DESC:FORM 2

THE PATENTS ACT 1970
(SECTION 39 OF 1970)

&

THE PATENT RULES, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

SYNERGISTIC FUNGICIDAL COMBINATION OF STROBILURIN, DITHIOLANE AND TRIAZOLE FUNGICIDE

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under the Companies Act, 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 a synergistic fungicidal composition comprising of a strobilurin fungicide, a dithiolane fungicide and a triazole fungicide.

Particularly, the present invention relates to a synergistic composition and formulations thereof capable of protecting crops from harmful effects of pathogenic fungi. The composition is valuable especially in the treatment of infections caused by pathogenic fungi on paddy crops.

BACKGROUND OF THE INVENTION
Pest, disease, and weeds are the frightening trio which is responsible for the considerable number of losses in agriculture. Besides these usual suspects, rodents, nematodes, plant parasites, and snails have also been able to impose enormous losses to the crops. The damage would run to alarming numbers where the management strategies are not adopted suitably.

Hence responsible crop production and management requires adoption and implementation of practices that critically address these issues of crop loss. Therefore, crop protection practices have become an important aspect of agriculture. Usage of fungicides as chemical means of controlling crop diseases pertains to be the at most priority to reduce yield losses under favorable conditions. With the increase in adoption of number of fungicides in the current agricultural practices, the pathogen population exposed to the repeated use of same fungicides develops resistance. Hence it results in the poor management of disease and to opt for alternative measures to reduce the resistance development in pathogen population. Thus, monitoring the resistance development in pathogen seems important context to have effective control of the disease by efficient fungicides.

The best approach for resistance management to fungicide is to device spray plan consisting of both combinations and alternating of fungicides with different modes of action. An at-risk fungicide should be used only in the season when necessary. To use at-risk fungicide, another product with different mode of action should be combined. The combination helps to slow the selection of the rate of resistance and control of resistant strains already present.

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.

Azoxystrobin is a methoxy acrylate fungicide and is a plant protection fungicide with protectant, curative, translaminar and systemic properties commonly used in agriculture.

Azoxystrobin chemically known as, Methyl(E)-2-(2-((6-(2-cyanophenoxy)pyrimidin-4-yl)oxy)phenyl)-3-methoxyacrylate. It is first disclosed in US 5,395,837 A and has the following structure:

Trifloxystrobin is a broad-spectrum foliar fungicide that has high levels of activity against many fungal pathogens within the Ascomycete, basidiomycetes, deuteromycetes and oomycetes, especially in the early stages in the infection cycle.

Trifloxystrobin chemically known as, Methyl (E)-methoxyimino-{(E)-a-[1-(a,a,a-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate. It is first disclosed in US 5,238,956 A and having following structure.

Isoprothiolane is a systemic fungicide with curative and protective effects. The active ingredient is used in rice cultivation to combat various fungal diseases such as rice blight, rice stem rot and Fusarium leaf spot on rice, also reducing plant-hopper populations following foliar applications. Isoprothiolane inhibits the penetration and elongation of infecting hyphae by inhibiting formation of infecting peg or cellulase secretion.

Isoprothiolane is chemically known as Di isopropyl 1,3-dithiolan-2-ylidenemalonate or bis(1-methylethyl) 2-(1,3-dithiolan-2-ylidene) propanedioate. It is first disclosed in US3,761,596 A and has the following structure:

Propiconazole is a triazole fungicide, also known as a DMI, or demethylation inhibiting fungicide due to its binding 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 mixture of four stereoisomers and chemically 1-[ [2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1,2,4-triazole. It is first disclosed in US 4,079,062A and has the following structure:

The fungicidal compounds forming the synergistic composition of this invention are independently known in the art for their effects on plant growth.

IN202121037852 assigned to Atul limited, discloses a synergistic fungicidal composition including: azoxystrobin in an amount ranging from 1% to 10% by weight of the composition; isoprothiolane in an amount ranging from 5% to 20% by weight of the composition; mancozeb in an amount ranging from 20% to 50% by weight of the composition.

IN 202111057805 assigned to Seedlings India Private Limited, discloses a synergistic pesticidal composition comprising pymetrozine, isoprothiolane and strobilurin fungicide.

