.
The formulation according to the present invention is in a most advantageous embodiment though not necessarily, a microemulsion. Microemulsions are clear, stable, isotropic liquid mixtures of water and surfactant in combination with active ingredients.
In an embodiment, the surfactant of the present invention may be selected from a polyaryl substituted aliphatic, aromatic alkoxylate or an alkoxylated polyaryl substituted phenol and derivatives and mixtures thereof.
In a further embodiment, the surfactant is preferably ethoxylated tristyryl phenol.
In an embodiment, the surfactant may be present within the dispersion of the present invention in an amount of from about 3% to about 37% by total weight.
In an embodiment, the hydrophilic phase comprises a water-soluble herbicide dissolved in a water miscible solvent. In an embodiment of the present invention, the water soluble herbicide is fomesafen sodium. The water-miscible solvent includes water.
It has been surprisingly found that in the absence of fomesafen sodium, the components of the present invention form a biphasic hydrophilic-hydrophobic system, and upon addition of fomesafen sodium, the biphasic system converts spontaneously to a thermodynamically stable, transparent and isotropic mixture.

It has further been found that an oil phase is inherently generated from the hydrocarbon portion of the surfactant, which in the presence of water results in an emulsion system in the absence of fomesafen sodium but did not result into an isotropic mutual dispersion as desired by the present inventors. Surprisingly, it was only subsequent to the addition of the water soluble herbicide, fomesafen sodium in particular, to the above emulsion that a micellar stabilized isotropic mutual liquid-liquid dispersion of the hydrophilic-hydrophobic phases was obtained.
Without wishing to be bound by theory, it is believed that in the absence of the water soluble active ingredient, the geometric packing of the surfactant in the presence of at least two liquids is incapable of self-aggregating into liquid micro-domains. A portion of the added water-soluble herbicidal active ingredient penetrates the palisade layer of the surfactant and favors the self-aggregation of the surfactant, in the presence of a co-solvent, to form organized self-aggregated micro-domains, which was unexpected and considered surprising.
The isotropic mixtures, conventionally known in the art as micro-emulsions, typically comprises small isolated oil droplets dispersed in water (oil-water dispersions) or small water droplets dispersed in large amount of oil (water-in-oil dispersions). In contrast, the dispersions of the present invention are transparent, isotropic bicontinuous hydrophobic-hydrophilic mixtures involving both hydrophobic and hydrophilic continuous domains separated by an interfacial film comprising a surfactant and/or a co-surfactant and, in the present invention, a portion of the water-soluble herbicide of the instant invention, which is fomesafen sodium in an embodiment. The term "mutual dispersion" as used herein shall denote such a dispersion involving a bicontinuous phase.
In an embodiment, the co-surfactant according to the present invention also functions as a co-solvent for the water soluble herbicide included within the mutual dispersions of the present invention. In this embodiment, the co-surfactant/co-solvent may be an alkanol having from 3 to 18 carbon chain length.

In an embodiment, the co-surfactant may be selected from 2-butanol, n-hexanol, octanol and decanol. The amount of the co-surfactant is not particularly limiting and varies from about 0.1 % to about 10 % by weight of the mutual dispersion of the present invention.
In another embodiment, the co-solvent may be selected from an alkyl cellosolve. These co-solvents impart the required viscosity to the highly loaded herbicidal isotropic liquid dispersion of the present invention. The cellosolve co-solvents according to the present invention include, but are not limited to, methyl cellosolve, ethyl cellosolve and Butyl cellosolve. The cellosolve concentration may vary with the active ingredient used in the mutual dispersions of the invention and are not considered particularly limiting.
It is known in the art that solutions are more stable than dispersions. However a clear solution system has a tendency to precipitate the active ingredient out of the formulation with the small variation in temperature or pH. The precipitation of the active ingredient increases the tendency of the formulation to turn turbid. The active ingredient precipitated out of the system in this manner many times settles down in the container and forms sediment. A formulation in the form of a clear solution not only gets evaporated completely but also gets washed out easily in rains. It has been found that the isotropic mutual dispersion of hydrophobic-hydrophilic phases according to the invention are more stable to rain wash and do not allow the active ingredient to precipitate out of the formulation.
Thus, the fomesafen sodium-surfactant-cosurfactant system of the present invention permits a micellar solubilization of a high loading of the herbicidal agrochemicals in the formulation, which was hitherto not possible.
In one of the embodiments, at least one of the liquids present within the formulations of the present invention is water while the second liquid is immiscible with water. The aqueous phase in the formulations of the present invention comprises water having dissolved therein a selected water-soluble

herbicide or mixtures thereof. The term "water-soluble" as used herein in relation to a herbicide or salt thereof means having a defined known solubility in deionized water at 20°C. In an embodiment, the water-soluble herbicides have a herbicidally active acid or anionic moiety and are present in the composition of the invention in the form of one or more water-soluble salts. The aqueous phase can optionally contain, in addition to the water-soluble herbicide, other salts contributing to the ionic strength of the aqueous phase.
A particular group of water-soluble herbicides are those that are normally applied post-emergence to the foliage of plants. Systemic movement in plants can take place via apoplastic (non-living) pathways, including within xylem vessels and in intercellular spaces and cell walls, via symplastic (living) pathways, including within phloem elements and other tissues composed of cells connected symplastically by plasmodesmata, or via both apoplastic and symplastic pathways. For foliar-applied systemic herbicides, the most important pathway is the phloem, and the present invention is believed to provide the greatest benefits where the water-soluble herbicide is phloem-mobile.
Illustratively water-soluble herbicides that can be used in compositions of the invention include water soluble salts of acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, chloroacetic acid, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, flumiclorac, fluoroglycofen, flupropanate, fomesafen, fosamine, glufosinate, glyphosate, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, quinclorac, sulfamic acid, 2,3,6-TBA, TCA, triclopyr and water-soluble salts thereof.
In an embodiment, the water soluble herbicide component according to the present invention may be combination of at least two herbicides such as described hereinabove. In a further embodiment, the water soluble herbicide component is

