DESC:FIELD OF THE INVENTION
[001] The present invention relates to the technical field of agrochemicals. In particular, the present invention relates to an agrochemical formulation comprising prothioconazole and trifloxystrobin, particularly a water dispersible granule (WG) formulation or a wettable powder (WP) and a process for preparing the same.

BACKGROUND OF THE INVENTION
[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] The triazole compounds are some of the most important systemic fungicides that include a variety of compounds, which controls a wide range of fungal diseases on a variety of crops. Prothioconazole is a member of the triazoles class of compounds and possesses a unique toxophore in this class of fungicides. Prothioconazole is a synthetic chemical produced primarily for its fungicidal properties. It is effective fungicidal properties can be attributed to its ability to inhibit CYP51A1 enzyme. It is used as a fungicide as seed treatment and foliar spray to treat a variety of diseases in cereals.
[004] Another class of fungicide is strobilurin fungicides that have been widely used in agricultural fields. These fungicides are designed to manage fungal pathogens by inhibiting enzyme activities in mitochondrial respiration. Strobilurins are quinone outside inhibitor (QoI) fungicides that bind to the quinol oxidation (Qo) site of cytochrome b and inhibit mitochondrial respiration. Trifloxystrobin is one such broad-spectrum foliar strobilurin fungicide that has high levels of activity against many fungal pathogens within the Ascomycete, Deuteromycete, Basidiomycete, and Oomycete classes and active against a wide range of fungal plant pathogens. Fungal diseases controlled by this active ingredient include grape and cucurbit powdery mildew, apple scab and powdery mildew, peanut leafspot, and brown patch of turfgrasses.
[005] Though prothioconazole and trifloxystrobin 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.
[006] Hence, to address such issues, formulations comprising multiple active ingredients are attempted. However, non-compatibility of active ingredients, difficulty in selecting specific agrochemically non-active components compatible with such active ingredients poses sever challenges in formulating compositions comprising multiple active ingredients and provide a suitable formulation.
[007] Oil dispersion formulations known in the art have higher risk of phytotoxicity (plant damage), especially in hot or dry conditions. Oil dispersion formulations may be less compatible with tank mixes and equipment, thereby posing multiple challenges at the time of their application in the field. Though oil dispersion is meant to be easily dispersed with water, there is a risk of separation of phase, hence they should be applied immediately after mixing or constantly agitated. These dispersions are typically more expensive to produce, and the solvents used may increase dermal toxicity to the applicator. Oil dispersion also clogs the nozzle of the spray during application. These formulations can pose a greater environmental risk if not applied properly.
[008] There is thus an unmet need in the art to provide a suitable formulation for binary fungicidal formulation comprising combination of two active ingredients namely prothioconazole and trifloxystrobin, especially a water dispersible granule (WG) formulation or wettable powder (WP) formulation comprising prothioconazole and trifloxystrobin that have advantages such as stability, advantages of lower dosages, safety for crops of interest, showing no phytotoxicity, especially under challenging conditions and hence environment friendly, easy to transport, easy to store, generating less dust and reducing exposure risk to the applicator.

SUMMARY OF THE INVENTION
[009] In an aspect, the present invention provides an agrochemical formulation comprising prothioconazole in an amount in the range of about 10% to about 60% by weight; trifloxystrobin in an amount in the range of 1% to about 30% by weight; and one or more agrochemical excipients.
[0010] In an aspect, the present invention provides a stable agrochemical fungicidal formulation, wherein the formulation is a water dispersible granule (WG) formulation or a wettable powder (WP) formulation.
[0011] In another aspect, the present invention provides a process for preparing a water dispersible granule (WG) formulation comprising prothioconazole and trifloxystrobin, wherein said process comprises:
a. mixing prothioconazole and trifloxystrobin along with one or more agrochemical excipients in a dry pre-mixing vessel to obtain a mixture;
b. milling the mixture to obtain a milled material of particle size ranging from 1 to 30 microns;
c. transferring the milled material to a post-mixing vessel and mixing to obtain a milled powder;
d. homogenising the milled powder with desirable particle size to obtain a homogeneous powder;
e. adding the homogeneous powder to demineralised water and granulating to prepare a uniform dough; and
f. extruding the uniform dough through an extruder to obtain extruded granules and drying the extruded granules in a dryer to obtain the water dispersible granule (WG).
[0012] In another aspect, the present invention provides a process for preparing the wettable powder (WP) formulation comprising prothioconazole and trifloxystrobin, wherein said process comprises:
i. mixing prothioconazole and trifloxystrobin along with one or more agrochemical excipients in a dry pre-mixing vessel to obtain a mixture;
ii. milling the mixture to obtain a milled material of particle size ranging from 03 to 30 microns; and
iii. transferring the milled material to a post-mixing vessel and mixing to obtain a homogenous wettable powder (WP).

