DESC:FORM 2

THE PATENTS ACT, 1970
(SECTION 39 OF 1970)
&
The Patents Rules, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

SYNERGISTIC FUNGICIDAL TRIPLE COMBINATION, COMPOSITION CONTAINING THEM, PROCESS FOR PREPARING AND USE THEREOF

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under Companies Act of 1956, having its principal place of business at Coromandel House, Sardar Patel Road, Secunderabad – 500 003, Telangana, India.

The following specification particularly describes the invention and the manner in which it is to be performed:
FIELD OF THE INVENTION
The present invention relates to synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide.

The present invention also relates to synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide, triazole fungicide, rheology modifier, dispersing agent and other agrochemical auxiliaries.

The present invention specifically relates to synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide at a weight in the ratio of 30 : 5 : 6 of first active ingredient to the second active ingredient and third active ingredient.

The present invention specifically relates to synergistic composition comprising combination of Mancozeb, Pyraclostrobin and Propiconazole.

The present invention also relates to a process for the preparation of synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide wherein the composition is prepared by high sheer dispersion and milling process.

BACKGROUND OF THE INVENTION
Fungicides are biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality, and profit. Fungicides are used both in agriculture and to fight fungal infections in animals. It is clear that, although pesticides remain indispensable in agriculture, a great potential still exists to improve their efficiency and thus reduce their input into the environmental and food chain. Depending on the field of application, and the mode of application, and depending on physical, chemical and biological parameters, the active substances are employed as active substance formulation in the form of a mixture with customary carriers, adjuvants and additives.

Mancozeb is a dithiocarbamate salt fungicides, non-systemic agricultural fungicide with multi-site, protective action on contact which mainly inhibit binding of bacteria in vivo oxidation of pyruvate and pyruvate oxidation processes involved in lipoic dehydrogenase II mercapto group (SH). Widely used in the beet, cabbage, cabbage, celery, peppers, beans, tomatoes, eggplant, potatoes, melons, such as watermelons, cotton, peanuts, wheat, corn, rice, hops, tea, rubber, citrus, grapes, mango, banana, lychee, pear, persimmon, peach, rose, rose, tobacco.

Mancozeb is chemically, manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt which is listed under FRAC code M:03 The "M" refers to Chemicals with Multi-Site Activity. "M" FRAC groups are defined as generally considered as a low risk group without any signs of resistance developing to the fungicides. The molecular formula is (C4H6MnN2S4)x(Zn)y and the structural formula is:

Mancozeb is a polymeric complex of the monomer illustrated which contains 20% manganese and 2.5% zinc. US 3,379,610 A discloses / claims Mancozeb.

Pyraclostrobin is a fungicide belonging to the group which is collectively known as strobilurins, which inhibit mitochondrial respiration. This leads to a reduction of energy-rich ATP that is available to support a range of essential processes in the fungal cell. Pyraclostrobin is a fungicide used to control major plant pathogens in cereals and other crops such as cereals including Wheat, Barley, Oats; Forage & Grain Maize, Triticale; Sugarbeet; Potatoes; Vegetables including Brassicas, Carrot; Beans, Vining Peas; Fruit including Strawberry, Blackcurrants.

Pyraclostrobin is chemically, methyl N-{2-[1-(4-chlorophenyl)pyrazol-3-yloxymethyl]phenyl}(N-methoxy)carbamate and has the following structure:

US 5,869,517 A claims pyraclostrobin generically.

Propiconazole is a triazole fungicide, also known as a DMI, or demethylation inhibiting fungicide due to its binding with and inhibiting the 14-alpha demethylase enzyme from demethylating a precursor to ergosterol. Without this demethylation step, the ergosterols are not incorporated into the growing fungal cell membranes, and cellular growth is stopped. It has a broad-spectrum systemic foliar fungicide for the control of a wide range of leaf and stem diseases in cereals.

