DESC:FIELD OF THE INVENTION
[001] The present disclosure relates to the technical field of agrochemicals. In particular the present disclosure relates to a binary fungicidal composition, formulations, particularly suspo-emulsion formulations and a process for preparing the same.

BACKGROUND OF THE DISCLOSURE
[002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[003] Kresoxim-methyl is chemically a carboxylic ester that is the methyl ester of (2E)-(methoxyimino){2-[(2-methylphenoxy)methyl]phenyl}acetic acid. It plays a role as a mitochondrial cytochrome-bc1 complex inhibitor, an environmental contaminant, a xenobiotic and an antifungal agrochemical agent against variety of fungal diseases of a wide range of crops.
[004] Metalaxyl M is chemically a methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl) alaninate. It is a systemic fungicide used to control plant diseases caused by Oomycete fungi.
[005] Though Kresoxim-methyl and Metalaxyl M are known fungicides, their long-term individual use results into developing immunity against them reducing their effectiveness, requiring very high doses and frequent application which can cause toxicity to the healthy flora and fauna in their vicinity and is unfavourable for environment sustainable development. Hence, to address such issues, formulations comprising multiple active ingredients are attempted. However, non-compatibility of active ingredients, poses sever challenges in formulating compositions comprising multiple active ingredients.
[006] For instance, Metalaxyl M has water solubility (26 g/L) in contrast to Kresoxim-methyl which has partial aromatic solubility leading to crystal growth when formulated as aqueous and non-aqueous based formulations respectively thus making difficulty to select suitable solvent to formulate the combination of these active ingredients. The use of aromatic petroleum solvents as a medium leads to visible, and measurable phyto-toxicity. Additionally, the cost of production of such binary formulations comprising two active ingredients is high.
[007] There is thus an unmet need in the art to provide a solvent free binary fungicidal formulation comprising combination of two active ingredients that can overcome one or more deficiencies such as requirement of higher concentrations if active ingredients, use of aromatic petroleum solvents, phytotoxicity to crop, adverse environmental impact, and high cost of production.