DETAILED DESCRIPTION OF THE INVENTION
[0013] The following is a detailed description of embodiments of the invention. The embodiments are in such detail as to clearly communicate the invention. 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 invention as defined by the appended claims.
[0014] 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.
[0015] 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.
[0016] 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.
[0017] 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.
[0018] 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.”
[0019] 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.
[0020] 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.
[0021] 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 invention. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the invention.
[0022] It should also be appreciated that the present invention 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.
[0023] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0024] 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.
[0025] The term, “water dispersible granule” (WG) as used herein refers to solid, non-dusty granular formulation which disperses or dissolves quickly when added to water to give a fine particle suspension and then sprayed.
[0026] The term, “wettable powder” (WP)” as used herein refers to formulation of fungicide where the active ingredient has been grinded into powder form to be mixed well with water and then sprayed.
[0027] The term, “agriculturally acceptable excipient or or agrochemical acceptable excipient” as used herein refers to any agriculturally acceptable inactive substance or mixture or adjuvant added to a formulation of a fungicidal active ingredient. Examples of agriculturally or agrochemically acceptable excipient include, but not limited to wetting agent(s), dispersing agent(s), stabilizing agent(s), binder(s), anti-foaming 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), a suspending agent, a stabilizer, 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), quenching agent (s), super spreader(s), etc.
[0028] The term, “weed” as used herein refers to unwanted plant harmful to plant of interest.
[0029] The term, “effective amount”, as used herein refers to the quantity of active agent, applied in an amount which will provide the required effect of fungicidal action. The particular amount is dependent upon many factors including, for example, type of formulations, fungal pathogen sought to be controlled, the crop to be protected and environmental conditions.
[0030] 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 fungal pathogen affecting the crop of interest.
[0031] The first active ingredient is prothioconazole known as fungicide used to control plant diseases.
[0032] The second active ingredient is trifloxystrobin known as fungicide having activity against many fungal pathogens in plants.
[0033] The present invention relates to a stable agrochemical formulation comprising prothioconazole and trifloxystrobin along with agrochemical excipients that can achieve one or more advantages including ability to formulate desired formulation, reducing dose of active ingredients, lowering production cost, obviating phytotoxicity, better selectivity, better bio-efficacy and enhanced fungicidal activity due to synergistic effect, and lowering undesirable environmental impact.
[0034] In an embodiment, the present invention provides a stable agrochemical fungicidal formulation, wherein the formulation is a water dispersible granule (WG) formulation or a wettable powder (WP) formulation.
[0035] In a preferred embodiment, the present invention provides an agrochemical fungicidal formulation, wherein the formulation is a water dispersible granule (WG) formulation.
[0036] In an embodiment, the present invention provides a stable solid agrochemical fungicidal formulation, wherein the solid formulation can be a water dispersible granule (WG) formulation or a wettable powder (WP).
[0037] In an embodiment, the present invention provides a water dispersible granule (WG) formulation comprising prothioconazole in an amount in the range of 10 to 60% by weight; trifloxystrobin in an amount in the range of 1 to 30% by weight; and one or more agrochemical excipients.
[0038] In a preferred embodiment, the present invention provides a water dispersible granule (WG) formulation comprising 40% by weight of prothioconazole; 10% by weight of trifloxystrobin; and one or more agrochemical excipients.