Propiconazole is a systemic foliar fungicide with a broad range of activity. It is used on grasses grown for seed, mushrooms, corn, wild rice, peanuts, almonds, sorghum, oats, pecans, apricots, peaches, nectarines, plums and prunes. On cereals it controls diseases caused by Erysiphe graminis, Leptosphaeria nodorum, Pseudocerosporella herpotrichoides, Puccinia spp., Pyrenophora teres, Rhynchosporium secalis, and Septoria spp. It is also used in combination with permethrin in formulations of wood preserver. Propiconazole exhibits strong anti-feeding properties against the keratin-digesting Australian carpet beetle Anthrenocerus australis.

Propiconazole is a mixture of four stereoisomers and chemically 1-[ [2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1,2,4-triazole. Propiconazole has the following structure:

US 4,079,062 A claims Propiconazole generically.

Though, conventionally each of these active ingredients are used individually, combination product is not approved which has applications compared to the mono product. Hence, there is increased interest in the use of active ingredients in combination to give synergistic results.

Accordingly, there is a need in the art to provide synergistic compositions of combinations which environmentally safer and stable herbicidal / insecticidal / acaricidal compositions having two active ingredients with different physical and chemical properties, which are environmentally safe, easy and effective combination formulation of two active with enhanced efficacy and stable product during storage.

It was surprisingly and unexpectedly found by the present inventors that a selective combination composition of two active ingredients comprising Mancozeb, Pyraclostrobin and Propiconazole, rheology modifier and dispersing agent and other agrochemical auxiliaries, possesses enhanced efficacy, improved penetration and long duration control of phytopathogens as compared to its other traditional formulations with long storage stability across a wide temperature range and having no adverse impact on photosynthetic activity in plant and fruit quality.

OBJECTIVE OF INVENTION
The main objective of the present invention is to provide synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide.

Another objective of the present invention is to provide synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide, triazole fungicide, rheology modifier, dispersing agent and other agrochemical auxiliaries.

Another objective of the present invention is to provide synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide at a weight in the ratio of 30 : 5 : 6 of first active ingredient to the second active ingredient and third active ingredient.

Another objective of the present invention is to provide synergistic composition comprising combination of Mancozeb, Pyraclostrobin and Propiconazole.

Another objective of the present invention is to provide a process for the preparation of synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide wherein the composition is prepared by high sheer dispersion and milling process.

SUMMARY OF INVENTION
Accordingly, the present invention provides a synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide.

In another embodiment, the present invention provides a synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide, rheology modifier, dispersing agent and other agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic composition comprising combination of polymeric dithiocarbamate fungicide complex with zinc salt, strobilurin fungicide and triazole fungicide at a weight in the ratio of 30 : 5 : 6 of first active ingredient to the second active ingredient and third active ingredient.

In yet another embodiment, the present invention provides a synergistic composition comprising combination of Mancozeb, Pyraclostrobin and Propiconazole.

In yet another embodiment, the present invention provides a synergistic composition comprising combination of Mancozeb, Pyraclostrobin and Propiconazole, wherein said composition is in the form of oil dispersion (OD).

In yet another embodiment, the present invention provides a synergistic composition comprising:
a) Mancozeb,
b) Pyraclostrobin
c) Propiconazole
d) rheology modifiers,
e) emulsifiers,
f) dispersing agents and
g) other agrochemical auxiliaries.

In yet another embodiment, the present invention provides a synergistic fungicidal composition comprising:
a) Mancozeb,
b) Pyraclostrobin
c) Propiconazole
d) rheology modifiers,
e) emulsifiers,
f) dispersing agents and
g) base oil.

In yet another embodiment, the present invention provides oil dispersion composition comprising combination of Mancozeb, Pyraclostrobin and Propiconazole at a weight in the ratio of 30 : 5 : 6 of Mancozeb, Pyraclostrobin and Propiconazole.

In yet another embodiment, the present invention provides oil dispersion composition comprising:
a) Mancozeb in the range of 1% to 40 % (w/w),
b) Pyraclostrobin in the range of 1% to 10% (w/w),
c) Propiconazole in the range of 1% to 10% (w/w),
d) rheology modifiers in a range of 1% to 10% (w/w),
e) emulsifiers in a range of 1% to 30% (w/w),
f) dispersing agents in a range of 1% to 10% (w/w), and
g) base oil in a range of 1% to 50% (w/w).