SUMMARY OF THE INVENTION
[008] In a general aspect the present disclosure provides a binary fungicidal composition comprising Metalaxyl-M and Kresoxim-methyl that can achieve one or more advantages including ability to formulate desired formulation, reducing dose of active ingredients, lowering production cost, obviating phyto-toxicity, better selectivity, better bio-efficacy, and lowering undesirable environmental impact.
[009] In one aspect, the present disclosure provides a binary fungicidal composition, wherein the composition is formulated as a suspo-emulsion formulation (SE), a ZC formulation (ZC), or a micro-emulsion (ME) formulation.
[0010] In one aspect, the present disclosure provides a binary fungicidal composition, wherein the composition is a suspo-emulsion formulation (SE).
[0011] In another aspect, the present disclosure provides a suspo-emulsion (SE) formulation comprising Metalaxyl-M and Kresoxim-methyl. The suspo-emulsion (SE) formulation comprises Metalaxyl-M and Kresoxim-methyl in a ratio of 1:10 to 10:1.
[0012] In another aspect, the present disclosure provides a suspo-emulsion (SE) formulation comprising Metalaxyl-M in an amount in the range of 0.1 to 15% by weight; and Kresoxim-methyl in an amount in the range of 1 to 30% by weight.
[0013] In another aspect, the present disclosure provides a suspo-emulsion (SE) formulation comprising 5% by weight of Metalaxyl-M and 12.5% by weight of Kresoxim-methyl.
[0014] In another aspect, the present disclosure provides a suspo-emulsion (SE) formulation comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) a second active ingredient Kresoxim-methyl;
(iii) vegetable oil;
(iv) one or more agrochemical excipients; and
(v) water.
[0015] In certain aspect of the present disclosure, one or more agrochemical excipients can be selected from a dispersing agent, a wetting agent, a suspending agent, an emulsifier, a stabilizer, an antifreezing agent, an antifoaming agent, a preservative, a rheology or viscosity modifier or combination thereof.
[0016] In one more aspect, the present disclosure provides a suspo-emulsion (SE) formulation comprising:
(a) an emulsion-in-water (EW) phase comprising:
(i) a first active ingredient Metalaxyl-M and at least one triglyceride containing long chain fatty acid of C12 to C22 having Metalaxyl-M dissolved therein; and
(ii) aqueous phase
(b) a suspension concentrate (SC) phase comprising:
(i) a second active ingredient Kresoxim-methyl;
(ii) water having Kresoxim-methyl suspended therein.
[0017] In one more aspect, the present disclosure provides a suspo-emulsion (SE) formulation comprising:
(i) 0.1 to 15% by weight of a first active ingredient Metalaxyl, preferably 5% by weight;
(ii) 1 to 30% by weight of a second active ingredient Kresoxim-methyl preferably 12.5% by weight;
(iii) 0.1 to 10.0% by weight at least one triglyceride containing long chain fatty acid of C12 to C22;
(iv) 0.3 to 20.0% by weight of a dispersing agent selected from methyl methacrylate-polyethylene glycol graft copolymers, modified styreneacrylic polymer, alkyl polyglycoside, lignosulphonates, phenyl naphthalene sulphonates, polyaromatic sulfonates thereof;
(v) 0.01 to 5.0% by weight of a wetting agent selected from nonionic proprietary surfactant blend, ethylene oxide and propylene oxide block copolymer, alkoxylated alcohol, alkoxylated alkyl/aryl phenol, fatty oil ethoxylate, phenyl naphthalene sulphonates;
(vi) 0.1 to 3.0% by weight of a suspending agent selected from sodium bentonite, silicates, polycarboxylates;
(vii) 0.01 to 4.0% by weight of emulsifiers selected from polyarylphenyl ether sulphate, ammonium salt;
(viii) 0.01 to 3.0% by weight of emulsifiers selected ethoxylated fatty alcohol;
(ix) 0.01 to 5.0% by weight of a stabilizer selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acrylates, polyvinyl acetates;
(x) 0.01 to 25.0% by weight of anti freezing agent selected from propylene glycol, polyethylene glycol, diethylene glycol, glycerol, and urea;
(xi) 0.1 to 10.0% by weight of antifoaming agent selected from the group comprising of perfluroalkylphosphonic acids, polydimethyl siloxane or mixtures thereof;
(xii) 0.01 to 2.0% by weight of preservative are isothiazoline derivatives such as alkylisothiozaline, benzene selected from 1,2-benzisothiazolin-3-one, formaldehyde, and sodium benzoate;
(xiii) 0.35 to 0.60% by weight of thickening agent selected from polysaccharides selected from xanthan gum, carboxy methyl cellulose, polycarboxylates, and silicates; and
(xiv) water.
[0018] In yet another aspect, the present disclosure provides a process for preparing a suspo-emulsion (SE) formulation comprising the steps of:
a) preparing an emulsion-in-water (EW) phase comprising dissolving Metalaxyl-M in at least one triglyceride containing long chain fatty acid of C12 to C22 and mixing with one or more emulsifiers to obtain oil phase, followed by mixing the oil phase with an aqueous phase including water and one or more agrochemical excipients to obtain EW phase;
b) preparing a suspension concentrate (SC) phase comprising suspending Kresoxim-methyl along with one or more agrochemical excipients in a continuous water phase to obtain SC phase;
c) adding the EW phase to the SC phase under continuous agitation for optimum period of time and mixing a thickening agent into the mixture of the EW phase and the SC phase under continuous stirring for 4 to 6 hours to obtain a homogeneous suspo-emulsion (SE) formulation.
[0019] In another aspect, the present disclosure provides a binary fungicidal composition, wherein the composition is a ZC formulation.
[0020] In another aspect, the present disclosure provides a ZC formulation comprising Metalaxyl-M and Kresoxim-methyl. The ZC formulation comprises Metalaxyl-M and Kresoxim-methyl in a ratio of 1:10 to 10:1.
[0021] In another aspect, the present disclosure provides a ZC formulation comprising Metalaxyl-M in an amount in the range of 0.1 to 15 % by weight; and Kresoxim-methyl in an amount in the range of 1 to 30 % by weight.
[0022] In another aspect, the present disclosure provides a ZC formulation comprising 5% by weight of Metalaxyl-M and 12.5 % by weight of Kresoxim-methyl.
[0023] In another aspect, the present disclosure provides a ZC formulation wherein Metalaxyl-M is microencapsulated and Kresoxim-methyl is suspension concentrate.
[0024] In another aspect, the present disclosure provides a ZC formulation comprising:
(a) a micro-encapsulated phase comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) water immiscible solvent having Metalaxyl-M; and
(iii) capsule forming agent;
(b) a suspension concentrate (SC) phase comprising:
(i) a second active ingredient Kresoxim-methyl;
(ii) water having Kresoxim-methyl suspended therein.
[0025] In another aspect, the present disclosure provides a ZC formulation comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) a second active ingredient Kresoxim-methyl;
(iii) water immiscible solvent selected from the group consisting of aromatic hydrocarbon or solvent naphtha;
(iv) capsule forming agent selected from polyurea polymers derived from a mixture of aromatic polyisocyanate and diamine such as methylene diisocyanate, diphenylmethane-diisocyanate, poly methylene poly phenyl isocyanate;
(v) emulsifier selected from anionic nonionic blend such as tri styryl phenol phosphate ester, ethopropoxylated polyaryl phenol, ethylene oxide and propylene oxide block co-polymer.
(vi) one or more agrochemical excipients; and
(vii) water.
[0026] In certain aspect of the present disclosure, one or more agrochemical excipients are selected from a dispersing agent, a wetting agent, a suspending agent, a stabilizer, an antifreeze agent, an antifoaming agent, a preservative, pH adjusters, buffers, a rheology or viscosity modifier or combination thereof.
[0027] In another aspect, the present invention provides a ZC formulation comprising:
a) 0.1 to 15% by weight of a first active ingredient Metalaxyl-M;
b) 1 to 30% by weight of a second active ingredient Kresoxim-methyl;
c) 0.1 to 15% by weight of water immiscible solvent selected from the group consisting of aromatic hydrocarbon C9 solvent or solvent naphtha;
d) 0.1 to 5.0% by weight of a capsule forming agent selected from polyurea polymers derived from a mixture of aromatic polyisocyanate and diamine such as methylene diisocyanate, diphenylmethane-diisocyanate, poly methylene poly phenyl isocynate;
e) 0.1 to 10% by weight of a dispersing agent selected from ethopropoxylated polyarylphenol phosphate amine salt, nonyl phenol ethoxylates, kraft ligno sulphonate, cetyl styryl alcohol;
f) 0.1 to 8% by weight of non-ionic emulsifiers selected from EO/PO polyaryl phenol, dodecyl benzene sulphonate, calcium salt of alkyl benzene sulphonate;
g) 0.1 to 6% by weight of a stabilizer selected from, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acrylates, polyvinyl acetates;
h) 0.05 to 5% by wight of a pH neutralizer selected from potassium hydroxide solution, trisodium phosphate, sodium hydroxide, mono ethanol amine or liquid ammonia;
i) 0.1 to 5% by weight of a dispersing agent selected from modified styrene acrylic polymer, EO/PO polyaryl phenol;
j) 0.1 to 5% by weight of a wetting agent selected from nonionic proprietary surfactant blend, ethylene oxide and propylene oxide block co-polymer;
k) 0.1 to 15% by weight of antifreezing agent selected from propylene glycol, polyethylene glycol, diethylene glycol, glycerol, urea;
l) 0.1 to 5% by weight of preservative selected from 1,2-benzisothiazolin-3-one, sodium benzoate, formaldehyde;
(xv) 0.1 to 8% by weight of an antifoaming agent include silicone emulsions, polydimethyl siloxane;
m) 0.1 to 2.0% by weight of thickening agent selected from polysaccharides selected from xanthan gum, carboxy methyl cellulose, polycarboxylates, silicates; and
n) water.
[0028] In yet another aspect, the present disclosure provides a process for preparing the ZC formulation comprising the steps of:
a) preparing a micro-encapsulated phase comprising steps of:
(i) preparing an oil phase by mixing Metalaxyl-M with a water immiscible solvent followed by addition of a capsule forming agent;
(ii) preparing an aqueous phase by combining water, an emulsifier, a dispersing agent, preservative and an antifreeze agent and raising the temperature to 55 – 60°C;
(iii) dispersing the oil phase slowly into the aqueous phase at an elevated temperature using a high shear mixer to form an emulsion and adding pH neutralizer;
(iv) maintaining the emulsion under stirring for a time period ranging from 2 hour to 3 hours at a temperature of 40°C to 60°C, followed by cooling the emulsion to room temperature to obtain micro-encapsulated phase comprising Metalaxyl-M;
b) preparing a suspension concentrate (SC) phase comprising steps of:
(i) preparing a slurry by combining Kresoxim-methyl, water, a dispersing agent, a wetting agent, an antifreezing, an anti-foaming agent, a preservative;
(ii) wet milling the slurry in a bead mill to form a suspension concentrate (SC) of Kresoxim-methyl;
(iii) mixing the microencapsulated phase and the suspension concentrate (SC) to form a mix under agitation and adding a thickening agent to the mix to obtain the homogeneous ZC formulation.
[0029] In another aspect, the present disclosure provides a binary fungicidal composition, wherein the composition is a micro-emulsion (ME) formulation.
[0030] In another aspect, the present disclosure provides a micro-emulsion (ME) formulation comprising Metalaxyl-M and Kresoxim-methyl. The formulation comprises Metalaxyl-M and Kresoxim-methyl in a ratio of 1:10 to 1:10.
[0031] In another aspect, the present disclosure provides a micro-emulsion (ME) formulation comprising Metalaxyl-M in an amount in the range of 0.1 to 15% by weight; and Kresoxim-methyl in an amount in the range of 1 to 30% by weight.
[0032] In another aspect, the present disclosure provides a micro-emulsion (ME) formulation comprising 1.3% by weight of Metalaxyl-M and 3.2% by weight of Kresoxim-methyl.
[0033] In another aspect, the present disclosure provides a micro-emulsion (ME) formulation comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) a second active ingredient Kresoxim-methyl;
(iii) water miscible solvent selected from the group consisting of ester of lactic acid like ethyl acetate and one or more monohydric alcohol solvent selected from a group consisting of n-butanol, and tetrahydro furfuryl alcohol;
(iv) one or more agrochemical excipients; and
(v) water.
[0034] In certain aspect of the present disclosure, one or more agrochemical excipients are selected from an antifreeze agent, a non-ionic emulsifier or combination thereof.
[0035] In another aspect, the present disclosure provides a micro-emulsion (ME) formulation comprising:
a) 0.1 to 15 % by weight of a first active ingredient Metalaxyl-M;
b) 1 to 30% by weight of a second active ingredient Kresoxim-methyl;
c) 10 to 70% by weight of water miscible solvent selected from the group consisting of ester of lactic acid, ethyl acetate, ethyl lactate; and 10 to 70% by weight of monohydric alcohol solvent selected from a group consisting of n-butanol, and tetrahyro furfuryl alcohol;
d) 1 to 20% by weight of an antifreeze agent selected from polyethylene glycol, glycerol, propylene glycol, and urea;
e) 1 to 30% by weight of non-ionic emulsifier selected from tristyryl phenol ethoxylate amine salt, and ethoxlated tristyrylphenol; and
f) 1 to 20% by weight demineralised water.
[0036] In yet another aspect, the present disclosure provides a process for preparing the micro-emulsion (ME) formulation comprising the steps of:
(i) preparing an organic phase by combining Metalaxyl-M, Kresoxim-methyl, water miscible solvent, and monohydric alcohol solvent;
(ii) preparing an aqueous phase by combining water, an antifreeze agent, and a non-ionic emulsifier; and
(iii) dispersing the organic phase into the aqueous phase using a high shear mixer to form a homogeneous micro-emulsion formulation.
[0037] In an aspect, the present disclosure relates to treating fungal diseases caused by targeting Early blight, late blight of tomato, potato, Downey and powdery mildew of grapes by applying the binary formulation comprising Metalaxyl-M, and Kresoxim-methyl at an effective dose.
[0038] In an aspect, the present disclosure relates to treating fungal disease of the crops such as tomato, potato, grapes.
[0039] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.