[0039] In the water dispersible granule (WG) formulation disclosed in the present invention, one or more agrochemical excipients can be selected from a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or combinations thereof.
[0040] In an embodiment, the present invention provides a water dispersible granule (WG) formulation comprising:
a. about 10% to about 60% of prothioconazole by weight of the formulation;
b. about 1% to about 30% of trifloxystrobin by weight of the formulation;
c. about 0.1% to about 20% by weight of the formulation, a wetting agent;
d. about 0.1% to about 30% by weight of the formulation, a dispersing agent;
e. about 0.1% to about 5% by weight of the formulation, an anti-foaming agent; and
a. about 0.1% to about 90% by weight of the formulation, inert carriers.
[0041] In an embodiment, the present invention provides a process for preparing water dispersible granule (WG) formulation, wherein said process comprises the steps of:
i. mixing prothioconazole, trifloxystrobin along with one or more agrochemical excipients at a mixing speed ranging from 10 to 1000 rpm for a time period ranging from 10 to 60 minutes to obtain a mixture;
ii. milling the mixture to obtain a milled material of particle size ranging from 1 to 30 microns;
iii. mixing the milled material at a speed of 10 rpm to 500 rpm for a time period ranging from 0.3 to 6 hours to obtain a milled powder;
iv. homogenising the milled powder for 1 hour to 4 hours to obtain a homogeneous powder with desirable particle size;
v. adding the homogeneous powder to demineralised water and granulating to prepare a uniform dough; and
vi. extruding the dough through an extruder to obtain extruded granules and drying the extruded granules in a dryer to obtain the water dispersible granule (WG) formulation.
[0042] In the process for preparing water dispersible granule (WG) formulation of the present invention, one or more agrochemical excipients can be selected from a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or combination thereof.
[0043] In another embodiment, the present invention provides an agrochemical fungicidal formulation, wherein the formulation is a wettable powder (WP) formulation.
[0044] In another embodiment, the present invention provides a wettable powder (WP) formulation comprising prothioconazole in an amount in the range of 10 to 60% by weight; trifloxystrobin in an amount in the range of 1 to 30% by weight; and one or more agrochemical excipients.
[0045] In a preferred embodiment, the present invention provides a wettable powder (WP) formulation comprising about 60% by weight of prothioconazole; about 10% by weight of trifloxystrobin; and one or more agrochemical excipients.
[0046] In the wettable powder (WP) formulation disclosed in the present invention, one or more agrochemical excipients can be selected from a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or a combination thereof.
[0047] In another embodiment, the present invention provides a wettable powder (WP) formulation comprising:
i. about 10% to about 60% by weight of the formulation, prothioconazole;
ii. about 1% to about 30% by weight of the formulation, trifloxystrobin;
iii. about 0.1% to about 10% by weight of the formulation, a wetting agent;
iv. about 0.1% to about 15% by weight of the formulation, a dispersing agent;
v. about 0.1% to about 2% by weight of the formulation, an anti-foaming agent; and
vi. about 1% to about 90%, preferably about 1 to about 60% by weight of the formulation, inert carriers.
[0048] In an embodiment, the present invention provides a process for preparing the wettable powder (WP) formulation. The said process comprises the steps of:
i. mixing prothioconazole, trifloxystrobin, along with one or more agrochemical excipients in a dry pre-mixing vessel at a mixing speed ranging from 10 to 1000 rpm for a time period ranging from 1 to 60 minutes to obtain a mixture;
ii. milling the mixture to obtain a milled material of particulate size ranging from 3 to 30 microns; and
iii. transferring the milled material to a post-mixing vessel and mixing at a blending speed of 10 rpm to 1000 rpm for a time period ranging from 0.3 to 6 hours to obtain a homogenous wettable powder (WP).
[0049] In the process for preparing the wettable powder (WP) formulation of the present invention, one or more agrochemical excipients can be selected from a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or a combination thereof.
[0050] The present invention discloses novel formulation comprising one or more agrochemical excipients selected from group comprising a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or a combination thereof.