In yet another embodiment, the present invention provides oil dispersion composition comprising:
a) Mancozeb in the range of 1% to 40 % (w/w),
b) Pyraclostrobin in the range of 1% to 10% (w/w),
c) Propiconazole in the range of 1% to 10% (w/w),
d) Surfom ESP 8105 in a range of 1% to 10% (w/w),
e) iso C12 alkylbenzene sulfonate calcium salt in 2-ethylhexanol in a range of 1% to 10% (w/w),
f) ethoxylated castor oil in a range of 1% to 10% (w/w),
g) castor oil ethoxylate, oleate of 1% to 10% (w/w),
h) isotridecanolethoxylate in a range of 1% to 10% (w/w), and
i) palm methyl ester in a range of 1% to 50% (w/w).

In another embodiment, the present invention provides a process for the preparation of composition comprising the steps of:
a) blending all the active ingredients, rheology modifier, dispersing agent and other agrochemical auxiliaries to high sheer dispersion at a temperature in the range of 30 to 50 ?C,
b) milling the homogenised mixture to obtain particles of size in the range of 15-20 µ,
c) stirring the milled mixture, and cooling to room temperature,
d) collecting the sample.

In another embodiment, the present invention provides a process for the preparation of oil dispersion composition comprising the steps of:
a) charging palm methyl ester in the high sheer disperser and stirring followed by heating to 45-50°C,
b) adding Propiconazole and iso C12 alkylbenzene sulfonate calcium salt in 2-ethylhexanol, castor oil ethoxylate oleate, isotridecanolethoxylate under continuous stirring for 20 min,
c) adding Surfom ESP 8105, Pyraclostrobin and Mancozeb in small lots over a period of ~1.5 hours under continuous stirring.
d) milling the above mixture (wet milling) to attain the desired particle size distribution (D90 should be ~ 20 micron),
e) cooling and packing the oil dispersion.

DETAILED DESCRIPTION OF THE INVENTION
The term "comprising", which is synonymous with "including", "containing", or "characterized by" here is defined as being inclusive or open-ended, and does not exclude additional, unrecited elements or method steps, unless the context clearly requires otherwise.

The present invention provides composition comprising combination of Mancozeb, Pyraclostrobin and Propiconazole in a ratio of 30 : 5 : 6 of first active ingredient to the second active ingredient and third active ingredient. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

The combination compositions of the present invention can be used on a paddy rice, dry-seeded rice crops. This product is also used as a foliar application in labeled crops.

The composition of the present invention could be applied to plants, seeds, fruits, soil as preventive and curative state.

The emulsifier used in the composition allows the active ingredient in the solvent to mix with water, this form an emulsion. The emulsifying surfactant system enabling the composition to form an oil-in-water emulsion when the formulation is added to water is typically a mixture of two or more surfactants, at least one of which is a nonionic surfactant and optionally at least one of which is an anionic surfactant.

The surfactants customarily employed in formulation technology, which are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, MunichNienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for preparation of the herbicidal compositions according to the invention.

Anionic surfactants suitable for use in the invention may be any known in the art. The anionic surfactants may be polyarylphenol polyalkoxyether sulfates and/or phosphates; C8-18 alcohol polyalkoxyether phosphates, carboxylates, and/or citrates; alkyl benzenesulfonic acids; C8-20 alkyl carboxylates including fatty acids; C8-20 alcohol sulfates; C8-20 alcohol phosphate mono- and diesters; C8-20 alcohol and (C8-20alkyl)phenol polyoxyethylene ether carboxylates, sulfates and sulfonates; C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene phosphate mono- and diesters; C8-20 alkylbenzene sulfonates, naphthalene sulfonates and formaldehyde condensates thereof; lignosulfonates; C8-20 alkyl sulfosuccinates and sulfosuccinamates; C8-20 acyl glutamates, sarcosinates, isethionates and taurates; water-soluble soaps and mixtures thereof.