acifluorfen sodium in combination with an agriculturally acceptable salt of glyphosate; acifluorfen sodium in combination with an agriculturally acceptable salt of bentazone or an agriculturally acceptable salt of glyphosate with an agriculturally acceptable salt of paraquat such as for example, paraquat dichloride or paraquat dimetilsulfate; a water soluble salt of asulam such as asulam sodium in combination with water soluble salt of any other herbicide; a water soluble salt of endothall acid in combination with water soluble salt of any other herbicide; and a water soluble salt of triclopyr in combination with a water soluble salt of any other herbicide.
A particular water soluble herbicide used in the present invention is the sodium salt of fomesafen.
The hydrophobic phase of the mutual dispersions of the present invention includes at least one water-insoluble herbicide. In an embodiment, the water-insoluble herbicide may be a known combination partner for fomesafen sodium.
In yet another embodiment, the water-insoluble herbicide is clodinafop-propargyl.
Therefore, in this aspect, the present invention provides an agrochemical isotropic mutual dispersion of an aqueous phase and an organic phase with at least one surfactant being disposed at the interface between said aqueous and organic phases, wherein said aqueous phase comprises a herbicidally effective amount of fomesafen sodium dissolved in water and wherein said organic phase comprises clodinafop-propargyl dissolved in a solvent system comprising a non-polar organic solvent in combination with a co-solvent.
The non-polar organic solvent is not particularly limiting and may be conveniently selected from N,N-dimethyl (C6-C12) alkylamides or its combination with N,N-dimethyloctanamide or decanamide (commercially available under AMD-810® series); a dibasic ester solvent having 59-67% glutarate content, 20-28% succinate content and 9-17% adipate content by weight distribution (DIB); acetophenone; and C-IX aromatic solvent; or combinations thereof. However, the

non-polar organic solvents may include other hydrocarbon/ aromatic solvents not included herein.
In yet another aspect, the present invention provides a process for the preparation of an agrochemical isotropic mutual dispersion of at least two immiscible liquids, said process comprising:
(a) dissolving a herbicidally effective amount of at least one water soluble herbicide in water and adding at least one surfactant and a co-solvent to obtain a hydrophilic phase;
(b) mixing a herbicidally effective amount of at least one water insoluble herbicide in an organic solvent to obtain a hydrophobic phase; and
(c) adding a predetermined quantity of said hydrophilic phase to a predetermined quantity of said hydrophobic phase.
In another aspect, the process according to the present invention comprises mixing an effective amount of water soluble herbicidal active ingredient in water and adding at least one surfactant and a predetermined quantity of an alkyl co-solvent. The hydrophobic phase comprising a water insoluble herbicide dissolved in a non-polar organic solvent is thereafter added to the hydrophilic phase preferably under stirring to obtain a clear formulation.
In an embodiment, the hydrophobic mixture obtained in step (b) of this aspect may be optionally filtered.
In one embodiment, the isotropic mutually dispersed liquid mixture according to the present invention may be spontaneously or coercively formed on a simple mixing of the components. In this embodiment, the formulation is a microemulsion formulation wherein the water-soluble herbicidal active ingredient may be dissolved in water or a water miscible co-solvent.
However, a thermodynamically stable dispersion according to the present invention is possible using more than two immiscible liquids, which could be stabilized by the adsorbed surfactant-cosurfactant-water soluble herbicide

tripartite system of the present invention at each liquid-liquid interface. In this embodiment, the selective surfactant-cosurfactant-water soluble herbicide tripartite system of the present invention stabilizes the micro-domains present in each said immiscible liquid, thereby enabling each said microdomain present within three or more immiscible liquids to receive and accommodate at least a portion of a plurality of herbicidal active ingredients. This distribution of said plurality of the herbicidal active ingredient(s) within the microdomains in each immiscible liquid portion was considered surprising.
The selection of application rates for a composition of the invention containing a specific combination of a water-soluble herbicide fomesafen sodium and clodinafop-propargyl to provide a desired level of herbicidal activity is within the skill of an ordinary agricultural technician. One skilled in the art will recognize that individual plant conditions, weather and growing conditions, as well as the specific exogenous chemical substance selected, can affect the results achieved in using a composition of the present invention. In an embodiment, the application rates for fomesafen sodium varies from about 100 to about 2500 g a.e./ha, more particularly from about 250 to about 1500 g a.e./ha. 30 to 60 g active/hectare.
In another aspect, the present invention provides a method for controlling an undesired weed at a location. This method comprises applying the mutual dispersions according to the present invention at the desired location.
The method of the present invention where the water-soluble herbicide is fomesafen sodium and the water-insoluble herbicide is clodinafop propargyl is applicable to any and all plant species on which fomesafen sodium and/or clodinfop propargyl are biologically effective as herbicides. This encompasses a very wide variety of plant species worldwide.
Herbicidal compositions of water soluble herbicides alone or in combination are used to control a very wide variety of plants worldwide. The high loaded water soluble herbicidal compositions of the present invention can be diluted at the time

