DESC:FORM 2

THE PATENTS ACT 1970
(SECTION 39 OF 1970)

&

THE PATENT RULES, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

PESTICIDAL COMPOSITION COMPRISING FIPRONIL AND METALAXYL

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 pesticidal composition comprising an insecticidal compound, a fungicidal compound and one or more suitable additives in synergistically effective amounts.
Particularly, the present invention relates to pesticidal composition comprising Fipronil, Metalaxyl and one or more suitable additives.
More particularly, the present invention relates to a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil and Metalaxyl with one or more agrochemical additives.
BACKGROUND OF THE INVENTION
Pesticides are substances or mixtures of substances that are mainly used in agriculture or in public health protection programs in order to protect plants from pests, weeds or diseases, and humans from vector-borne diseases, such as malaria, dengue fever, and schistosomiasis. Insecticides, fungicides, herbicides, rodenticides, and plant growth regulators are typical examples of pesticides.
In many economically important crops and cash crops such as rice, peppers, grapes and other agricultural crops, fungal infection and insect infestation may occur simultaneously. In order to control this farmer usually apply compositions comprising either single active or combinations of actives. Control of plant diseases and pests is an inevitable work in efficiently performing the agricultural production, and in order to achieve this purpose, synthetic pesticides have been used, resulting in making a remarkable achievement.
Fipronil is a broad-spectrum insecticide that belongs to the phenylpyrazole chemical family. It was first registered for use in the United States in the 1990s. Agricultural use of Fipronil in the United States increased from 1998 to 2005. Fipronil has been widely used in seed coatings and granular soil treatments to control unwanted arthropods in many kinds of food, horticultural, and turf plants. Various spray and spot on products containing Fipronil have been widely utilized to control fleas, ticks and mange mites on pet animals. Targeted pests and non-target organisms are poisoned by feeding upon or having contact with treated hosts (plant or animal), as well as through exposure to the insecticide in the environment.
Fipronil is not volatile. It binds to soils and sediment particles, and it is biodegraded in soil, which provides some protection against runoff and surface water contamination. Soils with higher organic carbon concentrations are more effective at binding Fipronil than soils with low organic carbon. Soil binding and biodegradation also help protect against percolation into groundwater.
Because of its effectiveness on various pests, Fipronil is used as the active ingredient in flea control products for pets and home roach traps as well as field pest control for corn, golf courses, and commercial turf. Its widespread use makes its specific effects the subject of considerable attention. This includes ongoing observations on possible off-target harm to humans or ecosystems as well as the monitoring of resistance development.
Fipronil, chemically known as 5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile. The structure of Fipronil is as follows:

Metalaxyl is an acylalanine fungicide with systemic function. It can be used to control Pythium in a number of vegetable crops, and Phytophthora in peas.
Since 1975 it has been known to those skilled in the art that the Metalaxyl R-enantiomer is far superior to the S-enantiomers in terms of fungicidal action and is in practice regarded as the actual mechanism of action. Commercial Metalaxyl is available in the form of the racemate. Likewise, mixtures of Metalaxyl racemate with mancozeb, chlorothalonil, copper preparations, folpet, fluazinam or cymoxanil have become known commercially and otherwise. Owing to its high activity, there has in the past never been any practical necessity to resolve the racemate, of which half consists of the desired R-enantiomer. Today, Metalaxyl is a standard formulation for controlling downy mildew varieties (Oomycetes).
Metalaxyl is methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-DL-alaninate. The structure of Metalaxyl is as follows:

In an embodiment of the invention, the pesticidal composition comprising combination of an insecticide and a fungicide.
The mixing of insecticides with fungicides results in incompatibility of physical nature and also may alter efficacy of the active ingredients. Hence, it requires due trial and experimentation to assess the compatibility of fungicides with insecticides and their influence on crops. Many pesticides with combination of one or more actives have been used by farmers. But still there is requirement for new combinations which can provide efficacy, low-cost benefit ratio, broad spectrum protection and decreased environmental load.
With increased use of chemical compounds as insecticides, herbicides, fungicides it has been observed that crops are becoming tolerant and resistant to use of composition comprising single active. Hence, there is a need for combination of actives belonging to different classes and groups to allow for broader disease control spectrum that combines curative and preventive actives and has a lower dosage. There is a need in the art for new combinations of broad-spectrum insecticidal compounds like Fipronil with different fungicides like Metalaxyl that help improve spectrum.
OBJECT OF THE INVENTION
One object of the present invention is to provide pesticidal composition comprising combination of an insecticide and a fungicide.
Another object of the present invention is to provide a pesticidal comprising combination of broad-spectrum insecticide and an acylalanine fungicide.
Another object of the present invention is to provide a pesticidal composition comprising combination of Fipronil and Metalaxyl.
Yet another object of the present invention is to provide a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil and Metalaxyl with one or more agrochemical additives.
In yet another object of the present invention is to provide pesticidal composition to control broad spectrum of phytopathogenic microorganisms and insect pests.
In yet another object of the present invention is to provide a pesticidal composition resulting in increased yield of the crop.
In yet another object of the present invention is to provide a pesticidal composition comprising an insecticidal and fungicidal combination that causes an enhanced insecticidal and fungicidal activity.
SUMMARY OF THE INVENTION
One aspect of the present invention is to provide a pesticidal composition comprising combination of an insecticide and a fungicide.
Another aspect of the present invention is to provide a pesticidal comprising combination of broad-spectrum insecticide and an acylalanine fungicide.
Another aspect of the present invention is to provide a pesticidal composition comprising combination of Fipronil and Metalaxyl.
Yet another aspect of the present invention is to provide a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil and Metalaxyl with one or more agrochemical additives.
Yet another aspect of the present invention is to provide a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil present in a range from 10% to 50% (w/w), Metalaxyl is present in a range from 10% to 50% (w/w) and other agrochemical additives.
Yet another aspect of the present invention, the pesticidal composition comprises one or more agrochemical additives selected from the group comprising, a wetting agent, a dispersing agent, a pigment, a rheology modifier, an adjuvant and a filler.
Yet another aspect of the present invention is to provide a water dispersible powder for slurry seed treatment (WS) composition comprising of:
a) Fipronil present in a range from 10% to 50% (w/w),
b) Metalaxyl present in a range from 10% to 50% (w/w),
c) wetting agent present in a range from 1% to 5% (w/w),
d) dispersing agent present in a range from 1% to 5% (w/w),
e) pigment present in a range from 0.5 % to 3% (w/w),
f) adjuvant or rheology modifier present in a range from 1% to 3% (w/w), and
g) filler present in a range from 1% to 75% (w/w).
Yet another aspect of the present invention is to provide a water dispersible powder for slurry seed treatment (WS) composition comprising of:
a) Fipronil is present in an amount of 40% (w/w),
b) Metalaxyl is present in an amount of 40% (w/w),
c) dialkyl naphthalene sulphonate sodium salt is present in an amount of 3% (w/w),
d) sodium ligno sulphonate is present in an amount of 3% (w/w),
e) permanent rubine L5B-01 is present in an amount of 1% (w/w),
f) amino acids present is present in an amount of 3% (w/w), and
g) china clay is present in an amount of 10% (w/w).
In yet another aspect of the present invention is to provide a process for the preparation of a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil and Metalaxyl with one or more agrochemical additives.
In yet another aspect of the present invention is to provide a process for the preparation of a water dispersible powder for slurry seed treatment (WS) composition, wherein the process comprising steps of:
a) weighing and mixing all the raw material in a pre-blender and mix it for 1 hour,
b) milling the sample through air jet mill instrument (Inlet pressure 2-3 kg/cm2) and grinding (pressure 6 kg/ cm2) to get the desired particle size < 15 micron,
c) collecting the Milled material, and post blending it for 1 hour,
d) packing the formulated material in a TLP (Triple laminated pouch).
The present invention relates to pesticidal composition with synergistic activity. The composition contains three components that mutually complement each other when used together and exhibit activity that is greater than the activities of individual components when used alone.
DESCRIPTION OF THE INVENTION
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.
The novel pesticidal composition of the present invention may be formulated as Granular composition (GR), 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) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), 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). Preferable composition of the present invention is water dispersible powder for slurry seed treatment (WS).
In addition, by treating the pesticidal composition of the present invention in the soil, it becomes possible to simultaneously control pests inhabiting the soil and pests inhabiting the ground. In addition, in this method, since the dosage and the number of times of application of the active ingredient are reduced and the long-lasting effect is long, it is possible to provide a comprehensive control method.
The present invention provides a combination of an insecticide and a fungicide that possess an enhanced efficacy over the individual active compound used in isolation.
One embodiment of the invention provides a pesticidal composition comprising combination of broad-spectrum insecticide and an acylalanine fungicide.
Another embodiment of the present invention provides a pesticidal composition comprising combination of Fipronil and Metalaxyl with one or more agrochemical additives.
Yet another embodiment of the present invention provides a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil and Metalaxyl with one or more agrochemical additives.