Exemplary polyarylphenol polyalkoxyether sulfates and phosphates include polyarylphenol polyethoxyether sulfates and phosphates, polyarylphenol polypropoxyether sulfates and phosphates, polyarylphenol poly(ethoxy/propoxy)ether sulfates and phosphates, and salts thereof. The term “aryl” includes, for example, phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof. Exemplary polyarylphenol polyethoxyether sulfates and phosphates include distyrylphenol polyethoxyether sulfates and phosphates, and tristyrylphenol polyethoxyether sulfates and phosphates. The polyarylphenol polyalkoxether sulfates and phosphates may have a degree of alkoxylation (e.g., ethoxylation) of between about 1 and about 50, preferably between about 2 and about 40, more preferably between about 5 and about 30. Commercially available polyarylphenol polyalkoxyether sulfates and phosphates include, for example, SOPROPHOR® 4 D 384 (tristyrylphenol (EO)16 sulfate ammonium salt), SOPROPHOR® 3 D 33 (tristyrylphenol (EO)16 phosphate free acid), SOPROPHOR® FLK (tristyrylphenol (EO)16 phosphate potassium salt) and SOPROPHOR® RAM/384 (tristyrylphenol polyethoxylated ether sulfate neutralized with polyethoxylated oleylamine). In other embodiments, the polyarylphenol polyalkoxyether sulfates and phosphates may be mono-arylphenol polyalkoxyether sulfates and phosphates, such as styrylphenol polyethoxyether sulfates and phosphates.

Exemplary C8-18 alcohol polyethoxyether phosphates, carboxylates and citrates include STEPFAC® 8180 (tridecylalcohol (EO)3 phosphate), STEPFAC® 8181 (tridecylalcohol (EO)6 phosphate), STEPFAC® 8182 (tridecylalcohol (EO)12 phosphate), EMCOL® CN-6 (tridecylalcohol (EO)6 carboxylate). The C8-18 alcohol polyethoxyether phosphates, carboxylates and citrates may have a degree of ethoxylation of between about 1 and about 25, preferably between about 1 and about 20.

Exemplary alkylbenzene sulfonic acids and salts thereof include dodecylbenzene sulfonic acid, and metal (for example sodium or calcium, Atlox™ 4838B, Rhodocal 60 Br, Calsogen 4814), ammonia or amine salts of the alkylbenzene sulfonic acids, including dodecylbenzene sulfonic acid. Amine neutralized versions include primary amines, diamines, triamines and alkanol amines.

Additional preferred anionic surfactants include (C8-12 alkyl)phenol polyoxyethylene ether sulfates, and (C8-12 alkyl)phenol polyoxyethylene phosphate mono- and diesters, accompanied in each case by monovalent counterions. In one embodiment the monovalent counterion for a (C8-12 alklyl)phenol polyoxyethylene ether sulfate or a (C8-12 alkyl)phenol polyoxyethylene phosphate is a protonated polyoxyethylene C12-20 alkylamine surfactant. More specifically, polyoxyethylene tallowamine salt of a nonylphenol polyoxyethylene ether sulfate, nonylphenol polyoxyethylene phosphate, and a blend of such nonylphenol polyoxyethylene phosphate with polyoxyethylene tallowamine.

The composition of the present invention may also include non-ionic surfactant as additional emulsifier, which is a water-soluble, 20 to 250 ethylene glycol ether groups containing polyadducts of ethylene oxide and propylene oxide, ethylene diamino polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl moiety, the substances normally contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of non-ionic surfactants are nonylphenol polyethoxy ethanols, vegetable oil polyglycol ethers such as Ethoxylated castor oil (Emulsogen EL 360, Breakthrough EMV-20), polyadducts of ethylene oxide and propylene oxide, tributyl phenoxy polyethoxy ethanol (ethylan NS 500), octyl phenoxy polyethoxy ethanol.

The emulsifiers are present in the composition in a range of about 1 to 30%, more preferably 1 to 20% of the total weight of the composition.