of application and can used effectively to control one or more plant species of one or more of the following genera without restriction: Abutilon, Amaranthus, Artemisia, Asclepias, Avena, Axonopus, Borreria, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, Erodium, Helianthus, Imperata, Ipomoea, Kochia, Lolium, Malva, Oryza, Ottochloa, Panicum, Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium, Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum, Typha, Ulex, Xanthium and Zea.
Particularly important annual broadleaf species for which the formulations of water soluble herbicides are exemplified without limitation are the following: velvetleaf (Abutilon theophrasti), pigweed (Amaranthus spp.), buttonweed (Borreria spp.), oilseed rape, canola, indian mustard, etc. (Brassica spp.), commelina (Commelina spp.), filaree (Erodium spp.), sunflower (Helianthus spp.), morningglory (Ipomoea spp.), kochia (Kochia scoparia), mallow (Malva spp:), wild buckwheat, smartweed, etc. (Polygonum spp.), purslane (Portulaca spp.), russian thistle (Salsola spp.), sida (Sida spp.), wild mustard (Sinapis arvensis) and cocklebur (Xanthium spp.).
Particularly important annual narrowleaf species for which the formulations of water soluble herbicides compositions are exemplified without limitation are the following: wild oat (Avena fatua), carpetgrass (Axonopus spp.), downy brome (Bromus tectorum), crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crus-galli), goosegrass (Eleusine indica), annual ryegrass (Lolium multiflorum), rice (Oryza sativa), ottochloa (Ottochloa nodosa), bahiagrass (Paspalum notatum), canarygrass (Phalaris spp.), foxtail (Setaria spp.), wheat (Triticum aestivum) and corn (Zea mays).
Particularly important perennial broadleaf species for which glyphosate compositions are exemplified without limitation are the following: mugwort (Artemisia spp.), milkweed (Asclepias spp.), Canada thistle (Cirsium arvense), field bindweed (Convolvulus arvensis) and kudzu (Pueraria spp.).

Particularly important perennial narrowleaf species for which fomesafen compositions are exemplified without limitation are the following: brachiaria (Brachiaria spp.), bermudagrass (Cynodon dactylon), yellow nutsedge (Cyperus esculentus), purple nutsedge (C. rotundus), quackgrass (Elymus repens), lalang (Imperata cylindrical perennial ryegrass (Lolium perenne), guineagrass (Panicum maximum), dallisgrass (Paspalum dilatatum), reed (Phragmites spp.), johnsongrass (Sorghum halepense) and cattail (Typha spp.).
Other particularly important perennial species for which fomesafen compositions are exemplified without limitation are the following: horsetail (Equisetum spp.), bracken (Pteridium aquilinum), blackberry (Rubus spp.) and gorse (Ulex europaeus).
Thus, the mutual dispersions of the present invention, and a method for treating plants with such compositions, can be useful on any of the above species. In a particular contemplated method, a plant treatment composition of the invention comprising fomesafen sodium is applied to foliage of crop plants genetically transformed to tolerate fomesafen sodium, and simultaneously to foliage of weeds or undesired plants growing in close proximity to such crop plants.
Application of plant treatment dispersions to foliage of plants is accomplished by spraying, using any conventional means for spraying liquids, such as spray nozzles or spinning-disk atomizers. The dispersions of the present invention can be used in precision farming techniques, in which apparatus is employed to vary the amount of exogenous chemical substance applied to different parts of a field, depending on variables such as the particular plant species present, plant growth stage, soil moisture status, etc. In one embodiment of such techniques, a global positioning system operated with the spraying apparatus can be used to apply the desired amount of the composition to different parts of a field.
A plant treatment formulation according to the present invention is diluted enough to be readily sprayed using standard agricultural spray equipment. Suitable

application rates for the present invention vary depending upon such factors as the type and concentration of active ingredient and the plant species involved. Useful rates for applying an aqueous composition to a field of foliage can range from about 25 to about 1,000 liters per hectare (1/ha), particularly about 50 to about 300 1/ha, by spray application.
EXAMPLES
The following examples are for the purposes of illustration only and are not intended to limit the scope of the present invention.
The best mode of making and using the present invention are described in the following examples. These examples are given only to provide direction and guidance in how to make and use the invention, and are not intended to limit the scope of the invention in any way.
Example: A

Sr. Raw material Amount (%, w/w) Role in the
No. dispersion
1 Fomesafen sodium salt 21.5 @ 37.07 Water soluble
58% solution active ingredient
2 Clodinafop propargyl 8.3 @ 8.74 Water insoluble
95% active ingredient
3 Solvent AMD-810 17.5 N,N-dimethyl (C6-C12) alkylamide solvent
4 Ethoxylated tristyryl phenol 32.5 Surfactant
5 n-Hexanol 1.3 Co-surfactant/Co-solvent
6 Water 2.89 Water miscible

solvent
Total 100
A required quantity of clodinafop-propargyl was dissolved in the solvent to obtain a clear solution. The solution was filtered to remove any suspended impurity. A continuous hydrophilic phase was prepared by adding fomesafen salt in water, ethoxylated tristyryl phenol surfactant and n-hexanol to prepare a clear viscous solution. The final mutual dispersion was obtained by adding the hydrophobic phase to the hydrophilic phase while stirring till homogenous dispersion was obtained.
The dispersion prepared above was tested for hea't stability and the following results were seen:

S No. Property O day 14 days Degradation
1 Appearance Light yellow Light yellow No color change, phase
liquid liquid separation or crystallization
2 Fomesafen
active
content 21.39 21.34 No degradation
3 Clodinafop
active
content 8.26 8.06 2.4% maximum degradation in 14-days AHS test; although it is highly reactive to water
4 Cold No No No effect on the
stability crystallization crystallization microemulsion before
in cold but increase in viscosity in cold but increase in viscosity or after dilution
5 Emulsion Clear Clear No degradation of

stability translucent translucent microemulsion
microemulsion on dilution in 20, 342, 500 ppm, no crystallization after 24-hour standing microemulsion on dilution in 20, 342, 500 ppm, no crystallization after 24-hour standing property
6 PH 6.91 6.88
The following examples were prepared utilizing the process of Example A with different solvent mixtures according to exemplary embodiments of the invention. The percentage weight of the surfactants and the quantity of water was accordingly adjusted to total quantity of the dispersion.