DETAILED DESCRIPTION OF THE INVENTION
[0040] The following is a detailed description of embodiments of the disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
[0041] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.
[0042] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0043] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[0044] As used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.
[0045] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”
[0046] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0047] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability.
[0048] The description that follows, and the embodiments described therein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles and aspects of the present disclosure. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the disclosure.
[0049] It should also be appreciated that the present disclosure can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.
[0050] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0051] Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
[0052] The term, “suspo-emulsion (SE)” as used herein refers to a formulation containing both solid and liquid active ingredients dispersed in an aqueous phase.
[0053] The term, “emulsion-in-water (EW)” as used herein refers to dispersion of an oil phase comprising active ingredient into a water continuous phase.
[0054] The term, “suspension concentrate (SC)” as used herein refers to concentrate consisting of having a solid active ingredient dispersed in water.
[0055] The term, “ZC” formulation as used herein refers to mixed formulations of aqueous capsule suspensions (CS) and aqueous suspension concentrates (SC).
[0056] The term, “micro-emulsion (ME)” as used herein refers to colloidal dispersions composition of oil phase, aqueous phase, surfactant, and co-surfactants.
[0057] The term, “agriculturally acceptable excipient” as used herein refers to any agriculturally acceptable inactive substance or mixture or adjuvant added to a formulation of an herbicidal active ingredient. Examples of agriculturally acceptable excipient include, but not limited to wetting agent(s), dispersing agent(s), stabilizing agent(s), binder(s), antifoaming agent(s), pH modifying agent(s), inert carrier(s), surfactant(s), antifreeze agent(s), clay(s), solvent(s), water, salt(s), polymer(s), emulsifying agent(s), suspension and density balancing agent(s), anti-crystalline agent (s), rheology modifier(s) or thickening agents, spreading agent (s), anti-caking agent(s), antioxidant (s), biocide(s) or preservative(s), capsule forming agent (s), quenching agent (s), super spreader(s), etc.
[0058] The term, fungicidal effective amount”, as used herein refers to the quantity of herbicidal active agent, applied in an amount which will provide the required control of weed on commercial crops. The particular amount is dependent upon many factors including, for example, type of formulations, the crop, weed sought to be controlled and environmental conditions.
[0059] The term, “control” or “controlling”, as used herein refers to preventing, reducing, killing, inhibiting the growth of, inhibiting the reproduction of, and/or eliminating at least one weed i.e. an undesirable plant in a crop growing environment.
[0060] The first active ingredient is Metalaxyl-M known as fungicide used to control plant diseases.
[0061] The second active ingredient is Kresoxim-methyl known as antifungal agrochemical agent against variety of fungal diseases of a wide range of crops.
[0062] The present disclosure provides a fungicidal composition comprising two active ingredients i.e. comprising Metalaxyl-M and Kresoxim-methyl. Specifically, the present disclosure relates to a binary fungicidal composition wherein the composition is a suspo-emulsion formulation comprising Metalaxyl-M and Kresoxim-methyl.
[0063] In one embodiment, the present disclosure provides a binary fungicidal composition comprising Metalaxyl-M and Kresoxim-methyl.
[0064] In an embodiment, the present disclosure provides a binary fungicidal formulation comprising the binary fungicidal composition comprising Metalaxyl-M and Kresoxim-methyl.
[0065] In an embodiment, the binary fungicidal formulation is a suspo-emulsion formulation (SE), a ZC formulation (ZC), or a micro-emulsion (ME) formulation.
[0066] In one embodiment, the present disclosure provides a binary fungicidal composition, wherein the composition is a suspo-emulsion formulation (SE), a ZC formulation (ZC), or a micro-emulsion (ME) formulation.
[0067] In a preferred embodiment, the present disclosure provides a binary fungicidal composition, wherein the composition is a suspo-emulsion formulation (SE).
[0068] In a preferred embodiment, the present disclosure provides a suspo-emulsion (SE) formulation comprising Metalaxyl-M and Kresoxim-methyl. In a preferred embodiment, the suspo-emulsion (SE) formulation comprises Metalaxyl-M and Kresoxim-methyl in a ratio of 1:10 to 10:1.
[0069] In a preferred embodiment, the present disclosure provides a suspo-emulsion (SE) formulation comprising Metalaxyl-M in an amount in the range of 0.1 to 15% by weight; and Kresoxim-methyl in an amount in the range of 1 to 30% by weight.
[0070] In an embodiment, the present disclosure provides a suspo-emulsion (SE) formulation comprising 5% by weight of Metalaxyl-M and 12.5% by weight of Kresoxim-methyl.
[0071] In a preferred embodiment, Metalaxyl-M is present in an amount in the range of 0.1 to 15% by weight, preferably 5% by weight of the SE formulation and Kresoxim-methyl is present in an amount in the range of 1 to 30% by weight, preferably 12.5% by weight of the SE formulation.
[0072] In one embodiment, the present disclosure provides a suspo-emulsion (SE) formulation comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) a second active ingredient Kresoxim-methyl;
(iii) at least one triglyceride containing long chain fatty acid of C12 to C22;
(iv) one or more agrochemical excipients; and
(v) water.
[0073] In an embodiment of the present disclosure, one or more agrochemical excipients can be selected from a dispersing agent, a wetting agent, a suspending agent, an emulsifier, a stabilizer, an ant freezing agent, an antifoaming agent, a preservative, a rheology or viscosity modifier or combination thereof.
[0074] In accordance of the present disclosure, the use of wetting agent, dispersing agent and rheology modifier system helps in achieving and maintaining low psd (d90-less than 20µ), nullifies sedimentation and caking, phase separation, flocculation allowing the SE formulation to stay in homogeneous state throughout its claimed shelf life.
[0075] In an embodiment of the present disclosure, the water can be demineralised water.
[0076] In an embodiment, the present disclosure provides a suspo-emulsion (SE) formulation comprising:
(a) an emulsion-in-water (EW) phase comprising:
(i) a first active ingredient Metalaxyl-M and at least one triglyceride containing long chain fatty acid of C12 to C22 having Metalaxyl-M dissolved therein; and
(ii) aqueous phase,
(b) a suspension concentrate (SC) phase comprising:
(i) a second active ingredient Kresoxim-methyl; and
(ii) water having Kresoxim-methyl suspended therein.
[0077] In one embodiment, the present disclosure provides a suspo-emulsion (SE) formulation comprising:
i. 0.1 to 15% by weight of a first active ingredient Metalaxyl, preferably 5% by weight;
ii. 1 to 30% by weight of a second active ingredient Kresoxim-methyl preferably 12.5% by weight;
iii. 0.1 to 10.0% by weight of at least one triglyceride containing long chain fatty acid of C12 to C22;
iv. 0.3 to 20.0% by weight of a dispersing agent selected from methyl methacrylate-polyethylene glycol graft copolymers, fatty alcohol ethoxylate, castor-oil based ethoxylates, fatty acid ethoxylates, and EO-PO block copolymers;
v. 0.01 to 5.0% by weight of a wetting agent selected from nonionic proprietary surfactant blend, alkyl phenol ethoxylate, fatty oil ethoxylate, phenyl naphthalene sulphonates, alkyl naphthalene sulfonates, sodium alkyl naphthalene sulfonate, sodium salt of sulfonated alkyl carboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, lignin derivatives, alkane sulfonates, alpha olefin sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, octyl phenol ether sulphate, anionic phosphate esters, disodium laureth sulfosuccinate, diisodecyl sodium sulfosuccinate, alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, alkyl ether phosphates, alkyl ether sulfates and alkyl sulfosuccinic monoesters, and dioctyl sulfosuccinate sodium salt or mixtures thereof;
vi. 0.1 to 3.0% by weight of a suspending agent selected from sodium bentonite, silicates, and polycarboxylates;
vii. 0.01 to 4.0% by weight of emulsifiers selected from polyarylphenyl ether sulphate, and ammonium salt;
viii. 0.01 to 3.0% by weight of emulsifiers, ethoxylated fatty alcohol;
ix. 0.01 to 5.0% by weight of a stabilizer, polyvinyl alcohol;
x. 0.01 to 25.0% by weight of antifreeze agent selected from propylene glycol, polyethylene glycol-400, diethylene glycol, glycerol, and urea;
xi. 0.1 to 10.0% by weight of antifoaming agent selected from polydimethyl siloxane, silicone defoamer, and perfluroalkylphosphonic acids, or mixtures thereof;
xii. 0.01 to 2.0% by weight of preservative selected from isothiazoline derivatives such as alkylisothiozaline, benzene selected from 1,2-benzisothiazolin-3-one, formaldehyde, and sodium benzoate;
xiii. 0.35 to 0.60% by weight of thickening agent selected from polysaccharides such as silica, bentonite, hydroxymethyl cellulose, xanthan gum, thickening silica, hydrated clay minerals, magnesium aluminium silicates, organic derivative of hectorite clay, and hydrophobic fumed silica or mixture thereof; and
xiv. water.
[0078] The dispersing agents can be selected from the group comprising of methyl methacrylate-polyethylene glycol graft copolymers, lignosulphonates, phenyl naphthalene sulphonates, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, alkali earth metal salt of alkylbenzene sulfonate ,calcium dodecylbenzene sulfonate, salts of sulfonated naphthalene, polystyrenated acrylated co-polymer, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids, and random copolymer of alcoxylated polyethylene glycol or mixtures thereof. The dispersing agents can be present in an amount of from about 0.3 to 20.0% by weight of the composition or formulation.
[0079] The wetting agents can be selected from the group comprising of nonionic proprietary surfactant blend. The wetting agents can be present in an amount of from about 0.01 to 5.0% by weight of the composition or formulation
[0080] The suspending agents can be selected from the group comprising of selected from sodium bentonite, silicates, and polycarboxylates. The suspending agents can be present in an amount of from about 0.1 to 3.0% by weight of the composition or formulation.
[0081] The emulsifiers can be selected from the group comprising of polyarylphenyl ether sulphate, ammonium salt, and ethoxylated fatty alcohol The emulsifiers can be present in an amount of from about 0.01 to 4.0 % by weight of the composition or formulation.
[0082] The emulsifiers can be ethoxylated fatty alcohol. The emulsifiers can be present in an amount of from about 0.01 to 3.0 % by weight of the composition or formulation.
[0083] The stabilizers can be selected from the group comprising of polyvinyl alcohol, and Gohsenol solution. The stabilizers can be present in an amount of from about 0.01 to 5.0% by weight of the composition or formulation.
[0084] The antifreeze agents can be selected from the group comprising of propylene glycol, polyethylene glycol-400, diethylene glycol, glycerol, and urea. The antifreeze agents can be present in an amount of from about 0.01 to 25.0 % by weight of the composition or formulation.
[0085] The antifoaming agents can be selected from the group comprising of polydimethyl siloxane, and silicone defoamer. The antifoaming agents can be present in an amount of from about 0.1 to 10.0% by weight of the composition or formulation.
[0086] The preservatives or biocides can be 1,2-benzisothiazolin-3-one. The preservatives or biocides can be present in an amount of from about 0.01 to 2.0 % by weight of the composition or formulation.
[0087] The rheology modifier or viscosity modifier or a thickening agent can be selected from the group comprising of sodium bentonite, fume silica, bentonite, diatomaceous earth, montmorillonite, attapulgites, hydroxymethyl cellulose, xanthan gum, polyvinyl alcohol, benton, thickening silica, hydrated clay minerals, magnesium aluminium silicates, organic derivative of hectorite clay, and hydrophobic fumed silica or mixtures thereof. The rheology modifier or viscosity modifier or a thickening agent can be present in an amount of from about 0.35 to 0.60 % by weight of the composition or formulation.
[0088] The triglyceride containing long chain fatty acid of C12 to C22, preferably sunflower oil. The triglyceride containing long chain fatty acid of C12 to C22 can be present in an amount of from about 0.1 to 10.0% by weight of the composition or formulation.
[0089] In one embodiment, the present disclosure provides a process for preparing a suspo-emulsion (SE) formulation comprising the steps of:
a. preparing an emulsion-in-water (EW) phase comprising dissolving Metalaxyl-M in at least one vegetable oil, and mixing with one or more emulsifiers to obtain oil phase, followed by mixing the oil phase with an aqueous phase including water and one or more agrochemical excipients to obtain EW phase;
b. preparing a suspension concentrate (SC) phase comprising suspending Kresoxim-methyl along with one or more agrochemical excipients in a continuous water phase to obtain SC phase;
c. adding the EW phase to the SC phase under continuous agitation for optimum period of time and mixing a thickening agent into the mixture of the EW phase and the SC phase under continuous stirring for 4 to 6 hours to obtain a homogeneous suspo-emulsion (SE) formulation.
[0090] In another embodiment, the present disclosure provides a binary fungicidal composition, wherein the composition is a ZC formulation.
[0091] In another embodiment, the present disclosure provides a ZC formulation comprising Metalaxyl-M and Kresoxim-methyl.
[0092] In a preferred embodiment, the ZC formulation comprises Metalaxyl-M and Kresoxim-methyl in a ratio of 1:10 and 10:1.
[0093] In a preferred embodiment, the present disclosure provides a ZC formulation comprising Metalaxyl-M in an amount in the range of 0.1 to 15% by weight; and Kresoxim-methyl in an amount in the range of 1 to 30% by weight.
[0094] In another embodiment, the present disclosure provides a ZC formulation comprising 5% by weight of Metalaxyl-M and 12.5% by weight of Kresoxim-methyl.
[0095] In another embodiment, the present disclosure provides a ZC formulation wherein Metalaxyl-M is microencapsulated and Kresoxim-methyl is suspension concentrate.
[0096] In another embodiment, the present disclosure provides a ZC formulation comprising:
a. a micro-encapsulated phase i.e. aqueous capsule suspensions (CS) comprising:
i. a first active ingredient Metalaxyl-M;
ii. water immiscible solvent having Metalaxyl-M; and
b. capsule forming agent;
i. a suspension concentrate (SC) phase comprising:
ii. a second active ingredient Kresoxim-methyl;
iii. water having Kresoxim-methyl suspended therein.
[0097] In another embodiment, the present disclosure provides a ZC formulation comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) a second active ingredient Kresoxim-methyl;
(iii) water immiscible solvent selected from the group consisting of aromatic hydrocarbon C9 or solvent naphtha; capsule forming agent selected from polyurea polymers derived from a mixture of aromatic polyisocyanate and diamine such as methylene diisocyanate;
(iv) non-ionic emulsifiers blend such as EO/PO polyaryl phenol, alkoxylated alcohols, ethoxylated alcohols, ethoxylated propoxylated alcohols, alkylphenolethoxylates, alkoxylated tristyrylphenols, tristyryphenol ethoxylate, alkoxylated tributylphenols, alkylaminethoxylates, ethoxylated propoxylated polyaryl phenol, ethoxylated poly adducts of ethylene oxide and propylene oxide, ethoxylated fatty acids, sorbitan esters and their ethoxylates, sorbitol esters, propylene glycol esters of fatty acids and polyglycerol esters, ethoxylated ricinoleic acid triglycerides, and castor oil ethoxylate or mixtures thereof;
(v) one or more agrochemical excipients; and
(vi) water.
[0098] In certain embodiment, one or more agrochemical excipients can be selected from a dispersing agent, a wetting agent, a suspending agent, a stabilizer, an antifreezing agent, an antifoaming agent, a preservative, pH adjusters, buffers, a rheology or viscosity modifier or combination thereof.
[0099] In another aspect, the present disclosure provides a ZC formulation comprising:
a. 0.1 to 15% by weight of a first active ingredient Metalaxyl-M;
b. 1 to 30% by weight of a second active ingredient Kresoxim-methyl;
c. 0.1 - 15% by weight of water immiscible solvent selected from the group consisting of aromatic hydrocarbon such as C9 solvent or solvent naphtha;
d. 0.1 - 10% by weight of a capsule forming agent selected from polyurea polymers derived from a mixture of aromatic polyisocyanate and diamine such as methylene diisocyanate;
e. 0.1 - 10% by weight of a dispersing agent, ethopropoxylated polyarylphenol phosphate amine salt;
f. 0.1 – 8.0% by weight of non-ionic emulsifiers selected from EO/PO polyaryl phenol, dodecyl benzene sulphonate, and calcium salt of alkyl benzene sulphonate;
g. 0.1 – 6.0% by weight of a stabilizer selected from, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acrylates, and polyvinyl acetates;
h. 0.05 – 5.0% by weight of a pH neutralizers selected from potassium hydroxide solution, sodium silicate, potassium silicate, magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate, dimethyl adipate, ortho phosphoric acid, oxalic acid, citric acid, and hydrochloric acid or mixtures thereof;
i. 0.1 – 5.0% by weight of a dispersing agent selected from modified styrene acrylic polymer, and EO/PO polyaryl phenol;
j. 0.1 – 5.0% by weight of a wetting agent selected from nonionic proprietary surfactant blend, ethylene oxide and propylene oxide block co-polymer;
0.1 - 15 % by weight of antifreeze agent selected from propylene glycol, polyethylene glycol 400, diethylene glycol, glycerol, and urea;
k. 0.1 – 5.0% by weight of preservative selected from 1,2-benzisothiazolin-3-one, sodium benzoate, and formaldehyde;
l. 0.1 – 8% by weight of an anti-foaming agent selected from polydimethyl siloxane, silicone defoamer, and silicone emulsions;
m. 0.1 – 2% by weight of thickening agent selected from polysaccharides such as xanthan gum, carboxy methyl cellulose, polycarboxylates, silicates fume silica, bentonite, diatomaceous earth, montmorillonite, attapulgites, hydroxymethyl cellulose, polyvinyl alcohol, benton, thickening silica, hydrated clay minerals, magnesium aluminium silicates, organic derivative of hectorite clay, and hydrophobic fumed silica or mixtures thereof; and
n. water.
[00100] The water immiscible solvent can be selected from the group comprising of aromatic hydrocarbon C9 or solvent naphtha. The water immiscible solvent can be present in an amount in the range 0.1 - 15% by weight of the composition or formulation.
[00101] The capsule forming agent can be selected from the group comprising of polyurea polymers derived from a mixture of aromatic polyisocyanate and diamine such as methylene diisocyanate. The capsule forming agent can be present in an amount in the range of 0.1 - 10%, preferably 0.1 to 5.0% by weight of the composition or formulation.
[00102] The dispersing agent can be selected from the group comprising of ethopropoxylated polyarylphenol phosphate amine salt. The dispersing agent can be present in an amount in the range of 0.1 to 10% by weight of the composition or formulation.
[00103] The non-ionic emulsifiers can be selected from EO/PO polyaryl phenol. The emulsifiers can be present in an amount in the range of 0.1 to 8% by weight of the composition or formulation.
[00104] The stabilizer can be selected from polyvinyl alcohol. The stabilizer can be present in an amount in the range of 0.1 to 6% by weight of the composition or formulation.
[00105] The pH neutralizer can be selected from the group comprising of potassium hydroxide solution, trisodium phosphate, sodium hydroxide, mono ethanol amine and liquid ammonia. The pH neutralizer can be present in an amount in the range of 0.05 to 5.0% by weight of the composition or formulation.
[00106] The dispersing agent can be selected from the group comprising of modified styrene acrylic polymer. The dispersing agent can be present in an amount in the range of 1.23 to 5.0 % by weight of the composition or formulation.
[00107] The wetting agent can be selected from the group comprising of nonionic proprietary surfactant blend. The wetting agent can be present in an amount in the range of 0.1 to 5 % by weight of the composition or formulation.
[00108] The antifreeze agent can be selected from the group comprising of propylene glycol, polyethylene glycol, diethylene glycol, glycerol, urea. The antifreeze agent can be present in an amount in the range of 0.1 to 15% by weight of the composition or formulation.
[00109] The preservative or biocide can be 1,2-benzisothiazolin-3-one. The preservative can be present in an amount in the range of 0.1 to 5% by weight of the composition or formulation.
[00110] The anti-foaming agent can be selected from the group comprising of polydimethyl siloxane, and silicone defoamer. The anti-foaming agent can be present in an amount in the range of 0.1 to 8% by weight of the composition or formulation.
[00111] The thickening agent can be selected from the group comprising of polysaccharides such as xanthan gum. The thickening agent can be present in an amount in the range of 0.1 to 2.0% by weight of the composition or formulation.
[00112] In an embodiment, the water can be demineralised water.
[00113] In another embodiment, the present disclosure provides a process for preparing the ZC formulation comprising the steps of:
a) preparing a micro-encapsulated phase comprising steps of:
(i) preparing an oil phase by mixing Metalaxyl-M with a water immiscible solvent followed by addition of a capsule forming agent;
(ii) preparing an aqueous phase by combining water, an emulsifier, a dispersing agent, preservative and an antifreeze agent and raising the temperature to 55 – 60°C;
(iii) dispersing the oil phase slowly into the aqueous phase at an elevated temperature using a high shear mixer to form an emulsion and adding pH neutralizer;
(iv) maintaining the emulsion under stirring for a time period ranging from 2 hour to 3 hours at a temperature of 40°C to 60°C, followed by cooling the emulsion to room temperature to obtain micro-encapsulated phase comprising Metalaxyl-M,
b) preparing a suspension concentrate (SC) phase comprising steps of:
(i) preparing a slurry by combining Kresoxim-methyl, water, a dispersing agent, a wetting agent, an antifreezing, an anti-foaming agent, a preservative;
(ii) wet milling the slurry in a bead mill to form a suspension concentrate of Kresoxim-methyl;
(iii) mixing the microencapsulated phase and the suspension concentrate to form a mix under agitation and adding a thickening agent to the mix to obtain the homogeneous ZC formulation.
[00114] In yet another embodiment, the present disclosure provides a binary fungicidal composition, wherein the composition is a micro-emulsion (ME) formulation.
[00115] In another embodiment, the present disclosure provides a micro-emulsion (ME) formulation comprising Metalaxyl-M and Kresoxim-methyl. The formulation comprises Metalaxyl-M and Kresoxim-methyl in a ratio of 1:10 to 1:10.
[00116] In another embodiment, the present disclosure provides a micro-emulsion (ME) formulation comprising Metalaxyl-M in an amount in the range of 0.1 to 15% by weight; and Kresoxim-methyl in an amount in the range of 1 to 30% by weight.
[00117] In another embodiment, the present disclosure provides a micro-emulsion (ME) formulation comprising 1.3 % by weight of Metalaxyl-M and 3.2 % by weight of Kresoxim-methyl.
[00118] In another embodiment, the present disclosure provides a micro-emulsion (ME) formulation comprising:
(i) a first active ingredient Metalaxyl-M;
(ii) a second active ingredient Kresoxim-methyl;
(iii) water miscible solvent selected from the group consisting of ester of lactic acid, ethyl acetate and one or more monohydric alcohol solvent selected from a group consisting of n-butanol, and tetrahyro furfuryl alcohol;
(iv) one or more agrochemical excipients; and
(v) water.
[00119] In an embodiment, one or more agrochemical excipients are selected from an antifreezing agent, a non-ionic emulsifier or combination thereof.
[00120] In another embodiment, the present disclosure provides a micro-emulsion (ME) formulation comprising:
a) 0.1 to 15 % by weight of a first active ingredient Metalaxyl-M;
b) 1 to 30 % by weight of a second active ingredient Kresoxim-methyl;
c) 10 to 70% by weight of water miscible solvent selected from the group consisting of ester of lactic acid, ethyl acetate, and ethyl lactate;
d) 10 to 70% by weight of monohydric alcohol solvent selected from a group consisting of n-butanol, and tetrahyro furfuryl alcohol;
e) 1 to 20% by weight of an antifreeze agent selected from polyethylene glycol, polyethylene glycol 400, propylene glycol, and diethylene glycol;
f) 1 to 30% by weight of non-ionic emulsifier selected from tristyryl phenol ethoxylate; and
g) water.
[00121] The water miscible solvent can be selected from the group comprising of ester of lactic acid, ethyl acetate, ethyl lactate. The water miscible solvent can be present in an amount in the range of 10 to 70% by weight of the composition or formulation.
[00122] The monohydric alcohol solvent can be selected from the group comprising of n-butanol, tetrahyro furfuryl alcohol. The monohydric alcohol solvent can be present in an amount in the range of 10 to 70% by weight of the composition or formulation.
[00123] The antifreezing agent can be selected from the group comprising of polyethylene glycol, glycerol, propylene glycol, urea. The antifreezing agent can be present in an amount in the range of 1 to 20% by weight of the composition or formulation.
[00124] The non-ionic emulsifier can be selected from the group comprising of tristyryl phenol ethoxylate, alkoxylated alcohols, ethoxylated alcohols, ethoxylated propoxylated alcohols, alkylphenolethoxylates, alkoxylated tristyrylphenols, tristyryphenol ethoxylate, alkoxylated tributylphenols, alkylaminethoxylates, ethoxylated propoxylated polyaryl phenol, ethoxylated poly adducts of ethylene oxide and propylene oxide, ethoxylated fatty acids, sorbitan esters and their ethoxylates, sorbitol esters, propylene glycol esters of fatty acids and polyglycerol esters, ethoxylated ricinoleic acid triglycerides, Soprophor castor oil ethoxylate or mixtures thereof. The non-ionic emulsifier can be present in an amount in the range of 1 to 30% by weight of the composition or formulation.
[00125] In an embodiment, the water can be demineralised water.
[00126] In another embodiment, the present disclosure provides a process for preparing the micro-emulsion (ME) formulation comprising the steps of:
(i) preparing an organic phase by combining Metalaxyl-M, Kresoxim-methyl, water miscible solvent selected from the group consisting of ester of lactic acid, and n-butanol as a monohydric alcohol solvent;
(ii) preparing an aqueous phase by combining water, an antifreeze agent, and a non-ionic emulsifier; and
(iii) dispersing the organic phase into the aqueous phase using a high shear mixer to form a homogeneous micro-emulsion formulation.
[00127] In another embodiment, the present disclosure provides a binary fungicidal formulation comprising the binary fungicidal composition wherein the composition is a suspo-emulsion formulation (SE), a ZC formulation (ZC), or a micro-emulsion (ME) formulation in accordance with the present disclosure comprising Metalaxyl-M and Kresoxim-methyl.
[00128] In certain embodiment, in the methods of the present disclosure, the pH of the SE formulation is maintained between the range 4.0 – 7.0, preferably 4.5-6.5.
[00129] In an embodiment, the binary SE formulation comprising the combination of Metalaxyl-M and Kresoxim-methyl, surprisingly show synergistic activity at much lesser amounts as compared to the amounts when said ingredients used alone.
[00130] In certain embodiment, the present disclosure provides a binary fungicidal formulation comprising the binary fungicidal composition wherein the composition is a suspo-emulsion formulation (SE), a ZC formulation (ZC), or a micro-emulsion (ME) formulation in accordance with the present disclosure comprising Metalaxyl-M and Kresoxim-methyl for control of weeds like targeting early blight, late blight of tomato, potato, Downey and powdery mildew of grapes.
[00131] The binary formulations can be applied at the target site in a suitable manner for example by Foliar spray.
[00132] In an embodiment, the binary fungicidal composition comprising a combination of Metalaxyl-M and Kresoxim-methyl, and SE formulation, ZC formulation, and ME formulation comprising the same, preferably the SE formulation comprising the same are useful for controlling, preventing or destroying, and suppressing fungal diseases caused by targeting Early blight, late blight of tomato, potato, Downey and powdery mildew of grapes.
[00133] In an embodiment, the binary fungicidal composition comprising a combination of Metalaxyl-M and Kresoxim-methyl, and SE formulation, ZC formulation, and ME formulation comprising the same, preferably the SE formulation comprising the same are useful for controlling, preventing or destroying, and suppressing fungal diseases of crops tomato, potato, grapes.
[00134] While the foregoing describes various embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.
[00135] The present invention is further explained in the form of following examples. However, it is to be understood that the foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.