IN457787 assigned to Mr. Rajesh Kumar Agarwal, discloses a synergistic fungicidal water dispersible granules formulation comprising of a) Azoxystrobin in an amount in between 5% to 10.0% weight percent ratio with respect to said composition; b) Isoprothiolane in an amount in between 15.0% to 21.0 % weight percent ratio with respect to said composition; c) Validamycin as an antibiotic fungicide in an amount in between 2.0% to 6.0% weight percent ratio with respect to said composition.

Thus, the present invention relates to a defined combination of strobilurin fungicide selected from azoxystrobin or trifloxystrobin, a dithiolane fungicide isoprothiolane, and a triazole fungicide propiconazole, and compositions thereof, and methods for using such combinations in the control or prevention of fungal infections in agriculture.

OBJECTIVE OF THE INVENTION
One object of the present invention is to provide a synergistic fungicidal composition comprising of a strobilurin fungicide, a dithiolane fungicide and a triazole fungicide.
In an object of the present invention is to provide a synergistic fungicidal composition comprising azoxystrobin or trifloxystrobin as a strobilurin fungicide, isoprothiolane a dithiolane fungicide and propiconazole a triazole fungicide.

In another object of the present invention is to provide a process for preparing such compositions and a method of using such compositions effectively.

In another object of the present invention is to provide a fungicidal composition that can protect plants, particularly paddy crop, from the attack of fungal pathogens.

In another object of the present invention is to provide a fungicidal composition that exhibits synergistic activity /functional reciprocity.

SUMMARY OF THE INVENTION
The present invention is to provide a synergistic fungicidal composition comprising of a strobilurin fungicide, a dithiolane fungicide and a triazole fungicide.

One aspect of the present invention is to provide a synergistic fungicidal composition comprising of a) strobilurin fungicide selected from azoxystrobin, trifloxystrobin, present in a range from 3% (w/w) to 10% (w/w), b) isoprothiolane as a dithiolane fungicide, present in a range from 15% (w/w) to 30% (w/w), c) propiconazole as a triazole fungicide, present in a range from 4% (w/w) to 16% (w/w) and d) agrochemical additives.

In an aspect of the present invention, the composition is formulated as Suspo emulsion (SE), and emulsion concentrate (EC).

In an aspect of the present invention, the suitable agrochemical excipients are selected from an anionic and non-ionic emulsifier, a wetting agent, a dispersing agent, an antifreezing agent, a biocide, a defoamer, a rheology modifier, a solvent, co-solvent and a filler.
In an aspect of the present invention, an anionic and non-ionic emulsifier is selected form the group comprising of Alkyl ether phosphates (PA100), non-ionic combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200) polymeric ester, blend based on alkoxylated alcohol and calcium dodecylbenzene sulfonate (Ca-DDBS), Castor oil ethoxylate, Iso-C12 alkyl benzene sulfonate calcium salt, and tristyrylphenol ethoxylate, present in a range from 1% to 10% (w/w).

In an aspect of the present invention, the wetting agent is selected from the group comprising of polyoxyethylene alkyl ether, polyalkylene oxide block copolymer, alkoxylated phosphate ester, polyoxyethylene polyoxypropylene condensate, and Tristyrylphenol Ethoxylates (Tersperse 2288) present in a range from 1% to 5% (w/w).

In an aspect of the present invention, the dispersing agent is selected from the group comprising of polymethyl methacrylate-polyethylene glycol graft copolymer, modified styrene acrylic polymer, acrylic copolymer solution, poly alkoxylated butyl ether, tristyrylphenol ether phosphate TEA salt, Tristyrylphenol Ethoxylates (Tersperse 4894), and combination thereof, present in a range from 1% to 5% (w/w).

In an aspect of the present invention, the antifreezing agent is propylene glycol present in a range from 5% to 15% (w/w).

In an aspect of the present invention, the defoamer is Silicone antifoam emulsion, present in a range from 0.1% to 2% (w/w).

In an aspect of the present invention, the biocide is 1,2-benzisothiazalin-3-one, present in an amount of 0.01% to 0.5% (w/w).

In an aspect of the present invention, the rheology modifier is xanthan gum, present in an amount of 5% to 10% (w/w).