Example Solvent system Minimum Co-solvent Dose
No. Dose of
solvent
For
Fomesafen
(22.1%) +
Clodinafop
(8%)
Al N,N-dimethyl (C6-C12) alkylamide solvent 17.5% n-Hexanol 1%
A2 A dibasic ester solvent (DIB) 15% n-Hexanol 1%
A3 DIB + C-IX (70:30) 16% n-Hexanol 1%
A4 Acetophenone + C-IX (70:30) 12% n-Hexanol 1%
A5 Acetophenone 15% n-Hexanol 1%

A6
Aromatic hydrocarbon solvent like Solvesso-100,150 200 18% n- butanol 2%
Examples B, C and D
The following examples were prepared utilizing the process described above for Example A.

Ingredients Batches

B C D
Fomesafen sodium 21.3 @ 59.5% solution 35.80 35.80 35.80
Coldinafop-propargyl 8.3 @ 95% 8.74 8.74 8.74
N,N-dimethyl (C6-C12) alkylamide solvent 17.50
Acetophenone solvent 8.40
C-IX solvent (Naphta-L) 3.60 3.20
Dibasic ester (DIB) 12.80
Ethoxylated tristyryl phenol surfactant 32.50 32.50 32.50
n-Hexanol 1.00 1.00 1.00
Water 4.46 9.96 5.96
Total 100.00 100.00 100.00
Physicochemical properties
Odour No characteristic odor Characteristic odor of acetophenone No
characteristic
odor
Cold test at 0UC for 7 days No crystal formation No crystal formation No crystal formation

Emulsion stability at

30±2°C Transparent clear Transparent clear Transparent
0 hour solution solution clear solution
0.5 hour Same Same Same
2 hours Same Same Same
24 hours Same Same Same
Accelerated heat stability at 54±2θC, active content % age w/w
Fomesafen Na Ambient 21.39 21.59 21.08

14 days AHS 21.34 21.41 20.76
Clodinafop
propargyl Ambient 8.26 8.36 8.16

14 days AHS 8.06 8.14 8.02
pH as such (0 day/14 6.80/6.52 6.56/6.40 6.40/6.31
days)
pH 1% aqueous solution 6.42/6.31 6.61/6.40 6.33/6.10
(0 day/14 days)
Persistent foam (after 1 15 mL 12 mL 15 mL
min.) in mL
Micellar Entrapment
A series of the experiments were conducted to establish that the mutual dispersion of the invention provided a stable micellar solubilization of fomesafen sodium. The conductivity of an aqueous solution of fomesafen sodium was measured at different concentrations. The results were plotted on a graph with measured conductivity plotted on Y- axis and the corresponding concentration on the X-axis. It was observed that the conductivity increased with the salt concentration and dropped suddenly above a critical concentration. It is believed that at this inflection concentration, fomesafen sodium self-aggregated to form an aggregated structure.

In another series of experiments, the mutual dispersions according to the present invention exemplified by Example A were tested at various concentrations of fomesafen sodium active ingredients and the resulting conductivity was measured. The results were plotted on a graph with measured conductivity plotted on Y- axis and the corresponding concentration on the X-axis. It was observed that for a given concentration of fomesafen sodium, the conductivity of the mutual dispersion of the instant invention was surprisingly lower than the conductivity of an aqueous solution of fomesafen sodium at the same given concentration. It was believed that this surprising lowering of the conductivity of fomesafen sodium could be attributed to the entrapment of fomesafen sodium within the micellar aggregates contributed by the solvent-surfactant-cosurfactant system of the present invention.
Experiment 1
A comparative study of the conductivity of fomsafen salt solution was performed and compared against the conductivity of a mutual dispersion of Example A at different dilution levels from 0.4% to 21% concentrations of the solution as well as the mutual dispersion. In a simple solution, it was found that the conductivity increased with the increase in the salt concentration linearly. The conductivity measurements for the mutual dispersions according to the instant invention initially increased with increasing concentration, but at an inflection point concentration of about 10% w/w of fomesafen sodium, the conductivity started decreasing with increasing concentration. It was concluded that at this inflection point concentration, the surprising surfactant properties of fomesafen sodium caused it to self-aggregate upon its crossing the palisade layer of the hydrophobic phase and penetrate into the aqueous phase. It was further concluded that even at a lower concentration of about 0.4% to about as high as 21%, fomesafen sodium, in determined quantities, was able to penetrate in a self-aggregated state into the aqueous phase.

The conductivity values measured in the described experiment are tabulated as hereunder:

Fomesafen sodium concentration (5) Conductivity of the mutual dispersion according to the invention Conductivity of solution
0.40% 0.49 0.51
0.60% 0.69 0.76
0.80% 0.8 1.04
1% 1.1 1.47
2% 1.548 2.103
3% 2.05 2.94
4% 2.49 3.623
5% 2.879 4.339
6% 3.232 5.004
7% 3.54 5.672
8% 3.798 6.33
9% 4.049 6.98
10% 4.069 7.676
11% 4.1 8.19
12% 3.9 8.81
13% 3.9 9.42
14% 3.66 10
15% 3.4 10.6
16% 3.2 11.12
17% 2.8 11.5
18% 2.35 12.01
19% 1.8 12.57
20% 1.2 13
21% 0.508 13.45
The measured values were plotted in a graph, which accompanies the specification as Figure 1.
Example 2
A similar experiment was conducted with the concentration of fomesafen sodium decreasing from the starting 50% to about 20%. An aqueous phase was prepared with fomesafen sodium with water. An organic phase of the present invention was added gradually to gradually decrease the concentration from 52.59% to about

21.36%. A similar concentration of the conventional salt solution was maintained using water as diluents.