[0051] The wetting agents can be selected from the group comprising of but not limited to sodium cetyl oleyl sulphate, sodium salt of alkyl naphthalene sulfonate, sodium salt of isopropyl naphthalene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, alpha olefin sulfonate, phenyl naphthalene sulfonates, sodium salt of sulfonated alkyl carboxylate, dioctyl sulfosuccinate sodium salt and sodium isopropyl naphthalene sulfonate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, alkane sulfonates, alpha olefin sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, octyl phenol ether sulphatedisodium laureth sulfosuccinate, diisodecyl sodium sulfosuccinate, or the mixture thereof, preferably sodium lauryl sulphate, sodium salt of alkyl naphthalene sulfonate.
[0052] The dispersing agents can be selected from the group comprising of but not limited to alkyl naphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, styrene (meth)acrylic copolymer sodium salt, isopropyl naphthalene sulfonate formaldehyde condensate, polyesters, polyamides, poly-carbonates, acrylic polymers and copolymers, styrene copolymers, butadiene copolymers, polyolefins copolymers, sodium alkyl aryl sulfonates, maleic anhydride copolymers, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sodium alkyl benzene sulfonates, polystyrenated acrylated co-polymer, salts of polyacrylic acids, or mixtures thereof, preferably sodium lignosulphonate sodium polyalkylnaphthalene sulphonate-formaldehyde condensate.
[0053] The anti-foaming agent can be selected from the group comprising of perfluroalkylphosphonic acids, polydimethyl siloxane or mixtures thereof, preferably polydimethyl siloxane.
[0054] The inert carriers can be selected from the group comprising of but not limited to natural ground minerals, such as kaolin alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, and calcium phosphates and calcium hydrogen phosphates, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, bentonite, river sand, zeolites, sand and dolomite, or synthetic granules of inorganic and organic ground materials, urea, potassium dihydrogen phosphate, superphosphate, diatomite, white carbon, precipitated calcium carbonate, sawdust, and starch such as maize starch, ammonium sulphate, precipitated silica, china clay or mixture thereof, preferably maize starch, precipitated silica, ammonium sulphate, sodium salt of ethylenediaminetetraacetate (Na-EDTA), china clay, kaolin.
[0055] The water dispersible (WG) and wettable powder (WP) formulation comprising the binary combination of prothioconazole and trifloxystrobin, surprisingly show synergism in effecting high disease resistance.
[0056] In certain embodiment, the present invention provides a stable agrochemical fungicidal formulation comprising prothioconazole and trifloxystrobin for control of fungal pathogen like targeting sheath blight of paddy, sheath rot of paddy, blast of rice, powdery mildew, downey mildew of grapes, powdery mildew, anthracnose of chilli, early and late blight of tomato.
[0057] The binary formulations can be applied at the target site in a suitable manner for example by a foliar spray.
[0058] The present invention relates to treating fungal diseases caused by sheath blight, sheath rot, blast of rice, powdery mildew, downey mildew of grapes, powdery mildew, anthracnose of chilli, early and late blight of tomato by applying the binary formulation comprising prothioconazole, and trifloxystrobin at an effective dose. The present invention relates to treating fungal disease of the crops rice, grapes, chilli, tomato.
[0059] The water dispersible granule (WG) formulation and the wettable powder formulation comprising prothioconazole and trifloxystrobin have advantages such as better stability, lower dosages, safe for crop of interest, showing no phytotoxicity, safer for plants, especially under challenging conditions and hence environment friendly and less harmful to living organisms or non-target organisms, easy to transport, storage, generating less dust, thereby reducing exposure risks for the applicator, less likely to leave residues that can clog sprayers.
[0060] While the foregoing describes various embodiments of the invention, other and further embodiments of the invention 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.
[0061] 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
[0062] The present invention 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 I - WATER DISPERSIBLE GRANULE (WG) FORMULATION COMPRISING PROTHIOCONAZOLE + TRIFLOXYSTROBIN
1. Water Dispersible Granule (WG) formulation
[0063] The following Table 1 shows the water dispersible granule formulation comprising prothioconazole + trifloxystrobin in accordance with exemplary embodiments.