EXAMPLES
[00136] The present disclosure is further explained in the form of following examples. However, it is to be understood that the following examples are merely illustrative and are not to be taken as limitations upon the scope of the invention.

EXAMPLE 1
BINARY SE FORMULATION COMPRISING METALAXYL-M + KRESOXIM-METHYL
1. Composition of Binary SE formulation
[00137] The following Table 1 shows the composition for a binary SE formulation comprising Metalaxyl-M + Kresoxim-methyl in accordance with exemplary embodiments.
Table 1: Composition for binary SE formulation comprising Metalaxyl-M + Kresoxim-methyl
Sl. No Ingredient Amount in %
(range) Ingredient class
1 Metalaxyl-M Technical 0.1 to 15% Active Ingredient
2 Kresoxim-methyl Technical 1.0 to 30% Active Ingredient
3 Methyl methacrylate-polyethylene glycol graft copolymers 0.3 – 20.0 Dispersing agent
4 Copolymer condensate of ethylene and propylene oxide (Atlox™ 4894) 0.01 – 5.0 Wetting agent
5 Sodium bentonite 0.1 – 3.0 Suspending agent
6 Polyarylphenyl ether sulphate, ammonium salt 0.01 - 4.0 Emulsifier
7 Ethoxylated fatty alcohol
0.01 - 3.0 Emulsifier
8 Polyvinyl alcohol 0.01 – 5.0 Binder/ stabilizer
9 Triglyceride containing long chain fatty acid of C12 to C22 Vegetable oil e.g. Sunflower oil 0.1 - 10.0 Adjuvant
10 Propylene glycol 0.01 – 25.0 Antifreeze agent
11 Polydimethyl siloxane 0.1 – 10.0 Antifoaming agent
12 1,2-benzisothiazolin-3-one 0.01 – 2.0 Biocide
13 AG-RHO POL 23 W 0.35 - 0.60 Rheology/viscosity modifier
14 Demineralised water Q.S Medium