Concentration of fomesafen sodium (%) Conductivity of the mutual dispersions of the present invention Conductivity of a solution
52.59% 20.14 20.14
50% 16.68 21.25
45% 13.56 26.27
40% 8.56 22.06
35% 4.85 20.41
30% 2.42 19.01
25% 1.019 16.43
21.30% 0.508 13.45
The results were plotted to obtain the graph accompanying the present specification as figure 2. It was found that for the conventional solution, the conductivity decreased linearly with the decreasing concentration. The mutual dispersions of the present invention exhibited surprisingly reduced conductivity vis-a-vis the conductivity of the conventional salt solution. It was again concluded that fomesafen sodium self-aggregated and penetrated into the aqueous micro-domain, which resulted into a reduced conductivity. A further evidence on self-aggregation of fomsafen sodium came from the observation that the dilution of the conventional salt solution exhibited an initial increase in conductivity due to the breakage of fomesafen sodium and after complete breakage of the aggregates, the conductivity began decreasing linearly with decreasing concentration.
It is believed that this self-aggregation of fomesafen sodium occurred due to the surfactant properties inherent within fomesafen sodium, which was considered surprising.
Surprisingly, it was found that the average diameter of the micro-domains formed by self-aggregation of the hydrophilic and hydrophobic phases were even less than about 0.1 micron. The reduced micro-domain size substantially increased the

penetration of the active ingredient entrapped within the microdomain and enhanced the penetration of the entrapped active ingredient within the target weeds. Moreover, the size of the hydrophobic phase microdomains of the present invention afforded a large contact area with the treated surface thereby substantially improving the distribution and efficacy of the formulations according to the present invention.
It was concluded that the hydrophilic micro-domains comprising fomesafen sodium formed bicontinuous isotropic mutual dispersion with the hydrophobic micro-domains comprising clodinafop-propargyl thereby preventing the contact between the two active ingredients. The isotropic system was a clear dispersion, which upon dilution with an appropriate medium resulted into microemulsion or emulsifiable concentrate. It was found that in the absence of a hydrophilic phase, the hydrophobic phase comprising coldinfop-propargyl-organic solvent-surfactant formed a milky emulsion on dilution. The addition of a little quantity of fomesafen sodium to the dilution resulted into a clear mutual dispersion, evidencing the surprising surface active properties of fomesafen sodium, which was hitherto unknown.
Further surprisingly, it was found that the formulations according to the present displayed superior low temperature stability and remained flowable even at sub-freezing temperatures. Without wishing to be bound by theory, it is believed that the selective solvent-surfactant-cosurfactant system of the present invention provides an ultralow interfacial surface tension between the two immiscible liquids such that the two microdomains are effectively physically separated from each other, which ensures their flowability in otherwise freezing conditions, which was considered surprising.

Example E:

Example E El E2 E3 E4 E5 E6
Sr ingredient Fomesafen Maximum Maximum Maximum Normal lower
No. s and concentrated concentrated concentrated formulation concentrati
Clodinafop formulation, formulation, formulation, Fomesafen on
ratio 1:0.362 Fomesafen Fomesafen Fomesafen and Fomesafen
and and and Clodinafop and
Clodinafop Clodinafop Clodinafop ratio Clodinafop
ratio 1:0.362 ratio 0.35:1 ratio 1:0.04 1:0.362 ratio 1:0.362
active Fomesafen- Fomesafen Fomesafen Fomesafen Fomesafen
concentrat Fomesafen- 25 7.5% with 50% with -22.1+ 2.21% with
ion 29+Clodinaf +Clodinafop- Clodinafop Clodinafop Clodinafop Clodinafop
op-10.5 9.05 21% 2% -8 0.8%
1 Fomesafe n sodium salt @58 38.1 3.707
%soln. 50.00 43.28 13.45 86.2
2 Clodinafo
P propargyl 8.74 0.874
(2)96 10.95 9.58 22.08 2.19
3 Solvent 17.5 1.75
AmD-810 9.5 16.27 22 4
4 Sopropho 32.5 3.25
re BSU 29 30.15 28 3
5 n- __
Butanol — — 1 3
6 n- 1.3 0.13
Hexanol 0 0.20 ~ ~
7 Water( 1.86 90.289
QS) 0.55 0.52 13.47 1.61
Total 100 100.00 100 100 100 100
Remark 1)AS such 1)AS such 1)AS such 1)AS such 1)AS such 1)AS such
formulation formulation formulation formulation formulatio formulatio
in ambient in ambient in ambient in ambient n in n in
is clear is clear is clear is clear ambient is ambient is
2) diluted 2) diluted 2) diluted 2) diluted clear clear
microemulsi microemulsi microemulsi microemulsi 2) diluted 2) diluted
on is clear on is clear on is clear on is clear microemul microemul
for 2 hr for 2 hr for 2 hr for 2 hr sion is sion is
and 24 hr and 24 hr and 24 hr clear for 2 hr and 24 clear for 2 hr and 24
hr hr

Example E7:
The following experiment was performed to show that the present
formulation was stable even after dilution.
The composition of Example E5 is diluted with water having dilution ratio of 2:98. After dilution the sample is put in the Nanosizer instrument wherein the particle size is measured directly by the readings appearing on the instrument.
Fomesafen sodium salt (22.1%) + Clodinafop propargyl (8 %) ME gives following particle size on dilution

PARTICLE DETAIL FOMESAFEN
SODIUM
(22.1%)
CLODINAFOP
PROPARGYL
ME SALT
+
(8 %) CLODINAFOP PROPARGYL 9.6 EC (NORMAL EC)
Z-
average % intensity average average

diameter in nm 12.26 783.2
Peak-1 % intensity 67.2 46.7

diameter in nm 8.554 4622
Peak-2 % intensity 32.8 29.9

diameter in nm 237.3 956.5
Peak-3 % intensity -- 23.3

diameter in nm -- 137.6
Remark Translucent
microemulsion
dilution on milky emulsion on dilution
In view of the above it is observed that the Zeta potential is closer to - 30mV showing stability of droplet and thus the dispersion.
Example F: With Other surfactant system showing better and stable formulation on dilution with temperature range of 20-40 °C