In an aspect of the present invention, the co-solvent is selected from cyclohexanone, N,N-dimethyl octan/decanamide and combination thereof present in a range from 30% to 50% (w/w).

In an aspect of the present invention, the solvent is selected from the group comprising of xylene, Petroleum naphtha refinery stream (Solvent C-9), Solvent naphtha (Aromatic solvent C12), and 3,5,5-Trimethylcyclohex-2-en-1-one (Isophorone), present in a range from 10% to 20% (w/w).

In an aspect of the present invention, the filler is water, present in Q.S.

In another aspect of the present invention provides a process for the preparation of a synergistic fungicidal composition comprising of a) azoxystrobin or trifloxystrobin, b) isoprothiolane and c) propiconazole with suitable agrochemical additives.

In another aspect of the present invention provides an improved stable and ready to use fungicidal composition, having superior bio-efficacy compared to the individual formulations.

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.

It is to be noted that, as used in the specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
As used herein, the terms "crops" and "vegetation" can include, for instance, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.

As used herein, immature vegetation may be understood to include small vegetative plants prior to reproductive stage, and mature vegetation may be understood to include vegetative plants during and after the reproductive stage.

As used herein, the term “synergistic composition” may be understood to include effective combination of more than one agrochemical that allows the application of the said agrochemical in a much lower dosage, which results in a less dosage treatment for the crops.

As used herein, the term “agrochemical additives” may be understood to include a range of surfactants, dispersing agents, pigments, solvents, co-solvents, defoamers, and emulsions, crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, light absorbers, mixing aids, neutralizers or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, lubricants, thickeners, anti-freezing agents, sterilization agents, biocide, adjuvant among others.

Suitable additives may be a solid or liquid and are generally a substance commonly used in formulation processing process, for example, natural or regenerated minerals, solvents, dispersing agents, wetting agents, adhesives, thickeners, stabilizers, binders, or fertilizers.

As used herein, the terms "fungicide" refers to biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores.

As used herein, a "fungicidally effective amount" may be understood to include an amount of an active ingredient that causes a "fungicide effect," i.e., an adversely modifying effect including, for instance, a deviation from natural growth or development, killing, regulation, desiccation, growth inhibition, growth reduction, and retardation of fungi or their spores.

As used herein, applying fungicide or fungicidal composition may be understood to include delivering it directly to the targeted fungi or their spores on the plant thereof or to the area where control of fungi is desired. Methods of application include but are not limited to pre-emergently contacting soil or water, post-emergently contacting the fungi or area adjacent to the fungi on the plants.

The fungicidal composition of the present invention may be formulated as capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) Tablet (TB), Water dispersible granules (WG or WDG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW) among others. Preferably, the composition of the present invention is formulated as Suspo emulsion (SE), and emulsion concentrate (EC).

One embodiment of the present invention provides a synergistic fungicidal composition comprising of a strobilurin fungicide, a dithiolane fungicide and a triazole fungicide.

In an embodiment of the present invention provides a synergistic fungicidal composition comprising of a) strobilurin fungicide selected from azoxystrobin, trifloxystrobin, present in a range from 3% (w/w) to 10% (w/w), b) isoprothiolane as a dithiolane fungicide, present in a range from 15% (w/w) to 30% (w/w), c) propiconazole as a triazole fungicide, present in a range from 4% (w/w) to 16% (w/w) and d) agrochemical additives.

In an embodiment of the present invention, the composition is formulated as Suspo emulsion (SE), and emulsion concentrate (EC).

According to the present invention, the suitable agrochemical excipients are selected from an anionic and non-ionic emulsifier, a wetting agent, a dispersing agent, an antifreezing agent, a biocide, a defoamer, a rheology modifier, a solvent, co-solvent and a filler.

According to the present invention, an anionic and non-ionic emulsifier is selected form the group comprising of Alkyl ether phosphates (PA100), non-ionic combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200), polymeric ester, blend based on alkoxylated alcohol and calcium dodecylbenzene sulfonate (Ca-DDBS), Castor oil ethoxylate, Iso-C12 alkyl benzene sulfonate calcium salt, and tristyrylphenol ethoxylate, present in a range from 1% to 10% (w/w).