The compositions of the present invention contain additional dispersing agents selected from and not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters (Sophrophor Bsu); aliphatic alcohol ethoxylates such as isotridecanolethoxylate (Lutensol TO 5); alky ethoxylates; EO-PO block copolymers; and graft copolymers, polycarboxylates, alkyl naphthalene sulfonates (such as Morwet IP, Morwet EFW), sodium salt of naphthalene sulfonate condensate (Morwet D-425), phenol sulphonic acid condensates, alkyl sulfonates, alkenyl sylfonates, mixture of alkyl sulfonates and alkenyl sylfonates (Lissapol D), alkyl suflosuccinates (Geropon), L-Wet, methyl oleyltaurates and poly vinyl alcohols. Preferred dispersing agents are polycarboxylates, alkyl naphthalene sulfonates, phenol sulphonic acid condensates, lignosulphonates, methyl oleyltaurates and poly vinyl alcohols, STEPSPERSE DF-600 is a blend of nonionic surfactant and sodium lignosulfonate, BREAK-THRU® DA 646 is a non-ionic dispersant based on a specialty polyether, BREAK-THRU® DA 647, a modified polyether, is a non-ionic dispersant, BREAK-THRU® DA 655 is a polyether phosphate, BREAK-THRU® DA 675 is a non-ionic, aqueous based organically modified polymer, Atlox Metasperse™ 550S Modified styrene acrylic polymer. Dispersing agents disclosed in US 6,677,399; US 6,767,865; EP 1 16 470; US 9,526,241 can be used in the present invention. Once the granule has been diluted in water, ready for spraying (with the aid of the wetting agent), a dispersant is required to maintain the particles in suspension and prevent them from agglomerating. The dispersing agent is a compound which ensures that the particles remain suspended in water. The dispersing agent can be ionic or non-ionic or a mixture of such surface active agents or graft co-polymer dispersant.

The dispersing agent is present in the composition in a range of about 1 to 10%, more preferably 1 to 8% of the total weight of the composition.

The compositions of the present invention contain a rheology modifier which is selected from the group consisting of hydrophobic and hydrophilic fumed and precipitated silica particles, gelling clays including bentonite, hectorite, laponite, attapulgite, sepiolite, smectite, Surfom ESP 8105, hydrophobically/organophilic modified bentonite, hectorite, hydrogentated castor oil (trihydroxystearin) or castor oil organic derivatives.

The rheology modifier is present in the composition in a range of about 1 to 10 % of the total weight of the composition.

The compositions of the present invention contain a base oil as medium for suspension for the OD composition, which is selected from a vegetable or mineral oils or esters of vegetable or mineral oils.

Suitable vegetable oils are all oils which can customarily be employed in agrochemical agents and can be obtained from plants. By way of example, sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, corn oil, cottonseed oil, and soya bean oil (Epoxidized soybean oil (ESO)) may be mentioned. Possible esters are palm methyl ester, ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, iso-propyl myristate, iso-propyl palmitate, methyl oleate, methyl soyate, methyl palmitate, ethyl oleate, by way of example. rape seed oil methyl ester, methyl soyate and palm methyl ester are preferred.

The base oil is present in the composition in a range of about 1 to 50 % of the total weight of the composition.

Preferably, the synergistic herbicidal composition can be formulated as oil-based suspension concentrates (OD). An oil dispersion (OD) is a stable suspension of active ingredient(s) in an organic fluid, which may contain other dissolved active ingredient(s), intended for dilution with water before use. OD formulations are metastable systems, like emulsions, oil-in-waters (EW) and suspension concentrates (SC). Therefore, after transportation and storage it may be necessary to re-homogenise the formulation, either by shaking or by stirring. OD, like SC formulations, do not disperse as spontaneously as EC formulations upon dilution in water. Therefore the spray solution has to be stirred in order to obtain a homogeneous dispersion before application.

The parameters which best describe the performance characteristics are:
- pourability (to ensure that the OD can be poured from its container);
- dispersion stability, wet sieve and persistent foam tests (to ensure the sprayability and stability of the diluted suspension);
- storage at elevated temperature (to ensure the absence of crystal growth upon storage).