Exam pl
e 16
Sir .no Ingredients % w/w
1 Fomesafen sodium salt 22.1@58 %soln. 38.10
2 Clodinafop propargyl 8.3@ 95 8.74
3 Agnique AMD 810 17.5
4 Soprophore BSU 16
Castor oil ethoxylate (16 EO) 16
5 n- Butanol 2.00
6 Water 1.66
Total 100
Physicochemical Properties ambient 14 days AHS
1 Appearance light yellow liquid light yellow liquid
2 Fomesafen -Na 22.1 22.09
3 Clodinafop Prop. 8.5 8.57
4 pH (as such) 6.68 6.55
5 Emulsion stability Very good microemulsion and stable for 24 hr in 20,342,500 ppm Very good microemulsion and stable for 24 hr in 20,342,500 ppm
Example G:

Exampl e 17
Sir .no Ingredients %w/w
1 Fomesafen sodium salt 21.5 @58 %soln. 37.07
2 Clodinafop propargyl 8.3@ 95 8.74
3 solvent C-9 18
4 Soprophore BSU 10
5 n- Butanol 4
6 Water 22.19
Total 100
Physicochemical Properties ambient 14 days AHS
1 Appearance light yellow liquid light yellow liquid
2 Fomesafen -Na 21.06 20.97
3 Clodinafop Prop. 9.15 8.87
4 pH (as such) 6.68 6.55
5 Emulsion stability Very good emulsification and stable for 24 hr in 20,342,500 ppm Very good emulsification and stable for 24 hr in 20,342,500 ppm

Examples of Other water-soluble herbicides and water insoluble herbicides [Example H1 to H5]:
Example-Hl: Tank mix partner 2,4-D amine 250 em/lit SL+ Clodinafop 8 EC
Sr.no
ingredients % w/w Role in formulation
1 2,4-D amine salt 23 @58 % soln. 39.66 Active ingredient
2 Clodinafop propargyl 8.3@ 95 8.74 Active ingredient
3 Solvent AmD-810 17.5 solvent
4 Soprophore BSU 32.5 Emulsifier
5 n-Hexanol 0.50 Co-solvent
6 Water 1.10 solvent
Total 100
Example- H2: Tank mix partner Imazapic 22 SL+ Clodinafop 8 EC
Sr.no
ingredients % w/w Role in formulation
1 Imazapic ammonium salt 22.5 @56 % soln. 40.18 Active ingredient
2 Clodinafop propargyl 8.3@ 95 8.74 Active ingredient
3 Solvent AmD-810 17.5 solvent
4 Soprophore BSU 32.5 Emulsifier
5 n-Hexanol 0.50 Co-solvent
6 Water 0.58 solvent
Total 100
Example-H3: Combination of Aciflurofen and Clodinafop
Sr.no
ingredients % w/w Role in formulation
1 Aciflurofen sodium salt 17.5 @43 % soln. 40.7 Active ingredient
2 Clodinafop propargyl 8.3@ 95 8.74 Active ingredient
3 Solvent AmD-810 20 solvent
4 Soprophore BSU 30 Emulsifier
5 n-Hexanol 0.56 Co-solvent
Total 100

Example-H4:
Sr.n
0 Ingredients % w/w Role in formulatio
n
1 Fluroxypyr Methyl heptyl Ester 10.85 @97% 11.19 Active ingredient
2 Picloram TIPA salt 13.54@58% 23.34 Active
ingredient
3 solvent c-9 18.00 solvent
4 n- Butanol 7.50 Co-solvent
5 Soprpphore BSU 32.00 Emulsifier
6 Water 7.97 solvent
7 Total 100
Example-H5: Tank mix partner Bentazone sodium 29.2 +Aciflurfen sodium 13.4
(Storm) + Clodinafop 8 EC
Sr.no
ingredients % w/w Role in formulation
1 Bentazone sodium 14.6 @55 % soln. 25.17 Active ingredient
2 Aciflurfen sodium 6.7 @46 14.56 Active ingredient
3 Clodinafop propargyl 8.3@ 95 8.74 Active ingredient
4 Solvent AmD-810 18.55 solvent
5 Soprophore BSU 32.5 Emulsifier
6 n-Hexanol 0.50 Co-solvent
7 water 00 solvent
Total 100
Efficacy
A comparative trial was conducted using the formulations according to the present invention. The mutual dispersions according to the present invention were prepared according to the exemplary embodiments of examples A, B, C and D above. It was surprisingly found that the tested samples exhibited good control on the target weeds on the tested crops.

Wherein the aforegoing reference has been made to components having known equivalents, then such equivalents are herein incorporated as if individually set forth. Accordingly, it will be appreciated that changes may be made to the above described aspects and embodiments of the invention without departing from the principles taught herein. Additional advantages of the present invention will become apparent for those skilled in the art after considering the principles in particular form as discussed and illustrated. Thus, it will be understood that the invention is not limited to the particular embodiments described or illustrated, but is intended to cover all alterations or modifications which are within the scope of the invention.
One or more advantages of the invention:
1. The mutual dispersions of the present invention permit a high loading of fomesafen sodium and clodinafop-propargyl without any degradative interaction. These active ingredients are otherwise known to degrade each other in aqueous formulations, wherein they are in direct contact with each other.
2. There is no phase separation despite a high loading of the active ingredients. Conventionally, a greater than 5% loading of clodinfop-propargyl in a microemulsion formulation leads to spontaneous phase separation, in contrast to the exemplary stability seen in the mutual dispersions of the instant invention.
3. A further advantage of the invention was the low solvent requirement despite a high loading of the herbicides. There was no recrystallization of the herbicides seen after prolonged storage and after dilution despite a high loading of the active ingredients.