According to the present invention, the wetting agent is selected from the group comprising of polyoxyethylene alkyl ether, poly alkylene oxide block copolymer, alkoxylated phosphate ester, polyoxyethylene polyoxypropylene condensate, and Tristyrylphenol Ethoxylates (Tersperse 2288), present in a range from 1% to 5% (w/w).

According to the present invention, the dispersing agent is selected from the group comprising of polymethyl methacrylate-polyethylene glycol graft copolymer, modified styrene acrylic polymer, acrylic copolymer solution, poly alkoxylated butyl ether, tristyrylphenol ether phosphate TEA salt, Tristyrylphenol Ethoxylates (Tersperse 4894), and combination thereof, present in a range from 1% to 5% (w/w) .

According to the present invention, the antifreezing agent is propylene glycol present in a range from 5% to 15% (w/w).

According to the present invention, the biocide is 1,2-benzisothiazalin-3-one, present in an amount of 0.01% to 0.5% (w/w) .

According to the present invention, the defoamer is Silicone antifoam emulsion, present in a range from 0.1% to 2% (w/w).

According to the present invention, the rheology modifier is xanthan gum, present in an amount of 5% to 10% (w/w).

According to the present invention, the solvent is selected from cyclohexanone, N,N-dimethyl octan/decanamide and combination thereof present in a range from 30% to 50% (w/w).

According to the present invention, the solvent is selected from the group comprising of xylene, Petroleum naphtha refinery stream (Solvent C-9), Solvent naphtha (Aromatic solvent C 12), and 3,5,5-Trimethylcyclohex-2-en-1-one (Isophorone), present in a range from 10% to 20% (w/w).

According to the present invention, the filler is water, present in Q.S.

In another embodiment of the present invention is to provide a process for the preparation of a synergistic fungicidal composition comprising of a) azoxystrobin or trifloxystrobin, b) isoprothiolane and c) propiconazole with suitable agrochemical additives.
The fungicidal composition of the present invention is having curative, preventive and systemic fungicidal properties for protecting cultivated plants. As has been mentioned, said active ingredient mixtures can be used to inhibit or destroy the pathogens that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops or useful plants, while at the same time those parts of plants which grow later are also protected from attack by such pathogens. Active ingredient mixtures have the special advantage of being highly active against diseases in the soil that mostly occur in the early stages of plant development.

The present invention is further illustrated by the following examples which are provided merely to be exemplary of the inventions and is not intended to limit the scope of the invention. Certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the present invention.

EXAMPLES:
Example-1: The illustrative embodiments show the composition of Azoxystrobin or trifloxystrobin + Isoprothiolane + propiconazole:

Table 1: Azoxystrobin 6.0% + Isoprothiolane 20% + Propiconazole 8.0% SE:
S. No. Composition Function Charge in (%)
1. Azoxystrobin Active ingredient 6.0
2. Isoprothiolane Active ingredient 20.0
3. Propiconazole Active ingredient 8.0
4. Alkyl ether phosphates (PA100) Anionic and Non-ionic emulsifier 1.0
5. non-ionic combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200) Anionic and Non-ionic emulsifier 1.0
6. Polymethyl methacrylate-polyethylene glycol graft copolymer Dispersing agent 1.5
7. Polyoxyethylene alkyl ether Wetting agent 1.5
8. Propylene glycol Antifreezing agent 10.0
9. 1,2-benzisothiazalin-3-one Biocide 0.1
10. Silicone antifoam emulsion Defoamer 0.5
11. Xanthan gum Rheology modifier 5.0
12. Xylene Solvent 15.0
13. Water Filler Q.S.