The OD compositions of the present invention show low gravitational separation without a substantial increase in viscosity (measured at a shear rate of 200). This could be achieved by the use of low density particles with a density equal or less than 0.27 g/cm3 that are importantly combined with a reduced amount of a rheological modifier such that the low density particles balance the density from the dispersed particulates and that the rheological modifier is sufficient to hold the low density particles within the suspension without increasing the viscosity to the level that would be required without low density particles.

The compositions of the present invention can be diluted with water or water solutions of agronomic compounds before use to produce a sprayable suspension composition which is used in treating plants or increasing plant growth, Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the agrochemical active ingredient at a concentration of at least 0.001 g/l.

A particular mode of administering the composition of the present invention is the administration to the aboveground parts of plants, in particular to the leaves thereof (leaf-application). The number of applications and the administered doses are chosen in accordance with the biological and climatic conditions of life of the causative agent. The antifungal compositions though, can also be applied to the soil and get into the plants through the root system (systemic activity), in case the locus of the plants is sprayed with a liquid composition or if the components are added to the soil in a solid formulation e.g. in the form of granulate (soil application).

When using the active compound combinations according to the invention, the application rate can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active-compound combination application rates are generally between 0.1 and 10000 g/ha, preferably between 100 and 2500 g/ha. For seed dressing, the active compound combination application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 20 g per kilogram of seed. For the treatment of the soil, the active-compound combination application rates are generally between 0.1 and 10000 g/ha preferably between 1 and 5000 g/ha.

The following examples describes the nature of the invention which are given only for the purpose of illustrating the present invention in more detail and are not limitative and relate to solutions.

EXAMPLES
Example 1: Composition of Mancozeb 30% + Pyraclostrobin 5 % + Propiconazole 6 % OD
S. No. Ingredients/Raw Materials Composition (% w/w)
1 Mancozeb @85 %(b) 30.0 35.30
2 PyraclostrobinTechnical@97.2 (b) 5.0 5.14
3 PropiconazoleTechnical@95.15% (b) 6.0
6.31
4 Iso C12 alkylbenzene sulfonate calcium salt in 2-ethylhexanol (Calsogen 4814) 4.0
5 Ethoxylated castor oil (Emulsogen EL 360) 4.0
6 Castor oil ethoxylate, oleate (Breakthrough EMV-20) 2.0
7 Isotridecanolethoxylate (Lutensol TO 5) 4.0
8 Surfom ESP 8105 2.8
9 Palm Methyl Ester 36.45
Total 100

Manufacturing process:

All the raw materials were weighed, dispensed and the mixture was mixed in a High Sheer Disperser for 60 to 120 minutes at a temperature of 30 to 50 ?C. The mixture was milled to obtain the desired particle size (D90 ~ 20 micro) and stirred at room temperature for another 4 hours. The oil suspension was cooled and collected.

Field Bio-efficacy studies:

Trial – 1: Rice Sheath blight, Leaf spot complex and Dirty panicle
The sheath blight is caused by the fungal pathogen Rhizoctonia solani. This is potentially devasting disease can infect rice foliage at any stage of crop development. Its major threat to many crops and can also affect the crop stand and yield. Rhizoctonia solani fungus is cosmopolitan, polyphagous, widely distributed in tropical, subtropical, and temperate regions and for its development required hot and humid environment. The fungus spreads in the field by growing its runner hyphae from tiller to tiller, from leaf to leaf, and from plant to plant, resulting in a circular pattern of damage. The infection spreads most quickly when susceptible varieties are grown under favourable conditions such as warm temperature (28 to 32°C), high humidity (95% or above), and dense stands with a heavily developed canopy.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Pyraclostrobin + Propiconazole + Mancozeb against Rhizoctonia solani fungus in rice crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Rice crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting. The visual observations were recorded for % disease control from ten hills per plot. The observations were recorded before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 1: sheath blight disease control in rice:
Compositions Dose (gram active per hectare) % Sheath blight control
7 DAA 14 DAA
Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD (Example 1) 717.5 95 85
Pyraclostrobin 5% CS 87.5 40 25
Propiconazole 6% EC 105 50 35
Mancozeb 30% WP 525 20 15
OD – Oil Dispersion, WP – Wettable powder, EC – Emulsion concentrates, CS – Capsule suspension, and DAA - Days after application.