Yet another embodiment of the present invention provides a water dispersible powder for slurry seed treatment (WS) composition comprising of:
a) Fipronil is present in a range from 10% to 50% (w/w),
b) Metalaxyl is present in a range from 10% to 50% (w/w),
c) wetting agent is present in a range from 1% to 5% (w/w),
d) dispersing agent is present in a range from 1% to 5% (w/w),
e) pigment is present in a range from 0.5 % to 3% (w/w),
f) adjuvant or rheology modifier is present in a range from 1% to 3% (w/w), and
g) filler is present in a range from 1% to 75% (w/w).
Yet another embodiment of the present invention provides a water dispersible powder for slurry seed treatment (WS) composition comprising of:
a) Fipronil is present in an amount of 40% (w/w),
b) Metalaxyl is present in an amount of 40% (w/w),
c) dialkyl naphthalene sulphonate sodium salt is present in an amount of 3% (w/w),
d) sodium ligno sulphonate is present in an amount of 3% (w/w),
e) permanent rubine L5B-01 is present in an amount of 1% (w/w),
f) amino acids present is present in an amount of 3% (w/w), and
g) china clay is present in an amount of 10% (w/w).
Yet another embodiment of the present invention provides a pesticidal composition comprises one or more agrochemical additives selected from the group comprising, a wetting agent, a dispersing agent, a pigment, a rheology modifier, an adjuvant and a filler.
The wetting agent is a compound that facilitates rapid wetting of the powder when added to the water. The wetting agent employed in the formulation composition is selected from the group consisting of non-ionic surfactants, anionic surfactant and a mixture of anionic and non-ionic surfactant and polymeric surfactant.
Wetting agent is selected from the group comprising of alkylnaphthalene sulfonate condensate (ANS) blend, dialkyl naphthalene sulphonate sodium salt, linear alcohol derivative, and polyethylene glycol nonyl phenyl ether ammonium sulfate.
Dispersing agent is a chemical substance, which is typically a surfactant, that is added to a suspension of solid or liquid particles in a liquid (such as a colloid or emulsion) to improve the separation of the particles and to prevent their settling or clumping. They can disperse active ingredients in the formulation and prevent agglomeration after dispersal in water.
The dispersing agent is selected from the group comprising of sodium poly alkyl naphthalene sulphonate, phenol sulfonic acid-formaldehyde, phenol sulfonic acid-formaldehyde polycondensation as sodium salt, acrylic copolymer, sodium salt of methyl naphthalene sulfonate, sodium polycarboxylate, sodium methyl oleoyl taurate, sodium ligno sulphonate and sodium lauryl sulphate or combination thereof.
Pigments are insoluble and are applied not as solutions but as finely ground solid particles mixed with a liquid. The suitable pigment of the present invention is Permanent Rubin L5-B-01 (12-Hydroxystearic acid, oligomers, reaction products with stearic acid).
Rheology modifiers are sometimes referred to as thickeners or viscosity modifiers, but they do much more than just thicken a formulation. A good rheology modifier structures the formulation but when a force is applied it becomes flowable and easily poured. Flowable formulations require a rheology modifier to prevent sedimentation phenomena. Rheology modifiers produce a “three-dimensional” gel network in the continuous phase resulting in a non-Newtonian fluid, which provides stability to the formulation. The rheology modifier must give high viscosity, so the product does not separate during long-term storage but still allow the product to be easily poured from the package. The suitable rheology modifier of the present invention is silicon dioxide.
Adjuvants are materials added to crop protection products or agrochemicals to enhance the efficacy of active ingredients and improve the overall performance of the product. The suitable adjuvant of the present invention is amino acids.
Filler refers to solid chemicals that are added to an herbicide formulation to aid in the delivery of the active ingredient. Filler is selected from the group comprising of, but not limited to, natural minerals such as corn starch, lactose monohydrate, quartz, talc, kaolin, pyrophyllite, montmorillonite, attapulgite, bentonite clay, china clay, kieselguhr, chalk, zeolite, calcite, sericite, acid clay, diatomaceous earth, natural rock, Fuller’s earth, meerschaum, gibbsite, dolomite or pumice; synthetic minerals such as precipitated silica, fumed silica, sodium silicate, alumina, aluminum silicate, aluminum hydroxide; inorganic salts such as calcium carbonate, ammonium sulfate or other ammonium salts, sodium sulfate, potassium chloride. The suitable filler of the present invention is china clay.
In yet another embodiment of the present invention provides a process for the preparation of a water dispersible powder for slurry seed treatment (WS) composition comprising of Fipronil, and Metalaxyl with one or more agrochemical additives.
In yet another embodiment of the present invention provides a process for the preparation of a water dispersible powder for slurry seed treatment (WS) composition, wherein the process comprising steps of:
a) weighing and mixing all the raw material in a pre-blender and mix it for 1 hour,
b) milling the sample through air jet mill instrument (Inlet pressure 2-3 kg/cm2) and grinding (pressure 6 kg/ cm2) to get the desired particle size < 15 micron,
c) collecting the Milled material, and post blending it for 1 hour,
d) packing the formulated material in a TLP (Triple laminated pouch).
The composition of the present invention and method provided may be utilized to control weeds or battle undesired vegetation in crops or other settings, including but not limited to cereals, such Maize, soyabeans, wheat, triticale, and industrial vegetation management. Preferably, the undesirable vegetation includes species from the families of broadleaved and grass weeds, more preferably from the families of Aeschynomene, Ageratum, Amaranthus, Bidens, Brachiaria, Cenchrus, Cyperus, Digitaria, Echinochloa, Eclipta, Eleusine, Eragrostis Fimbristylis, Galinsoga, Ischaemum, Leptochloa, Monochoria, Panicum, Paspalum, Polygonum, Portulaca, Richardia, Sesbania, Setaria, Sida, Sorghum, most preferably Echinochloa, Leptochloa, Ischaemum, Monochoria, and Cyperus, or combinations thereof. It has been surprisingly found that the novel herbicidal composition of the present invention delays the appearance of the resistant strains of weeds and achieves effective and economical control of undesired weeds.
The composition achieves improved biological activity by enhancing overall control of weeds over a shorter period. Additional benefits of using the herbicidal composition of the present invention includes reduced risk of occupational hazard, lower cost of application, better cost: benefit ratio to the end user, reduced fuel, and labor cost, saving in applicator’s time and loss caused by mechanical damage to the crop and soil.