Procedure of preparation of Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% SE Composition:

Step 1: Preparation of EW (A)
• An EW was prepared by incorporating Isoprothiolane and Propiconazole technical in suitable solvent (xylene) followed by addition of anionic and non-anionic emulsifiers (Alkyl ether phosphates (PA100), and non-ionic combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200)).
• Required quantity of antifreezing agent (propylene glycol) and filler (water) were added to the resultant mixture and kept under stirring.
Step 2: Preparation of Aqueous Slurry (B)
• Required quantity of dispersing agent (polymethyl methacrylate-polyethylene glycol graft copolymer) and wetting agents (polyoxyethylene alkyl ether) were added to propylene glycol followed by addition of defoamer (Silicone antifoam emulsion) and biocide (1,2-benzisothiazalin-3-one).
• Required quantity of Azoxystrobin Technical was added to the above and mixed under stirring.
• post addition of water, stir the mixture for homogenization for about 1 hour (the mixture should be thoroughly homogenized).
Step 3:
• In this step, EW (A) portion was added to the Aqueous Slurry (B) and mixed under stirring.
Step 4: Wet Milling of Slurry
• Pass the wet slurry from Vessel No. 1 through Dyno-Mill at temperature less than 30 °C and collect material in Vessel No. 2 (Post-Mixer).
• Maintain continuous Stirring in both the vessels to avoid the sedimentation.
• Submitting the sample to Quality Control Department to check the Particle Size distribution (PSD). The PSD of the material should be d90 < 5 µ. If the d90 is higher than > 5 µ then grind the mixture further till the PSD value complies the specification.
Step 5: Preparation of 2.0% Gel (Gel Suspension)
• Add 2.0 parts by weight of rheology modifier (Xanthan gum) in 4.0 parts by weight of Propylene glycol then add this slurry into 94.0 parts by weight of distilled water and stir the mixture until it gets lumps free homogeneous mixture.
• Keep this gel as such for 4-5 hours to get a translucent homogeneous gel.
Step 6: Gelling of Wet Milled Slurry.
• Add required quantity of Gel (prepared above) to the wet slurry in Vessel No 2 and stir the mixture for ~2 h for homogenization.
• Submit the sample for total Quality Control for complete analysis.
Step 7: Packing the sample in COEX container.

Table 2: Azoxystrobin/Trifloxystrobin 3.0% + Isoprothiolane 15.0% + Propiconazole 4.0% SE
S. No. Composition Function Charge in (%)
1. Azoxystrobin (or) trifloxystrobin Active ingredient 3.0
2. Isoprothiolane Active ingredient 15.0
3. Propiconazole Active ingredient 4.0
4. Alkoxylated Phosphate Ester Wetting agent 2.5
5. Poly alkoxylated butyl ether Dispersing agent 2.5
6. Blend based on
alkoxylated alcohol and calcium dodecylbenzene sulfonate (Ca-DDBS) Anionic and Non-ionic blend emulsifier 5.0
7. Castor oil ethoxylate Non-ionic emulsifier 5.0
8. Propylene glycol Antifreezing agent 5.0
9. 1,2-benzisothiazalin-3-one Biocide 0.01
10. Silicone antifoam emulsion Defoamer 0.1
11. Xanthan gum Rheology modifier 10.0
12. Solvent naphtha (Aromatic solvent C 12) solvent 10.0
13. Water Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1

Table 3: Azoxystrobin/Trifloxystrobin 10.0% + Isoprothiolane 30.0% + Propiconazole 16.0% SE
S. No. Composition Function Charge in (%)
1. Azoxystrobin (or) trifloxystrobin Active ingredient 10.0
2. Isoprothiolane Active ingredient 30.0
3. Propiconazole Active ingredient 16.0
4. Tristyrylphenol Ethoxylates (Tersperse 2288) Wetting agent 5.0
5. Tristyrylphenol Ethoxylates (Tersperse 4894) Dispersing agent 5.0
6. Iso-C12 alkyl benzene sulfonate calcium salt Anionic and Non-ionic blend emulsifier 2.5
7. Tristyrylphenol Ethoxylate Non-ionic emulsifier 2.5
8. Propylene glycol Antifreezing agent 5.0
9. 1,2-benzisothiazalin-3-one Biocide 0.5
10. Silicone antifoam emulsion Defoamer 2.0
11. Xanthan gum Rheology modifier 5.0
12. 3,5,5-Trimethylcyclohex-2-en-1-one (Isophorone) Solvent 10.0
13. Water Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1