We claim,
1. An agrochemical isotropic mutual dispersion of a hydrophilic phase and a hydrophobic phase with at least one surfactant being disposed at the interface between said hydrophilic and hydrophobic phases, wherein said hydrophilic phase comprises a herbicidally effective amount of at least one water soluble herbicidal salt dissolved in a water miscible solvent and wherein said hydrophobic phase comprises a herbicidally effective amount of a water insoluble herbicide dissolved in a solvent system comprising a non-polar organic solvent.
2. The agrochemical isotropic mutual dispersion as claimed in claim 1, wherein water soluble herbicidal salt is selected from water soluble salts of acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, chloroacetic acid, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, flumiclorac, fluoroglycofen, flupropanate, fomesafen, fosamine, glufosinate, glyphosate, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, quinclorac, sulfamic acid, 2,3,6-TBA, TCA and triclopyr.
3. The agrochemical isotropic mutual dispersion as claimed in claim 1, wherein water soluble herbicidal salt is fomesafen sodium in the range of 7.5% to 50 % by total weight.
4. The agrochemical isotropic mutual dispersion as claimed in claim 1 or claim 3, wherein water insoluble herbicidal salt is clodinafop-propargyl in the range of 2% to 27% by total weight.
5. The agrochemical isotropic mutual dispersion as claimed in claim 4, wherein fomasafen sodium and clodinafop propargyl is present in the ratio of 0.35:1 and 1:0.04.

6. The agrochemical isotropic mutual dispersion as claimed in claim 1, wherein surfactant is selected from polyaryl substituted aliphatic, aromatic alkoxylate or an alkoxylated polyaryl substituted phenol and derivatives and mixtures in an amount of about 3 % to about 37 % by total weight.
7. The agrochemical isotropic mutual dispersion as claimed in claim 1, wherein non-polar organic solvent is selected from N,N-dimethyI (C6-C12) alkylamides or its combination with N,N-dimethyloctanamide or decanamide; a dibasic ester solvent having 59-67%, glutarate content, 20-28% succinate content and 9-17% adipate content by weight distribution (DIB); acetophenone; and C-IX aromatic solvent; or combinations.
8. The agrochemical isotropic mutual dispersion as claimed in claim 1, wherein said dispersion further comprises co-surfactant and co-solvent.
9. The agrochemical isotropic mutual dispersion as claimed in claim 1 and 8, wherein co-surfactant is selected from 2-butanol, n-hexanol, octanol and decanol in the range of 0.1 % to about 10 % by weight of the mutual dispersion.
10. The agrochemical isotropic mutual dispersion as claimed in claim 1 and 8, wherein co-solvent is selected from cellosolve such as methyl cellosolve, ethyl cellosolve and Butyl cellosolve
11. The agrochemical isotropic mutual dispersion of a hydrophilic phase and a hydrophobic phase with at least one surfactant being disposed at the interface between said hydrophilic and hydrophobic phases, wherein said hydrophilic phase comprises a herbicidally effective amount of fomesafen sodium dissolved in water and wherein said hydrophobic phase comprises a clodinafop-propargyl dissolved in a solvent system comprising a non-polar organic solvent.
12. The agrochemical isotropic mutual dispersion as claimed in claim 1 and 11, wherein the said dispersion is in the form of emulsifiable concentrate (EC) or microemulsion (ME).
13. A process for the preparation of an agrochemical isotropic mutual dispersion, said process comprising:

a. dissolving a herbicidally effective amount of at least one water
soluble herbicide in water and adding at least one surfactant and a
co-solvent to obtain a hydrophilic phase;
b. mixing a herbicidally effective amount of at least one water
insoluble herbicide in an organic solvent to obtain a hydrophobic
phase; and
c. adding a predetermined quantity of said hydrophilic phase to a
predetermined quantity of said hydrophobic phase.