Table 1: Water dispersible granule (WG) comprising Prothioconazole + Trifloxystrobin
Sr. No Ingredient %w/w Ingredient class
1 prothioconazole technical 10 to 60 Active ingredient
2 trifloxystrobin technical 1 to 30 Active ingredient
3 sodium salt of alkyl naphthalene sulfonate 0.1 to 8 Wetting agent
4 sodium lauryl sulphate 0.1 to 10 Wetting agent
5 styrenated methacrylated copolymer 0.1 to 10 Dispersing agent
6 sodium lignosulphonate 0.1 to 15 Dispersing agent
7 sodium polyalkylnaphthalene sulphonate- formaldehyde condensate 0.1 to 12 Dispersing agent
8 polydimethyl siloxane 0.1 to 2 Anti-foaming agent
9 precipitated silica 0.1 to 15 Inert Carrier
10 maize starch 0.1 to 10 Inert Carrier
11 china clay / kaolin Q.S. Inert Carrier
Total 100%

[0064] The following Table 2 shows the water dispersible granule (WG) formulation-1, i.e. 40% by wt. of prothioconazole + 10% by wt. of trifloxystrobin in accordance with exemplary embodiments.

Table 2: WG Formulation-1 (40% Prothioconazole + 10% Trifloxystrobin)
Sr. No Ingredients %w/w Ingredient class
1 prothioconazole technical 40 Active ingredient
2 trifloxystrobin technical 10 Active ingredient
3 sodium salt of alkyl naphthalene sulfonate 2 Wetting agent
4 sodium lauryl sulphate 1 Wetting agent
5 styrenated methacrylated copolymer 3 Dispersing agent
6 sodium lignosulphonate 6 Dispersing agent
7 sodium polyalkylnaphthalene sulphonate-formaldehyde condensate 3 Dispersing agent
8 polydimethyl siloxane 0.5 Anti-foaming agent
9 precipitated silica 2 Inert Carrier
10 maize starch 3 Inert Carrier
11 china clay / kaolin Q.S. Inert Carrier
Total 100%

[0065] The following Table 3 shows WG formulation-1, WG formulation-2 and WG formulation-3 comprising prothioconazole and trifloxystrobin in accordance with exemplary embodiments.

Table 3: WG Formulation-1, WG Formulation-2 and WG Formulation-3
Sr. No. Ingredient Formulation 1 Formulation 2 Formulation 3 Ingredient class
1 prothioconazole technical 40 15 30 Active ingredient
2 trifloxystrobin technical 10 2 15 Active ingredient
3 sodium salt of alkyl naphthalene sulfonate 2 3 2.5 Wetting agent
4 sodium lauryl sulphate 1 2 0.5 Wetting agent
5 styrenated methacrylated copolymer 3 5 7 Dispersing agent
6 sodium lignosulphonate 6 10 8 Dispersing agent
7 sodium polyalkylnaphthalene sulphonate-formaldehyde condensate 3 2 5 Dispersing agent
8 polydimethyl siloxane 0.5 0.6 0.6 Anti-foaming agent
9 precipitated silica 2 3 1 Inert Carrier
10 maize starch 3 5 5 Inert Carrier
11 china clay / kaolin (Q.S) (Q.S) (Q.S) Inert Carrier

[0066] The maize starch was obtained from Universal starch-chem limited, Mumbai (India).

2. Process of Preparation of WG formulation.
[0067] As per some specific exemplary embodiments WG formulation was prepared. The WG formulation comprising prothioconazole + trifloxystrobin as per above Table 1 to Table 3 was formulated following the below method:
In a clean and dry pre-mixing vessel take all the ingredients - china clay, maize starch, precipitated silica, polydimethylsiloxane, sodium salt of alkyl naphthalene sulfonate, sodium lauryl sulphate, styrenated methacrylated copolymer, sodium lignosulphonate, sodium polyalkylnaphthalene sulphonate-formaldehyde condensate, prothioconazole technical and trifloxystrobin technical. Mix all the ingredients for 30 minutes. Pass the above mixture through an airjet mill to achieve particle d90 = below 18 microns. Transfer the above milled material to a clean post mixing vessel and mix well for another 2 hours to get homogeneous powder.
Take the above powder to a suitable sigma mixer or plough shear mixer or rapid mixer granulator and add required quantity of demineralised water to prepare uniform dough. Extrude the dough through an axial extruder or radial extruder like basket extruder, twin extruder, cone extruder. Dry the extruded granules in fluidized bed dryer to achieve desire moisture level. Sieve the dry WG through vibro shifter to eliminate fines and oversize granules.