The present compositions can be applied to the undesirable vegetation and/or weeds or their locus using conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation or paddy water, and by other conventional means known to those skilled in the art.
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: Fipronil 40% + Metalaxyl 40% (WS)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 40.0
2. Metalaxyl Fungicide 40.0
3. Dialkyl naphthalene sulphonate sodium salt Wetting agent 3.0
4. Sodium Ligno sulphonate Dispersing agent 3.0
5. Permanent Rubin L5-B-01 Pigment 1.0
6. Amino acids adjuvant 3.0
7. China clay Filler 10.0
Total 100

Manufacturing process:
All the raw materials were weighed, dispensed and mixed in a pre-blender for 1 hour. The mixture was passed through air jet milling instrument, inlet pressure 2-3 kg/cm2 and grinding pressure - 6kg/cm2 to get the desired particle size D90 < 15 microns. The milled material was collected and packed in a triple laminated pouch.

Example-2: Fipronil 10% + Metalaxyl 10% (WS)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 10.0
2. Metalaxyl Fungicide 10.0
3. Permanent Rubin L5-B-01 Pigment 0.5
4. Alkylnaphthalene sulfonate (ANS) condensate blend Wetting agent 5.0
5. phenol sulfonic acid-formaldehyde-polycondensation as sodium salt Dispersing agent 3.0
6. China clay Filler 71.5
Total 100

Manufacturing process:
All the raw materials were weighed, dispensed and mixed in a pre-blender for 1 hour. The mixture was passed through air jet milling instrument, inlet pressure 2-3 kg/cm2 and grinding pressure - 6kg/cm2 to get the desired particle size D90 < 15 microns. The milled material was collected and packed in a triple laminated pouch.