The trial results show excellent efficacy of Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD combinations against sheath blight disease of rice. The solo application of three active ingredients tested here, were also not able to provide satisfactory control of sheath blight disease. The combination of Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD found very promising against rice sheath blight in terms of efficacy as well as residual control.

Trial – 2: Rice leaf spot complex
The leaf spot is caused by the fungal pathogens Helminthosporium spp., Cercospora spp. Magnaporthe oryzae. This is potentially devasting disease can infect rice foliage. It leads to premature death of leaves and leaf sheaths, premature ripening of grains, and in severe cases, lodging of plants. Its major threat to many crops and can also affect the crop stand and yield. Leaf spot complex fungus is cosmopolitan and widely distributed in tropical, subtropical regions of Asia and for its development required hot and humid environment. The disease usually occurs in potassium deficient soils, and in areas with temperature ranging from 25-28°C. It appears during the late growth stages of the rice crop, starting at heading stage. Plants are most susceptible during panicle initiation onwards, and damage becomes more severe as plants approach maturity.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Pyraclostrobin, Propiconazole and Mancozeb against leaf spot complex fungus in rice crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. rice crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting. The visual observations were recorded for % disease control from ten hills per plot. The observations were recorded before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 2: Leaf spot complex control in rice
Compositions Dose (gram active per hectare) % Leaf spot control
7 DAA 14 DAA
Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD (Example 1) 717.5 90 80
Pyraclostrobin 5% CS 87.5 40 30
Propiconazole 6% EC 105 50 40
Mancozeb 30% WP 525 15 10
OD – Oil Dispersion, WP – Wettable powder, EC – Emulsion concentrates, CS – Capsule suspension, and DAA - Days after application.

The trial results in Table 2 show excellent efficacy of Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD combinations against leaf spot complex disease of rice. The solo application of three active ingredients tested here, were also not able to provide satisfactory control of leaf spot disease. The combination of Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD found very promising against rice leaf spot complex in terms of efficacy as well as residual control.

Trial – 3: Rice dirty panicle
The Dirty panicle disease or rice grain discoloration may be caused by many fungi, viz., Alternaria padwickii (Ganguly) M.B. Ellis; Curvularia lunata (Wakk) Boedjin; Fusarium moniliforme J. Sheld; and Bipolaris oryzae (Breda de Haan) Shoem. This is potentially devasting disease can infect rice foliage. Infection starts at the early boot stage and results in brown spots on rice hulls and the discoloration of rice grains. The germination of infected rice seeds is poor, and seedlings when they emerge, are abnormal. Infected rice seeds are also the source of the inoculum of the pathogenic fungi, which is distributed through seed storage to new crops. This disease is a major cause of rice seed destruction and leads to losses in yield, both qualitatively and quantitatively, of up to 80%. Dirty panicle disease has been reported in many countries where rice is a major crop, such as India, Pakistan, and Brazil. The disease usually occurs in potassium deficient soils, and in areas with temperature ranging from 25-28°C. It appears during the late growth stages of the rice crop, starting at heading stage. Plants are most susceptible during panicle initiation onwards, and damage becomes more severe as plants approach maturity.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Pyraclostrobin Propiconazole and Mancozeb against dirty panicle fungus in rice crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Rice crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting. The visual observations were recorded for % disease control from ten hills per plot. The observations were recorded at spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 3: Dirty panicle disease in rice
Compositions Dose (gram active per hectare) % Dirty panicle control
7 DAA 14 DAA
Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD (Example 1) 717.5 90 80
Pyraclostrobin 5% CS 87.5 30 25
Propiconazole 6% EC 105 50 40
Mancozeb 30% WP 525 15 10
OD – Oil Dispersion, WP – Wettable powder, EC – Emulsion concentrates, CS – Capsule suspension, and DAA - Days after application.

The trial results in table 3 show excellent efficacy of Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD combinations against dirty panicle disease of rice. The solo application of three active ingredients tested here, were also not able to provide satisfactory control of dirty panicle disease of rice. The combination of Pyraclostrobin 5% + Propiconazole 6% + Mancozeb 30% OD found very promising against rice dirty panicle disease in terms of efficacy as well as residual control.