[00138] The following Table 2 shows the composition for a binary SE formulation 1, i.e. composition comprising 5% Metalaxyl-M and 12.5% Kresoxim-methyl in accordance with exemplary embodiments.
Table 2: SE Formulation 1 (5% Metalaxyl-M and 12.5% Kresoxim-methyl)
Sl. No Ingredient Amount in % Ingredient class
1 Metalaxyl-M Technical 5.0 Active Ingredient
2 Kresoxim-methyl Technical 12.5 Active Ingredient
3 Modified styrene acrylic polymer 1.15 Dispersing agent
4 Copolymer condensate of ethylene and propylene oxide (Atlox™ 4894) 0.70 Wetting agent
5 Sodium bentonite 0.15 Suspending agent
6 Polyarylphenyl ether sulphate, ammonium salt 2.0 Emulsifier
7 Ethoxylated fatty alcohol 1.0 Emulsifier
8 Polyvinyl alcohol 0.50 Stabilizer
9 triglyceride containing long chain fatty acid of C12 to C22 Vegetable oil e.g. Sunflower oil 3.0 Oil medium
10 Propylene glycol 4.00 Antifreezing agent
11 Polydimethyl siloxane 0.6 Antifoaming agent
12 1,2-Benzisothiazolin-3-one 0.3 Biocide
13 AG-RHO POL 23 W 0.35 Rheology modifier
14 Demineralised water Q.S Aq. Medium
TOTAL 100%
[00139] The following Table 3 shows SE formulation 2 and 3 comprising Metalaxyl-M and Kresoxim-methyl in accordance with exemplary embodiments.
Table 3: SE Formulation 2 and Formulation 3
Sl. No. Ingredients Formulation-2 Formulation-3 Ingredient class
% w/w % w/w
1 Metalaxyl-M Technical 7.5 2.5 Active Ingredient
2 Kresoxim-methyl Technical 15.0 10.0 Active Ingredient
3 Modified styrene acrylic polymer 2.0 1.4 Dispersing agent
4 nonionic proprietary surfactant blend 1.0 0.72 Wetting agent
5 Sodium bentonite 0.6 0.5 Suspending agent
6 Polyarylphenyl ether sulphate, ammonium salt 1.5 2.0 Emulsifier
7 Ethoxylated fatty alcohol 1.5 1.0 Emulsifier
8 Polyvinyl alcohol 0.3 0.7 Stabilizer
9 triglyceride containing long chain fatty acid of C12 to C22 Vegetable oil e.g. Sunflower oil 5.0 3.0 Oil medium
10 Propylene glycol 5.0 4.0 Antifreeze agent
11 Polydimethyl siloxane 0.6 0.5 Antifoaming agent
12 1,2-Benzisothiazolin-3-one 0.3 0.3 Biocide
13 AG-RHO POL 23 W 0.32 0.35 Rheology modifier
14 Demineralised water QS Q.S Aq. Medium
15 Total 100.00 100.00

2. Process of Preparation of Binary SE formulation
[00140] As per some specific exemplary embodiments SE formulation was prepared. The binary SE formulation comprising Metalaxyl-M + Kresoxim-methyl as per above Table 1 to Table 3 was formulated following the below method:
(i) Preparation of Metalaxyl-M emulsion part (EW)

Into a clean and dry mixing vessel transfer the required quantity of vegetable oil, to this add Metalaxyl-M technical and mix to dissolve and add Polyarylphenyl ether sulphate, ammonium salt and mix well to dissolve completely. In another vessel charge the required quantity of demineralised water, Ethoxylated fatty alcohols, polyvinyl alcohol, Polydimethyl siloxane, 1, 2-Benzisothiazolin-3-one, propylene glycol and mix well. Add previously prepared Metalaxyl-M solution into it and mix under high-speed homogenizer at 5000 - 10000rpm at 22-25 degree Celsius for 1-2 hrs to obtain emulsion part (EW).
(ii) Preparation of suspension concentrate part (SC)
In a clean and dry pre-mixing vessel, weigh and charge required quantity of Demineralised water, Modified styrene acrylic polymer, nonionic proprietary surfactant blend, Propylene glycol, Polydimethyl siloxane, 1,2-Benzisothiazolin-3-one, Kresoxim-methyl technical and continue to mix under homogenizer at 30 to 150 rpm for 15-30 mins. Pass slurry through bead mill under cold water circulation (temp 10ºC-25oC) for particle size reduction, D90 in between 3-15micronTransfer milled slurry to post mixing vessel.
(iii) Preparation of Suspo emulsion (SE) formulation

In the post-mixing vessel add Metalaxyl-M emulsion (EW) part to SC part under agitation and add required quantity of AG-RHO POL 23 W. Stir the mixture at 10oC-25oC for 4-6 hours to get smooth and homogenous Suspo-emulsion (SE) formulation.

3. Accelerated Storage test (Stability Study) of (SE) formulation
[00141] According to the FAO/WHO manual, the “accelerated storage test” is considered as an indicative of product stability. That is accelerated storage test data provides an indication that the product is stable for at least two years at ambient temperature. Further, the FAO/WHO manual indicates storage at 54°C for 2 weeks as the default test conditions.
[00142] The “initial sample” is the sample at the room temperature which is before subjecting to the accelerated storage tests at 54°C for 2 weeks.
[00143] The “accelerated storage sample” is the sample after subjecting to the accelerated storage test.
[00144] The initial samples of the SE formulation of the above formulation 1 were subjected to the accelerated storage test to find out the product stability.
[00145] Table 4 shows the physical and chemical properties of the SE formulation 1 comprising 5% Metalaxyl-M and 12.5% Kresoxim-methyl as shown in Table 2 before (initial) and after the accelerated storage test (AHS).

Table 4: Physical and chemical properties of the SE formulation 1 as shown in Table 2 before and after the accelerated storage test

Sl. NO. TESTS SPECIFICATIONS Initial sample AHS (54C, 2 weeks)
1. Description White to off white colored
Suspo-emulsion free from extraneous matter Complies Complies
2. Active Ingredient content, % w/w
(i) Metalaxyl-M content
(ii) Kresoxim-methyl content

4.75 - 5.5

11.87 - 13.12

5.0

12.5

5.0

12.53
3. Dispersion stability 0 h : Dispersion complete

0.5 h : Cream/Free oil separated

Sediment at bottom (not to exceed 2 ml per 100 ml of 2% aqueous dispersion)

24 h : Re-dispersion Complete

24.5 h : Cream/Free oil separated

Sediment at the bottom (not to exceed 2 ml per 100 ml of 2% aqueous dispersion) Complete