Table 4: Trifloxystrobin 4.0% + Isoprothiolane 20% + Propiconazole 8.0% SE:
S. No. Composition Function Charge in (%)
1. Trifloxystrobin Active ingredient 4.0
2. Isoprothiolane Active ingredient 20.0
3. Propiconazole Active ingredient 8.0
4. Alkyl ether phosphates (PA100) Anionic and Non-ionic emulsifier 1.0
5. non-ionic combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200) Anionic and Non-ionic emulsifier 1.0
6. Polymethyl methacrylate-polyethylene glycol graft copolymer Dispersing agent 1.5
7. Polyoxyethylene alkyl ether Wetting agent 1.5
8. Propylene glycol Antifreezing agent 10.0
9. 1,2-benzisothiazalin-3-one Biocide 0.1
10. Silicone antifoam emulsion Defoamer 0.5
11. Xanthan gum Rheology modifier 5.0
12. Xylene Solvent 15.0
13. Water Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1
Table 5: Trifloxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% EC
S. No. Composition Function Charge in (%)
1. Trifloxystrobin Active ingredient 6.0
2. Isoprothiolane Active ingredient 20.0
3. Propiconazole Active ingredient 8.0
4. Alkyl ether phosphates (PA100) Anionic and Non-ionic blend emulsifier 8.0
5. combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200) Anionic and Non-ionic blend emulsifier 2.0
6. N, N-Dimethyl Octan/Decanamide Co-solvent 35.0
7. Cyclohexanone Co-solvent 10.0
8. Solvent C9 (Petroleum naphtha refinery stream) Solvent Q.S.

Manufacturing process: All the raw materials were weighed, dispensed and the mixture was mixed in vessel under continuous stirring and all the materials thoroughly mixed for around 30 minutes to obtain homogenous clear solution. The obtained solution was collected and packed.

Example 2: Efficacy study of Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% in Suspo emulsion (SE) form:

SYNERGY STUDIES:
The synergistic pesticidal action of the inventive mixtures calculated by Colby’s formula as follows:

Appropriate analysis of plant response to Fungicide combination is critical in determining the type of activity observed. The most widely used model is the one Gowing* derived and Colby** modified. Gowing described a mathematical formula for calculating the predicting response values for pesticide mixtures. He suggested the expected (E) percent inhibition of growth induced by pesticide A plus pesticide B and plus pesticide C is as follows, *(Jerry Flint et al, 1988)***

Three-way combination:

(AB+AC+BC) ABC
Expected (E) = A + B + C - +
100 10000

Where,

A = observed efficacy of active ingredient A at the same concentration as used in the mixture.
B = observed efficacy of active ingredient B at the same concentration as used in the mixture.
C = observed efficacy of active ingredient C at the same concentration as used in the mixture.

When the percentage of pesticidal control observed for the combination is greater than the expected percentage, there is a synergistic effect. (Ratio of O/E > 1, means synergism observed.)

Two-way combination:
AB
Expected (E) = A + B –
100
Where,
A = Percent weed control by fungicide A.
B = Percent weed control by fungicide B.
When the percentage of pesticidal control observed for the combination is greater than the expected percentage then the composition shows synergistic effect.

Reference:
*Gowing, D. P. 1960. Comments on tests of Fungicide mixtures. Weeds 8:379–391.
**Colby, S. R. 1967. Calculating synergistic and antagonistic responses of Fungicide combinations. Weeds 15:20–22

*** Jerry Flint et al, 1988. Analyzing Fungicide Interactions: A Statistical Treatment of Colby's Method. Weed Technology 2: 304-309

Trial 1: Bio-efficacy against rice blast:
The rice blast is caused by the fungal pathogen Magnaporthe oryzae. This is potentially devasting disease can infect rice foliage. The symptoms of rice blast include lesions that can be found on all parts of the plant, including leaves, leaf collars, necks, panicles, pedicels, and seed. It’s a major threat to rice crops and can also affect the crop stand and yield. Infection of rice occurs when conidia are deposited on rice tissues and germinate by producing a germ tube and an appressorium. The appressorium is a melanized structure, and from it develops an infection peg which penetrates the tissue. After penetration, the primary infection hypha grows rapidly and ramifies within susceptible tissues. Growth within tissues of resistant cultivars is often inhibited. Generally, rice blast is favored by moderate temperatures (240C) and periods of high moisture that are 12 hours or longer, conditions readily attainable in flooded rice fields. Spores produced as the primary inoculum on the overwintering tissues produce the initial infections on young seedlings when the spores that are deposited on leaves, germinate, and invade leaf tissues.