Documents

Orders

Section Controller Decision Date

Application Documents

# Name Date
1 2030-MUM-2011-OTHERS [15-01-2018(online)].pdf 2018-01-15
1 2030-MUM-2011-RELEVANT DOCUMENTS [26-09-2023(online)].pdf 2023-09-26
2 2030-MUM-2011-CORRESPONDENCE(IPO)-(CERTIFIED COPY)-(20-4-2022).pdf 2022-05-13
2 2030-MUM-2011-FER_SER_REPLY [15-01-2018(online)].pdf 2018-01-15
3 2030-MUM-2011-REQUEST FOR CERTIFIED COPY [18-04-2022(online)].pdf 2022-04-18
3 2030-MUM-2011-CLAIMS [15-01-2018(online)].pdf 2018-01-15
4 Notarised Certificate of Incorporation.pdf 2018-08-10
4 2030-MUM-2011-US(14)-ExtendedHearingNotice-(HearingDate-11-03-2021).pdf 2021-10-03
5 FORM 13 _Change name of the applicant.pdf 2018-08-10
5 2030-MUM-2011-US(14)-HearingNotice-(HearingDate-05-03-2021).pdf 2021-10-03
6 2030-MUM-2011-IntimationOfGrant23-04-2021.pdf 2021-04-23
6 2030-MUM-2011-GENERAL POWER OF ATTORNEY(27-4-2012).pdf 2018-08-10
7 2030-MUM-2011-PatentCertificate23-04-2021.pdf 2021-04-23
7 2030-MUM-2011-FORM 5(16-7-2012).pdf 2018-08-10
8 2030-MUM-2011-Written submissions and relevant documents [24-03-2021(online)].pdf 2021-03-24
8 2030-mum-2011-form 2.pdf 2018-08-10
9 2030-MUM-2011-Correspondence to notify the Controller [10-03-2021(online)].pdf 2021-03-10
9 2030-mum-2011-form 2(title page).pdf 2018-08-10
10 2030-MUM-2011-FORM 2(TITLE PAGE)-(16-7-2012).pdf 2018-08-10
10 2030-MUM-2011-Response to office action (Mandatory) [26-03-2019(online)].pdf 2019-03-26
11 2030-MUM-2011-ABSTRACT(16-7-2012).pdf 2018-08-10
11 2030-MUM-2011-FORM 2(16-7-2012).pdf 2018-08-10
12 2030-MUM-2011-CLAIMS(16-7-2012).pdf 2018-08-10
12 2030-MUM-2011-FORM 18(23-7-2012).pdf 2018-08-10
13 2030-MUM-2011-CORRESPONDENCE(16-7-2012).pdf 2018-08-10
13 2030-MUM-2011-FORM 13(27-4-2012).pdf 2018-08-10
14 2030-MUM-2011-CORRESPONDENCE(23-7-2012).pdf 2018-08-10
14 2030-mum-2011-form 1.pdf 2018-08-10
15 2030-MUM-2011-CORRESPONDENCE(27-4-2012).pdf 2018-08-10
15 2030-MUM-2011-FORM 1(9-8-2011).pdf 2018-08-10
16 2030-MUM-2011-CORRESPONDENCE(9-8-2011).pdf 2018-08-10
16 2030-MUM-2011-FER.pdf 2018-08-10
17 2030-mum-2011-drawing.pdf 2018-08-10
17 2030-MUM-2011-Correspondence-261015.pdf 2018-08-10
18 2030-mum-2011-correspondence.pdf 2018-08-10
18 2030-MUM-2011-DRAWING(16-7-2012).pdf 2018-08-10
19 2030-MUM-2011-DESCRIPTION(COMPLETE)-(16-7-2012).pdf 2018-08-10
19 2030-mum-2011-description(provisional).pdf 2018-08-10
20 2030-MUM-2011-DESCRIPTION(COMPLETE)-(16-7-2012).pdf 2018-08-10
20 2030-mum-2011-description(provisional).pdf 2018-08-10
21 2030-mum-2011-correspondence.pdf 2018-08-10
21 2030-MUM-2011-DRAWING(16-7-2012).pdf 2018-08-10
22 2030-MUM-2011-Correspondence-261015.pdf 2018-08-10
22 2030-mum-2011-drawing.pdf 2018-08-10
23 2030-MUM-2011-CORRESPONDENCE(9-8-2011).pdf 2018-08-10
23 2030-MUM-2011-FER.pdf 2018-08-10
24 2030-MUM-2011-FORM 1(9-8-2011).pdf 2018-08-10
24 2030-MUM-2011-CORRESPONDENCE(27-4-2012).pdf 2018-08-10
25 2030-MUM-2011-CORRESPONDENCE(23-7-2012).pdf 2018-08-10
25 2030-mum-2011-form 1.pdf 2018-08-10
26 2030-MUM-2011-CORRESPONDENCE(16-7-2012).pdf 2018-08-10
26 2030-MUM-2011-FORM 13(27-4-2012).pdf 2018-08-10
27 2030-MUM-2011-CLAIMS(16-7-2012).pdf 2018-08-10
27 2030-MUM-2011-FORM 18(23-7-2012).pdf 2018-08-10
28 2030-MUM-2011-ABSTRACT(16-7-2012).pdf 2018-08-10
28 2030-MUM-2011-FORM 2(16-7-2012).pdf 2018-08-10
29 2030-MUM-2011-FORM 2(TITLE PAGE)-(16-7-2012).pdf 2018-08-10
29 2030-MUM-2011-Response to office action (Mandatory) [26-03-2019(online)].pdf 2019-03-26
30 2030-MUM-2011-Correspondence to notify the Controller [10-03-2021(online)].pdf 2021-03-10
30 2030-mum-2011-form 2(title page).pdf 2018-08-10
31 2030-MUM-2011-Written submissions and relevant documents [24-03-2021(online)].pdf 2021-03-24
31 2030-mum-2011-form 2.pdf 2018-08-10
32 2030-MUM-2011-PatentCertificate23-04-2021.pdf 2021-04-23
32 2030-MUM-2011-FORM 5(16-7-2012).pdf 2018-08-10
33 2030-MUM-2011-IntimationOfGrant23-04-2021.pdf 2021-04-23
33 2030-MUM-2011-GENERAL POWER OF ATTORNEY(27-4-2012).pdf 2018-08-10
34 FORM 13 _Change name of the applicant.pdf 2018-08-10
34 2030-MUM-2011-US(14)-HearingNotice-(HearingDate-05-03-2021).pdf 2021-10-03
35 Notarised Certificate of Incorporation.pdf 2018-08-10
35 2030-MUM-2011-US(14)-ExtendedHearingNotice-(HearingDate-11-03-2021).pdf 2021-10-03
36 2030-MUM-2011-REQUEST FOR CERTIFIED COPY [18-04-2022(online)].pdf 2022-04-18
36 2030-MUM-2011-CLAIMS [15-01-2018(online)].pdf 2018-01-15
37 2030-MUM-2011-CORRESPONDENCE(IPO)-(CERTIFIED COPY)-(20-4-2022).pdf 2022-05-13
37 2030-MUM-2011-FER_SER_REPLY [15-01-2018(online)].pdf 2018-01-15
38 2030-MUM-2011-OTHERS [15-01-2018(online)].pdf 2018-01-15
38 2030-MUM-2011-RELEVANT DOCUMENTS [26-09-2023(online)].pdf 2023-09-26

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