3. Accelerated Storage test (Stability Study) of WG formulation
[0068] 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 14 days as the default test conditions.
[0069] 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.
[0070] The “accelerated storage sample” is the sample after subjecting to the accelerated storage test.
[0071] The initial samples of the WG formulation of the above formulation-1 (Table 2) were subjected to the accelerated storage test to find out the product stability.
[0072] Table 4 shows the physical and chemical properties of the WG formulation-1 comprising 40% prothioconazole + 10% trifloxystrobin as shown in Table 2 before (initial) and after the accelerated storage test (AHS).
Table 4: Physical and chemical properties of the WG formulation-1 as shown in Table 2 before and after the accelerated storage test.
Sr. No. Test Product Specifications Ambient
0 Day After 14 days AHS at 54° C
1 Description Light brown-colored granules, free from extraneous matter Complies Complies
2 Active Content
(% w/w) prothioconazole 38-42 40.0 39.06

trifloxystrobin 9.5 – 10.5 10.0
9.86

3 Suspensibility, (%m/m),min 80 89.19 86.99
4 Wettability, Sec, max 120 10 10
5 Wet sieve through 75µ test sieve, (passing % m/m), min 98 99.75 99.62
6 Degree of dispersion
(%w/w), min 80 87.33 80.58
7 Persistent foam (after 1min) mL, max 60 18 15
8 pH of 1% aqueous dispersion 6.0 – 8.0 7.59 7.51
9 Moisture content by Karl Fischer, %w/w, max 2.0 – 4.0 2.26 2.92
Min. = Minimum; Max. = Maximum

[0073] The results in Table 4 shows that the appearance of the ambient sample of the WG formulation before and after the accelerated storage test (at 54°C for 14 days) remained the same that is ‘light brown-coloured granules, free from extraneous matter’.
[0074] Further, the content of prothioconazole and trifloxystrobin was found to be 40% w/w, and 10% w/w, respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54±2°C for 14 days) the content of prothioconazole and trifloxystrobin was found to be the almost same, that is 39.06% w/w, and 9.86% w/w, respectively. It indicates that the content of prothioconazole and trifloxystrobin is not degraded, hence falls within the product specification range and hence the content of the active ingredients i.e. prothioconazole and trifloxystrobin in the WG formulation is stable.
[0075] The pH of the ambient sample of the WG formulation (1% aqueous dispersion) before subjecting it to the accelerated storage test was found to be 7.59. However, even after subjecting the ambient sample to the accelerated storage test the pH was found to be almost same, that is 7.51. It indicates that the formulation was adhering to the pH range of preferably 6.0 – 8.0 which indicates that the formulation is stable.
[0076] Tests such as persistent foam and wettability and wet sieve passing test were conducted for the ambient sample of the WG formulation, before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 18 ml and 15 ml indicating the less froth formation and wettability test showed product complies specifications and product is stable.
[0077] The dispersion stability test was conducted for the ambient sample of the WG formulation, before and after accelerated storage test. The results of the dispersion stability test indicated that, product complies specifications, and product is stable.
[0078] The wet sieve passing test showed passing of 99.75% w/w and 99.62% w/w of particles of the formulation through the 75µ wet sieve indicating the product complies specifications and product is stable.
[0079] 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.
[0080] In view of the above test results, WG formulation of the present invention prepared in accordance with the above examples are extrapolated to be stable for 2 years.
[0081] The advantages of the WG formulation of the present invention include stable formulation, storage stability, containing fine particles size ranging from 03 to 30 microns exhibiting 1 to 3 particle size growth, environmental friendly 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.
Batch No Particle Size D90
01 9.91 Microns
02 12.1 Microns

Experimental data 1:
[0082] Table 4A shows effect of Prothioconazole 40% + Trifloxystrobin 10% WG against Sheath blight and sheath rot of paddy, at Mandya, Karnataka, Kharif, 2022-2023.
TABLE 4A
Sr. No. Treatment Dosage % Sheath blight disease infection % Reduction over Untreated check % Sheath rot disease infection % Reduction over Untreated check
g a.i./ha Formulation (ml/g/ha) Before spray 15 days after spray Before spray 15 days after spray
1 Prothioconazole 40%+ Trifloxystrobin 10% WG 200 + 50 500 1.20 2.73 94.60 1.00 4.63 86.45
2 Prothioconazole 40%+ Trifloxystrobin 10% WG 190 + 47.5 475 1.50 3.14 93.77 1.13 4.97 85.46
3 Prothioconazole 16% SC 200 1250 1.45 9.95 80.28 125 12.02 64.83
4 Trifloxystrobin 25% WG 50 200 1.30 15.24 69.79 1.33 13.65 60.07
5 Azoxystrobin 18.2% + Difenoconazole 11.4% SC 91 +57 500 1.00 5.26 89.57 1.15 6.31 81.56
6 Kresoxim methyl 40% + Hexaconazole 8% WG 200 + 40 500 1.40 4.18 91.72 1.34 5.49 83.96
7 Tebuconazole 50% + Trifloxystrobin 25% WG 100 + 50 200 1.20 5.8 88.51 1.32 6.05 82.32
8 Untreated Check - - 1.50 50.44 - 1.29 34.19 -