The field trial was conducted to evaluate the efficacy of a three-way combination of azoxystrobin, isoprothiolane and propiconazole against Magnaporthe oryzae fungus in rice crop. The 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 6: blast disease control in rice:
Compositions Dose
(g AI/ha) Percent disease control – rice blast
07 DAA 14 DAA
Azoxystrobin 75 55 40
Propiconazole 100 50 40
Isoprothiolane 250 75 60
Azoxystrobin + Propiconazole 75 + 100 67 62
Propiconazole + Isoprothiolane 100 + 250 79 70
Azoxystrobin + Isoprothiolane 75 + 250 80.5 75
Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% SE 75 + 100 + 250 95 90
SE– Suspo emulsion, and DAA - Days after application.

The trial results show excellent efficacy of Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% SE combinations against blast disease of rice. The solo application of three active ingredients and its two-way combinations tested here, were also not able to provide satisfactory control of rice blast disease. The three-way combination of Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% SE was found to be very promising against rice blast in terms of efficacy as well as residual control.

Table 7: Percent rice blast disease control at 14 DAA
Compositions Dose
(g or ml/ha) % Rice Blast disease control
Expected Actual
Azoxystrobin 75 55 40
Propiconazole 100 50 40
Isoprothiolane 250 75 60
Azoxystrobin + Propiconazole 75 + 100 78 65
Ratio of O/E 0.83
Propiconazole + Isoprothiolane 100 + 250 82 75
Ratio of O/E 0.91
Azoxystrobin + Isoprothiolane 75 + 250 85.5 78
Ratio of O/E 0.91
Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% SE 75 + 100 + 250 85.6 90
Ratio of O/E 1.05
SE– Suspo emulsion, and DAA - Days after application.

The results in table 7 clearly demonstrate synergy between Azoxystrobin, Isoprothiolane, and propiconazole in controlling rice blast disease. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.

The three-way combination of Azoxystrobin 6% + Isoprothiolane 20% + Propiconazole 8% SE provided excellent control against rice sheath blight, dirty panicle, and false smut diseases. The combinations had shown synergistic effect on various disease control in rice.

Example 3: Efficacy study of Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% in Suspo emulsion (SE) form:
The rice blast is caused by the fungal pathogen Magnaporthe oryzae. This is potentially devasting disease can infect rice foliage. The symptoms of rice blast include lesions that can be found on all parts of the plant, including leaves, leaf collars, necks, panicles, pedicels, and seed. It’s major threat to rice crop and can also affect the crop stand and yield. Infection of rice occurs when conidia are deposited on rice tissues and germinate by producing a germ tube and an appressorium. The appressorium is a melanized structure, and from it develops an infection peg which penetrates the tissue. After penetration, the primary infection hypha grows rapidly and ramifies within susceptible tissues. Growth within tissues of resistant cultivars is often inhibited. Generally, rice blast is favored by moderate temperatures (240C) and periods of high moisture that are 12 hours or longer, conditions readily attainable in flooded rice fields. Spores produced as the primary inoculum on the overwintering tissues produce the initial infections on young seedlings when the spores that are deposited on leaves, germinate, and invade leaf tissues.

The field trial was conducted to evaluate the efficacy of innovative combination of trifloxystrobin, propiconazole and isoprothiolane against Magnaporthe oryzae fungus in rice crop. The 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 8: blast disease control in rice:
Compositions Dose
(g AI/ha) Percent disease control – rice blast
07 DAA 14 DAA
Trifloxystrobin 50 55 45
Propiconazole 100 50 40
Isoprothiolane 250 75 65
Trifloxystrobin + Propiconazole 50 + 100 65 60
Propiconazole + Isoprothiolane 100 + 250 78 70
Trifloxystrobin + Isoprothiolane 50 + 250 80 75
Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% SE 50 + 100 + 250 95 92
SE– Suspo emulsion, and DAA - Days after application.

The trial results show excellent efficacy of Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% SE combinations against blast disease of rice. The solo application of active ingredients and its two-way combinations tested here, were also not able to provide satisfactory control of rice blast disease. The three-way combination of Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% SE was found to be very promising against rice blast in terms of efficacy as well as residual control.