0 ml

0 ml

Complete

0 ml

0 ml Complete

0 ml

0 ml

Complete

0 ml

0 ml
4. Wet sieve passing through 75 µ sieve, % w/w, min 98 99.94 99.92
5. pH (1% aqueous suspension) 4.0 – 7.0 5.65 5.57
6. Persistent foam after 1 min, ml, max 40 14 12
7. Pourability as rinsed residue, % w/w, max. 1.0 0.33 0.32
Min. = Minimum; Max. = Maximum
[00146] The results in Table 4 show that the appearance of the ambient sample of the SE formulation before and after the accelerated storage test (at 54°C for 2 weeks) remained the same that is ‘White to off white colored Suspo-emulsion free from extraneous matter’.
[00147] Further, the content of Metalaxyl-M and Kresoxim-methyl was found to be 5.0% w/w, and 12.5% w/w, respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test the content of Metalaxyl-M and Kresoxim-methyl was found to be the almost same, that is 5.0% w/w, and 12.53% w/w, respectively. It indicates that the content of Metalaxyl-M and Kresoxim-methyl respectively falls within the product specification range and hence the content of the active ingredients i.e. Metalaxyl-M and Kresoxim-methyl in the SE formulation is stable.
[00148] The pH of the ambient sample of the SE formulation before subjecting it to the accelerated storage test was found to be 5.65. However, even after subjecting the ambient sample to the accelerated storage test the pH was found to be almost same, that is 5.57. It indicates that the SE formulation was adhering to the pH range of 4.0– 7.0 which indicates that the formulation is stable.
[00149] Tests such as persistent foam and pourability and wet sieve passing test were conducted for the ambient sample of the SE formulation, before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 14 ml and 12 ml indicating the less froth formation and pourability test showed low rinse residue of 0.33% and 0.32% indicating less wastage of the formulation.
[00150] The dispersion stability test was conducted for the ambient sample of the SE formulation, before and after accelerated storage test. The results of the dispersion stability test indicated that, there is no separation of oil and no sedimentation even after standing for 30 minutes which indicates that the formulation is stable.
[00151] The wet sieve passing test showed passing of 99.94%w/w and 99.92%w/w of particles of the formulation through the 75µ wet sieve indicating the low particle size of the formulation.
[00152] Thus, in all the tests, values of the tests remained almost same before and after accelerated storage test which indicates that the formulation is stable.
[00153] In view of the above test results, SE formulation of the present disclosure prepared in accordance with the above examples are extrapolated to be stable for 2 years of shelf life from the date of manufacturing.
[00154] The advantages of the SE formulation of the present disclosure include stable formulation, storage stability, containing fine particles size ranging from 1 to 10 microns exhibiting minimum particle size growth, environmental friendly due to the usage of vegetable oil and nullifying phyto-toxicity. The use of co-formulant wetting agent, dispersing agent, Rheology modifier helps in achieving and maintaining low psd (d90-5µ), nullifies sedimentation and caking, phase separation, flocculation.

EXAMPLE 2
BINARY ZC FORMULATION COMPRISING METALAXYL-M + KRESOXIM-METHYL
1. Composition of ZC formulation
[00155] The following Table 5 shows the composition for a binary ZC formulation comprising Metalaxyl-M + Kresoxim-methyl in accordance with exemplary embodiments.
Table 5: Composition for ZC formulation (ZC) - Metalaxyl-M 5% + Kresoxim-methyl 12.5% ZC
Sl. No. Ingredient Amount in % Ingredient class
1 Metalaxyl-M Technical 5.0 Active ingredient
2 Kresoxim-methyl Technical 12.5 Active ingredient
3 Solvent naphtha 5.0 Solvent
4 Methylene diisocyanate 0.6 Film forming agent
5 Ethopropoxylated polyarylphenol phosphate amine salt 1.2 Dispersing agent
6 EO/PO polyaryl phenol 0.9 Emulsifier
7 Polyvinyl alcohol 0.2 Binder/Stabilizing agent
8 Potassium hydroxide solution (25%) 0.05 pH neutralizer
9 Modified styrene acrylic polymer 1.23 Dispersing agent
10 nonionic proprietary surfactant blend 0.76 Wetting agent
11 Propylene glycol 2.25 Anti-freezing agent
12 1,2-Benzisothiazolin-3-one 0.12 Preservative
13 Polydimethyl siloxane 0.3 Anti-foaming agent
14 AG-RHO POL 23 W 0.20 Rheology modifier
15 De-mineralised water QS Medium/Carrier
Total 100

2. Process for preparing the ZC formulation:
[00156] As per some specific exemplary embodiments ZC formulation was prepared with composition as per Table 5.
(i) Preparation of Metalaxyl-M micro-encapsulation:
Add require quantity of solvent naphtha to Metalaxyl-M technical and mix to dissolve it in ambient temperature. To this add capsule forming agent methylene diisocyanate to prepare oil phase and stir at 10-25 degree Celsius for 15 minutes. Prepare aqueous phase by mixing ethopropoxylated polyarylphenol phosphate amine salt, EO/PO polyaryl phenol, 1,2-benzisothiazolin-3-one and demineralised water in a mixing vessel. Raise the temperature of the reaction vessel to 55-60°C. Add previously prepared oil phase to the aqueous phase under high shear at 5000rpm to get a median particle size between 5µ - 10µ. Transfer the slurry to another vessel and add 25% Potassium hydroxide solution at 200rpm for 5 minutes. Stir the mixture for 2 hr at 60°C after allowing the slurry to cool at 15-25 degree Celsius temperature to obtain Metalaxyl-M micro-encapsulation phase.
(ii) Preparation of Suspension phase:
Into a clean and dry premixing vessel, take required quantity of demineralised water, modified styrene acrylic polymer, nonionic proprietary surfactant blend, Propylene glycol, Polydimethyl siloxane, 1,2-Benzisothiazolin-3-one and Kresoxim-methyl technical. Stir the mixture under homogenizer for 30 minutes to make uniform slurry. Pass slurry through bead mill under cold water circulation (temp 10-15ºC) for particle size reduction, D90 5-15micron Transfer milled slurry to post mixing vessel and charge required quantity of AG-RHO POL 23 W gel and continue to mix for 4 hrs at 15-25 degree Celsius to get smooth and homogenous Suspension.
(iii) Preparation of final ZC formulation:
In a clean mixing vessel add Metalaxyl-M micro-encapsulation to Kresoxim-methyl suspension phase under agitation under stirrer for 30 minutes and add required quantity of AG-RHO POL 23 W gel and mix well to get homogeneous ZC formulation.
Table 6: Physical and chemical properties of the ZC formulation as shown in Table 5 before and after the accelerated storage test
S. No. TESTS PRODUCT SPECIFICATIONS INITIAL SAMPLE AHS (54C,
2 weeks)
1 Description White to off-white color suspension Complies Complies
2 Active content, (% w/w)
i. Kresoxim-methyl
ii. Metalaxyl-M
4.75 - 5.5
11.87 - 13.12
5.23
12.73
5.21
12.70
3 Suspensibility
i. Kresoxim-methyl
ii. Metalaxyl-M
Min 70
Min 70
95.56
96.20
95.52
96.54
4 Wet sieve, passing through 75µ sieve, % w/w
Min 98 99.89 99.85
5 Spontaneity of dispersion, % w/w Min 70 96.34 95.83
6 Persistent foam after 1 min, mL Max 40 12 10
7 pH of 1% aq. suspension 5.0 -8.0 5.64 5.52
8 Pourability, as Rinsed residue, % w/w Max 1.0 0.26 0.28
9 Particle size distribution, d(90), ? Max. 15.0 14.2 15.3

EXAMPLE 3
BINARY MICRO-EMULSION (ME) FORMULATION COMPRISING METALAXYL-M + KRESOXIM-METHYL
1. Composition of ME formulation
[00157] The following Table 7 shows the composition for a binary ME formulation comprising Metalaxyl-M + Kresoxim-methyl in accordance with exemplary embodiments.
Table 7: Composition for ME formulation - Metalaxyl-M 1.3% + Kresoxim-methyl 3.2% ME
Sl. No. Ingredient Amount in % Ingredient class
1 Metalaxyl-M Technical 1.3 Active ingredient
2 Kresoxim-methyl Technical 3.2 Active ingredient
3 Ester of lactic acid 30.0 Solvent
4 Butanol 30.0 Solvent
5 Polyethylene Glycol 8.0 Antifreezing agent
6 Tristyryl phenol ethoxylate 16.0 Non-ionic emulsifier
7 Demineralised water QS Medium/Carrier
Total 100

2. Process for preparing the ME formulations
[00158] As per some specific exemplary embodiments ME formulation was prepared with composition as per Table 7.
Preparing the ME formulations - Into a clean and dry jacketed pre-mixing vessel, weigh and charge required quantity of ester of lactic acid, n-butanol and mix at 15-25 degree Celsius for 15 minutes. Charge Kresoxim-methyl technical and Metalaxyl-M technical and continue to mix for another 15 minutes till it dissolves completely.
In another vessel take demineralised water, polyethylene glycol, tristyryl phenol ethoxylate, and continue to mix for 30 minutes to make an aqueous phase. Add previously prepared organic phase into the aqueous phase under a high shear mixture to obtain a homogeneous micro-emulsion (ME) formulation.
[00159] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
Table 8: Physical and chemical properties of the ME formulation as shown in Table 7 before and after the accelerated storage test
S. No TESTS PRODUCT SPECIFICATIONS INITIAL SAMPLE AHS (54C,
2 weeks)
1 Description White to off-white color suspension Complies Complies
2 Active content, (% w/w)
i. Kresoxim-methyl
ii. Metalaxyl-M
3.04 – 3.52
1.23 – 1.43
3.2
1.3
3.2
1.3
3 pH of 1% aq. suspension 5.0 - 8.0 5.45 5.43
4 Persistent foam after 1 min, mL Max 40 34 33
5 Emulsion stability
Time after allowing the dispersion to stand Limits of stability
0 h Initial dispersion complete Complies Complies
0.5 h “Cream”, maximum: 0.5ml 0ml 0ml
“Free oil”, maximum: 0ml 0ml 0ml
Sediment,maximum:2ml 0ml 0ml
24.0 h Re-dispersion complete Complies Complies
24.5 h “Cream”, maximum: 0.5ml 0ml 0ml
“Free oil”, maximum: 0ml 0ml 0ml
Sediment, maximum:2ml 0ml 0ml