[0083] The present invention relates to novel binary formulations of fungicides comprising combination of prothioconazole and trifloxystrobin with significantly higher efficacy in disease resistance as compared to when the fungicides are utilized individually.
[0084] The present invention relates to novel formulations of prothioconazole and trifloxystrobin coming together in a synergistic combination such that their application results in increased resistance to disease as compared to the fungicides when applied individually. The Colby ratio of synergism of the disclosed formulations of the present invention has been experimentally established to be 1.006.
[0085] The present invention further relates to novel formulations of prothioconazole and trifloxystrobin with negligible phytotoxicity. No phytotoxicity was observed in rice crops when the inventive formulation comprising binary combination of prothioconazole and trifloxystrobin was applied to the rice crops.
[0086] The data of Table 4A indicates that prothioconazole 40%+ trifloxystrobin 10% WG @ 500g/ha was found to be statistically superior than other treatments and recorded lowest sheath blight and sheath rot disease infection and showed better efficacy. Thus, the formulation exhibited synergistic activity on disease control.
[0087] The water dispersible granule (WG) formulation comprising the binary combination of prothioconazole and trifloxystrobin, surprisingly show synergistic activity at lesser amounts as compared to the amounts when the ingredients used alone.
[0088] The experimental data in Table 4A, showed that the results of the present agrochemical fungicidal formulation comprising prothioconazole 40% + trifloxystrobin 10% WG were better in comparison to the individual compounds prothioconazole 16% SC (suspension concentrate), trifloxystrobin 25% WG and also better with the conventional two-way combinations of azoxystrobin 18.2% + difenoconazole 11.4% SC, kresoxim methyl 40% + hexaconazole 8% WG and tebuconazole 50% + trifloxystrobin 25% WG.

EXAMPLE II - WETTABLE POWDER (WP) FORMULATION COMPRISING PROTHIOCONAZOLE + TRIFLOXYSTROBIN
1. WP formulation
[0089] The following Table 5 shows the WP formulation comprising prothioconazole and trifloxystrobin in accordance with exemplary embodiments.
Table 5: WP formulation - Prothioconazole + Trifloxystrobin
Sr. No Ingredients % w/w Ingredient class
1 prothioconazole technical 60 Active ingredient
2 trifloxystrobin technical 10 Active ingredient
3 sodium lauryl sulphate 2 Wetting agent
4 sodium lignosulphonate 10 Dispersing agent
5 sodium polyalkylnaphthalene sulphonate-formaldehyde condensate 2 Dispersing agent
6 polydimethylsiloxane 0.5 Anti-foaming agent
7 precipitated silica 2 Inert Carrier
8 ammonium sulphate 5 Inert Carrier
9 sodium salt of ethylenediaminetetraacetate (NA-EDTA) 1 Inert Carrier
10 china clay Q.S to 100% Inert Carrier

2. Process for preparing the WP formulation:
[0090] As per some specific exemplary embodiments WP formulation was prepared with ingredients as per Table 5.
In a clean and dry pre-mixing vessel take all the ingredients - china clay, sodium salt of ethylenediaminetetraacetate (Na-EDTA), precipitated silica, ammonium sulphate, polydimethylsiloxane, sodium polyalkylnaphthalene sulphonate-formaldehyde condensate, sodium lignosulphonate, sodium lauryl sulphate, prothioconazole technical and trifloxystrobin technical. Mix all the ingredients for 30 minutes. Pass the above mixture through an airjet mill to achieve particle d90 = below 18 microns. Transfer the above milled material to a clean post-mixing vessel and mix well for 2 hours to get homogeneous WP formulation.
[0091] 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.
[0092] The present invention provides a stable agrochemical fungicidal formulation comprising prothioconazole and trifloxystrobin that shows synergistic activity with higher bio-efficacy, excellence in penetration, drift reduction and improvement in rain fastness.
[0093] The present invention provides a stable agrochemical water dispersible granule (WG) fungicidal formulation and wettable powder (WP) formulation comprising prothioconazole and trifloxystrobin nullifying phyto-toxicity, safe to use, exhibiting a greater activity, better bio-efficacy, better selectivity, lowering undesirable environmental impact, lowering production and market cost and higher effectiveness against fungal pathogens in plants.
,CLAIMS:

1. An agrochemical formulation comprising prothioconazole in an amount in the range of about 10% to about 60% by weight; trifloxystrobin in an amount in the range of 1% to about 30% by weight; and one or more agrochemical excipients.

2. The agrochemical formulation as claimed in claim 1, wherein the formulation is a water dispersible granule (WG) or wettable powder (WP).

3. The agrochemical formulation as claimed in claim 1, wherein the one or more agrochemical excipients are selected from group comprising a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or combinations thereof.

4. The agrochemical formulation as claimed in claim 2, wherein the formulation is a water dispersible granule (WG) formulation comprising prothioconazole in an amount in the range of about 10% to about 60% by weight; trifloxystrobin in an amount in the range of 1% to about 30% by weight; and one or more agrochemical excipients.

5. The agrochemical formulation as claimed in claim 4, wherein the amount of each of the excipient in the total formulation is in the range of 0.1 to 20% by weight of a wetting agent; 0.1 to 30% by weight of a dispersing agent; 0.1 to 5% by weight of an anti-foaming agent; and 0.1 to 90% by weight of inert carriers.

6. The agrochemical formulation as claimed in claim 4, wherein the water dispersible granule (WG) formulation comprises 40% by weight of prothioconazole; 10% by weight of trifloxystrobin; and one or more agrochemical excipients.

7. A process for preparing the water dispersible granule (WG) as claimed in claim 4, said process comprises:
i. mixing prothioconazole and trifloxystrobin along with one or more agrochemical excipients at a mixing speed ranging from 10 to 1000 rpm to obtain a mixture;
ii. milling the mixture to obtain a milled material of particle size ranging from 1 to 30 microns and mixing the milled material at a speed of 10 rpm to 500 rpm to obtain a milled powder;
iii. homogenising the milled powder to obtain a homogeneous powder with desirable particle size;
iv. adding the homogeneous powder to demineralised water and granulating to prepare a uniform dough; and
v. extruding the dough through an extruder to obtain extruded granules and drying the extruded granules in a dryer to obtain the water dispersible granule (WG) formulation,
said one or more agrochemical excipients are selected from group comprising a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or a combination thereof.

8. The agrochemical formulation as claimed in claim 2, wherein the formulation is a wettable powder (WP) formulation comprising prothioconazole in an amount in the range of 10 to 60% by weight; trifloxystrobin in an amount in the range of 1 to 30% by weight; and one or more agrochemical excipients.

9. The agrochemical formulation as claimed in claim 8, wherein the amount of each of the excipient in the total formulation is in the range of 0.1 to 10% by weight of a wetting agent; 0.1 to 15% by weight of a dispersing agent; 0.1 to 2% by weight of an anti-foaming agent; and 1% to 60% by weight of inert carriers.

10. The agrochemical formulation as claimed in claim 8, wherein the wettable powder (WP) formulation comprises 60% by weight of prothioconazole; 10% by weight of trifloxystrobin; and one or more agrochemical excipients.

11. A process for preparing the wettable powder (WP) as claimed in claims 8, said process comprises:
i. mixing prothioconazole and trifloxystrobin along with one or more agrochemical excipients in a dry pre-mixing vessel to obtain a mixture;
ii. milling the mixture to obtain a milled material of particulate size ranging from 3 to 30 microns; and
iii. transferring the milled material to a post-mixing vessel and mixing to obtain a homogenous wettable powder (WP),
said one or more agrochemical excipients are selected from group comprising a wetting agent, a dispersing agent, an anti-foaming agent, inert carriers, or a combination thereof.