Table 9: Percent rice blast disease control at 14 DAA
Compositions Dose
(GAH) % Rice Blast disease control
Expected Actual
Trifloxystrobin 50 45
Propiconazole 100 40
Isoprothiolane 250 65
Trifloxystrobin + Propiconazole 50 + 100 67 60
Ratio of O/E 0.89
Propiconazole + Isoprothiolane 100 + 250 79 70
Ratio of O/E 0.88
Trifloxystrobin + Isoprothiolane 50 + 250 80.75 75
Ratio of O/E 0.92
Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% SE 50 + 100 + 250 88.45 92
Ratio of O/E 1.04
SE– Suspo emulsion, and DAA - Days after application.

The results in table 9 clearly demonstrate synergy between Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% SE in controlling rice blast disease. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination. The combination of Trifloxystrobin 4% + Isoprothiolane 20% + Propiconazole 8% SE provided excellent control against rice sheath blight, dirty panicle, and false smut diseases. The combinations had shown synergistic effect on various disease control in rice. ,CLAIMS:WE CLAIM:
1. A synergistic fungicidal composition comprising of
a) strobilurin fungicide selected from Azoxystrobin, trifloxystrobin, present in a range from 3% (w/w) to 10% (w/w),
b) isoprothiolane as a dithiolane fungicide, present in a range from 15% (w/w) to 30% (w/w),
c) propiconazole a triazole fungicide, present in a range from 4% (w/w) to 16% (w/w) and
d) agrochemical additives.

2. The composition as claimed in claim 1, wherein the composition is formulated as suspo emulsion (SE), and emulsion concentrate (EC).

3. The composition as claimed in claim 1, wherein the suitable agrochemical additives are selected from an anionic and non-ionic emulsifier, a wetting agent, a dispersing agent, an antifreezing agent, a biocide, a defoamer, a rheology modifier, a solvent, a co-solvent and a filler.

4. The composition as claimed in claim 3, wherein the anionic and non-ionic emulsifier is selected form the group comprising of Alkyl ether phosphates (PA100), non-ionic combination of a fatty alcohol polyglycol ether and hydrogenated castor oil ethoxylate (PS200), polymeric ester, Blend based on alkoxylated alcohol and calcium dodecylbenzene sulfonate (Ca-DDBS), Castor oil ethoxylate, Iso-C12 alkyl benzene sulfonate calcium salt, and tristyrylphenol ethoxylate, present in a range from 1% to 10% (w/w).

5. The composition as claimed in claim 3, wherein the wetting agent is selected from the group comprising of polyoxyethylene alkyl ether, poly alkylene oxide block copolymer, alkoxylated phosphate ester, polyoxyethylene polyoxypropylene condensate, and Tristyrylphenol Ethoxylates (Tersperse 2288), present in a range from 1% to 5% (w/w).

6. The composition as claimed in claim 3, wherein the dispersing agent is selected from the group comprising of polymethyl methacrylate-polyethylene glycol graft copolymer, modified styrene acrylic polymer, acrylic copolymer solution, Poly alkoxylated butyl ether, tristyrylphenol ether phosphate TEA salt, Tristyrylphenol Ethoxylates (Tersperse 4894), and combination thereof, present in a range from 1% to 5% (w/w).

7. The composition as claimed in claim 3, wherein the rheology modifier is xanthan gum, present in an amount of 5% to 10% (w/w).

8. The composition as claimed in claim 3, wherein the defoamer is Silicone antifoam emulsion, present in a range from 0.1% to 2% (w/w).

9. The composition as claimed in claim 3, wherein the solvent is selected from the group comprising of xylene, Petroleum naphtha refinery stream (Solvent C-9), Solvent naphtha (Aromatic solvent C 12), and 3,5,5-Trimethylcyclohex-2-en-1-one (Isophorone), present in a range from 10% to 20% (w/w).

10. The composition as claimed in claim 3, wherein the co-solvent is selected from cyclohexanone, N,N-dimethyl octan/decanamide and combination thereof, the filler is water, present in Q.S.

Dated this Sixteenth (16th) day of January, 2024

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