,CLAIMS:WE CLAIM
1. A synergistic fungicidal composition comprising:
a) Mancozeb,
b) Pyraclostrobin
c) Propiconazole
d) rheology modifiers,
e) emulsifiers,
f) dispersing agents and
g) base oil.

2. The composition as claimed in claim 1, wherein said is in the form of oil dispersion.

3. The composition as claimed in claim 1, wherein said rheology modifiers are selected from hydrophobic and hydrophilic fumed and precipitated silica particles, gelling clays including bentonite, hectorite, laponite, attapulgite, sepiolite, smectite, Surfom ESP 8105, hydrophobically/organophilic modified bentonite, hectorite, hydrogentated castor oil (trihydroxystearin) or castor oil organic derivatives.

4. The composition as claimed in claim 1, wherein said emulsifiers are selected from iso C12 alkylbenzene sulfonate calcium salt in 2-ethylhexanol, ethoxylated castor oil and castor oil ethoxylate oleate or combinations thereof.

5. The composition as claimed in claim 1, wherein said dispersing agents are selected from sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates, tristyrylphenol ethoxylate phosphate esters, aliphatic alcohol ethoxylates such as isotridecanolethoxylate, alky ethoxylates; EO-PO block copolymers; and graft copolymers, polycarboxylates, alkyl naphthalene sulfonates, sodium salt of naphthalene sulfonate condensate, phenol sulphonic acid condensates, alkyl sulfonates, alkenyl sylfonates, mixture of alkyl sulfonates and alkenyl sylfonates or combinations thereof.

6. The composition as claimed in claim 1, wherein said base oil is selected from sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, corn oil, cottonseed oil, soya bean oil and possible esters are palm methyl ester, ethylhexyl palmitate, ethylhexyl oleate, ethylhexyl myristate, ethylhexyl caprylate, iso-propyl myristate, iso-propyl palmitate, methyl oleate, methyl soyate, methyl palmitate and ethyl oleate.

7. The composition as claimed in claims 1 to 6, wherein said oil dispersion composition comprising:
a) Mancozeb in the range of 1% to 40 % (w/w),
b) Pyraclostrobin in the range of 1% to 10% (w/w),
c) Propiconazole in the range of 1% to 10% (w/w),
d) Surfom ESP 8105 in a range of 1% to 10% (w/w),
e) iso C12 alkylbenzene sulfonate calcium salt in 2-ethylhexanol in a range of 1% to 10% (w/w),
f) ethoxylated castor oil in a range of 1% to 10% (w/w),
g) castor oil ethoxylate, oleate of 1% to 10% (w/w),
h) isotridecanolethoxylate in a range of 1% to 10% (w/w), and
i) palm methyl ester in a range of 1% to 50% (w/w).

8. The process for the preparation of composition as claimed in claim 1, wherein said process comprising the steps of:
a) blending all the active ingredients, rheology modifier, dispersing agent and other agrochemical auxiliaries to high sheer dispersion at a temperature in the range of 30 to 50 ?C,
b) milling the homogenised mixture to obtain particles of size in the range of 15-20 µ,
c) stirring the milled mixture, and cooling to room temperature,
d) collecting the sample.

9. The process for the preparation of said oil dispersion composition as claimed in claim 7, wherein said process comprising the steps of:
a) charging palm methyl ester in the high sheer disperser and stirring followed by heating to 45-50°C,
b) adding Propiconazole and iso C12 alkylbenzene sulfonate calcium salt in 2-ethylhexanol, castor oil ethoxylate oleate, isotridecanolethoxylate under continuous stirring for 20 min,
c) adding Surfom ESP 8105, Pyraclostrobin and Mancozeb in small lots over a period of ~1.5 hours under continuous stirring.
d) milling the above mixture (wet milling) to attain the desired particle size distribution (D90 should be ~ 20 micron),
e) cooling and packing the oil dispersion.


Dated this Twenty Sixth (26th) day of August, 2021

__________________________________
Dr. S. Padmaja
Agent for the Applicant
IN/PA/883