Example 4
Field Tests.
[00108] The suspo-emulsion formulation (SE) of Example 1 was tested for its biological activity and the results are shown in Table 9 below:
Table 9: Field test results of the Formulation of Example 1 applied against late blight of tomato at Bangalore location in the Rabi season 2023.
Tr.
no. Treatment details Dose/ha
(ml or gm) Per cent Disease Index (PDI) (%) Per cent Disease Control (%)
Before spray 7days
after spray
1 Metalaxyl-M 5% + Kresoxim –methyl 12.5% SE

SE Formulation 1 2000 ml 1.60 2.4 89.26
2 Metalaxyl-M 5% + Kresoxim –methyl 12.5% SE

SE Formulation 1
(5% reduced dosage) 1900 ml 1.60 2.8 87.53
3 Metalaxyl-M 5% WP 2000 ml 2.40 6 .0 74.67
4 Kresoxim–methyl 44.3% SC 500 ml 1.60 6.8 72.75
5 Amisulbrom 20% SC 500 ml 2.00 6.8 68.9
6 Metalaxyl M 3.3%+ Chlorothalonil 33.1% SC 1000 ml 1.60 3.6 83.49
7 Kresoxim-methyl 18% + Mancozeb 54% WP 1388 gm 2.00 4.0 81.76
8 Metalaxyl 8%+ Mancozeb 64%WP 2500 gm 2.40 4.4 79.84
9 Untreated check -- 2.00 22.0 -

ADVANTAGES OF THE PRESENT INVENTION
[00160] The present disclosure provides a binary fungicidal composition comprising Metalaxyl-M and Kresoxim-methyl that shows synergistic activity with better bio-efficacy, excellence in penetration, drift reduction and improvement in rain fastness.
[00161] The present disclosure provides a binary suspo-emulsion fungicidal formulation comprising Metalaxyl-M and Kresoxim-methyl nullifying phyto-toxicity, exhibiting a greater activity, better bio-efficacy, better selectivity, lowering undesirable environmental impact, lowering production and market cost and higher effectiveness against targeting early blight, late blight of tomato, potato, Downey and powdery mildew of grapes.
[00162] SE formulation of the present disclosure include stable formulation, storage stability, containing fine particles size ranging from 1 to 10 microns exhibiting minimum particle size growth, environmental friendly due to the usage of vegetable oil and nullifying phyto-toxicity, nullifying sedimentation and caking, phase separation, flocculation.
[00163] The present disclosure provides a binary fungicidal formulation comprising Metalaxyl-M and Kresoxim-methyl that does not result in phytotoxicity on applied crop and is safe to use.
,CLAIMS:

1) A binary fungicidal composition comprising Metalaxyl-M and Kresoxim-methyl.
2) A binary fungicidal composition as claimed in claim 1, wherein the composition is formulated as a suspo-emulsion formulation (SE), a ZC formulation (ZC), or a micro-emulsion (ME) formulation.
3) A binary fungicidal composition as claimed in claim 2, wherein the composition is in the form of a suspo-emulsion formulation (SE).
4) A binary fungicidal composition as claimed in claim 3, where the suspo-emulsion formulation (SE) comprises:
a) 0.1 to 15% by weight of a first active ingredient Metalaxyl, preferably 5% by weight;
b) 1 to 30% by weight of a second active ingredient Kresoxim-methyl preferably 12.5% by weight;
c) 0.1 to 10.0% by weight at least one triglyceride containing long chain fatty acid of C12 to C22;
d) 0.3 to 20.0% by weight of a dispersing agent selected from methyl methacrylate-polyethylene glycol graft copolymers, modified styreneacrylic polymer, alkyl polyglycoside, lignosulphonates, phenyl naphthalene sulphonates, polyaromatic sulfonates thereof;
e) 0.01 to 5.0% by weight of a wetting agent selected from nonionic proprietary surfactant blend, ethylene oxide and propylene oxide block copolymer, alkoxylated alcohol, alkoxylated alkyl/aryl phenol, fatty oil ethoxylate, phenyl naphthalene sulphonates;
f) 0.1 to 3.0% by weight of a suspending agent selected from sodium bentonite, silicates, polycarboxylates;
g) 0.01 to 4.0% by weight of emulsifiers selected from polyarylphenyl ether sulphate, ammonium salt;
h) 0.01 to 3.0% by weight of emulsifiers selected ethoxylated fatty alcohol;
i) 0.01 to 5.0% by weight of a stabilizer selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acrylates, polyvinyl acetates;
j) 0.01 to 25.0% by weight of anti freezing agent selected from propylene glycol, polyethylene glycol, diethylene glycol, glycerol, and urea;
k) 0.1 to 10.0% by weight of antifoaming agent selected from the group comprising of perfluroalkylphosphonic acids, polydimethyl siloxane or mixtures thereof;
l) 0.01 to 2.0% by weight of preservative are isothiazoline derivatives such as alkylisothiozaline, benzene selected from 1,2-benzisothiazolin-3-one, formaldehyde, and sodium benzoate;
m) 0.35 to 0.60% by weight of thickening agent selected from polysaccharides selected from xanthan gum, carboxy methyl cellulose, polycarboxylates, and silicates; and
n) water.
5) A binary fungicidal composition as claimed in claim 1, wherein the composition is in the form of a ZC formulation.
6) A binary fungicidal composition as claimed in claim 5, where the ZC formulation comprises:
a) 0.1 to 15% by weight of a first active ingredient Metalaxyl-M;
b) 1 to 30% by weight of a second active ingredient Kresoxim-methyl;
c) 0.1 to 15% by weight of water immiscible solvent selected from the group consisting of aromatic hydrocarbon C9 solvent or solvent naphtha;
d) 0.1 to 5.0% by weight of a capsule forming agent selected from polyurea polymers derived from a mixture of aromatic polyisocyanate and diamine such as methylene diisocyanate, diphenylmethane-diisocyanate, poly methylene poly phenyl isocynate;
e) 0.1 to 10% by weight of a dispersing agent selected from ethopropoxylated polyarylphenol phosphate amine salt, nonyl phenol ethoxylates, kraft ligno sulphonate, cetyl styryl alcohol;
f) 0.1 to 8% by weight of non-ionic emulsifiers selected from EO/PO polyaryl phenol, dodecyl benzene sulphonate, calcium salt of alkyl benzene sulphonate;
g) 0.1 to 6% by weight of a stabilizer selected from, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acrylates, polyvinyl acetates;
h) 0.05 to 5% by wight of a pH neutralizer selected from potassium hydroxide solution, trisodium phosphate, sodium hydroxide, mono ethanol amine or liquid ammonia;
i) 0.1 to 5% by weight of a dispersing agent selected from modified styrene acrylic polymer, EO/PO polyaryl phenol;
j) 0.1 to 5% by weight of a wetting agent selected from nonionic proprietary surfactant blend, ethylene oxide and propylene oxide block co-polymer;
k) 0.1 to 15% by weight of antifreezing agent selected from propylene glycol, polyethylene glycol, diethylene glycol, glycerol, urea;
l) 0.1 to 5% by weight of preservative selected from 1,2-benzisothiazolin-3-one, sodium benzoate, formaldehyde;
(xvi) 0.1 to 8% by weight of an antifoaming agent include silicone emulsions, polydimethyl siloxane;
m) 0.1 to 2.0% by weight of thickening agent selected from polysaccharides selected from xanthan gum, carboxy methyl cellulose, polycarboxylates, silicates; and
n) water.
7) A binary fungicidal composition as claimed in claim 1, wherein the composition is in the form of a micro-emulsion (ME) formulation.
8) A binary fungicidal composition as claimed in claim 7, where the micro-emulsion (ME) formulation comprises:
a) 0.1 to 15 % by weight of a first active ingredient Metalaxyl-M;
b) 1 to 30% by weight of a second active ingredient Kresoxim-methyl;
c) 10 to 70% by weight of water miscible solvent selected from the group consisting of ester of lactic acid, ethyl acetate, ethyl lactate; and 10 to 70% by weight of monohydric alcohol solvent selected from a group consisting of n-butanol, and tetrahyro furfuryl alcohol;
d) 1 to 20% by weight of an antifreeze agent selected from polyethylene glycol, glycerol, propylene glycol, and urea;
e) 1 to 30% by weight of non-ionic emulsifier selected from tristyryl phenol ethoxylate amine salt, and ethoxlated tristyrylphenol; and
f) 1 to 20% by weight demineralised water.