Example-3: Fipronil 20% + Metalaxyl 20% (WS)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 20.0
2. Metalaxyl Fungicide 20.0
3. Permanent Rubin L5-B-01 Pigment 2.0
4. Sodium salt of methyl naphthalene sulfonate Dispersing agent 2.5
5. phenol sulfonic acid-formaldehyde-polycondensation as sodium salt Dispersing agent 2.5
6. China clay Filler 53.0
Total 100

Manufacturing process:
All the raw materials were weighed, dispensed and the mixture were mixed in a pre-blender for 1 hour. The mixture was passed through air jet milling instrument, inlet pressure 2-3 kg/cm2 and grinding pressure - 6kg/cm2 to get the desired particle size D90 < 15 microns. The milled material was collected and packed in a triple laminated pouch.

Example-4: Fipronil 30% + Metalaxyl 30% (WS)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 30.0
2. Metalaxyl Fungicide 30.0
3. Permanent Rubin L5-B-01 Pigment 3.0
4. Linear Alcohol Derivative Wetting agent 4.5
5. Sodium polycarboxylate Dispersing agent 2.5
6. Silicon dioxide, Rheology modifier 2.5
7. China clay Filler 27.5
Total 100

Manufacturing process:
All the raw materials were weighed, dispensed and mixed in a pre-blender for 1 hour. The mixture was passed through air jet milling instrument, inlet pressure 2-3 kg/cm2 and grinding pressure - 6kg/cm2 to get the desired particle size D90 < 15 microns. The milled material was collected and packed in a triple laminated pouch.

Example 5: Fipronil 45% + Metalaxyl 45% (WS)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 45.0
2. Metalaxyl Fungicide 45.0
3. Permanent Rubin L5-B-01 Pigment 1.0
4. Sodium Ligno sulphonate Dispersing agent 3.0
5. Sodium lauryl sulphate Dispersing agent 1.0
6. Silicon dioxide Rheology modifier 2.5
7. China clay Filler 2.5
Total 100

Manufacturing process:
All the raw materials were weighed, dispensed and mixed in a pre-blender for 1 hour. The mixture was passed through air jet milling instrument, inlet pressure 2-3 kg/cm2 and grinding pressure - 6kg/cm2 to get the desired particle size D90 < 15 microns. The milled material was collected and packed in a triple laminated pouch.

SYNERGY STUDIES:
After calculating % disease control, the synergism was calculated by below formula:
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 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 is as follows, *(Jerry Flint et al, 1988)***

If A1 = the percent inhibition of growth by pesticide A at given rate
B1 = the percent inhibition of growth by pesticide B at given rate then,
B1 (100 – A1)
E = A1 +
100
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.)
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

FIELD BIO-EFFICACY TRIALS:

Trial 1: Bio-efficacy against Tomato root rot:
The late blight is caused by the Oomycete group of fungal pathogen Phytophthora nicotianae. The Phytophthora nicotianae is recorded from tomato from Australia, American Samoa, Cook Islands, Federated States of Micronesia, Fiji, Papua New Guinea, and Samoa. Phytophthora nicotianae is also reported on other hosts from Australia, American Samoa, Cook Islands, Federated States of Micronesia, Fiji, New Caledonia, Niue, Papua New Guinea, Samoa, Tonga, and Wallis & Futuna.
Major hosts for the diseases are tomato, passionfruit, bele (Fiji). Note, that the oomycete (water molds) causes a similar disease on capsicum, citrus, papaya, pineapple, and tobacco. A dark-brown rot develops in the taproot and lower stem (called the crown). Brown areas of rot may develop on the stem above and below soil level. Eventually, these areas of rot girdle the stems and roots. As the roots rot the plants wilt and die. Low hanging fruit or those touching the soil become infected by greyish-green rots, which expand quickly and show broad dark rings. The skin of the fruit stays firm at first. Under humid conditions white cottony growth of the oomycete develops on the surface of the fruit. Later, the fruit develops soft rots as bacteria and fungi invade. Water molds survive in the soil as thick-walled resting spores called 'chlamydospores'. When conditions are right, the chlamydospores germinate and produce spores called 'sporangia'. Another spore is produced inside the sporangia called 'zoospores', and these are capable of swimming short distances in the water between soil particles. If they reach the root or stem, they infect, and the disease begins. The water molds spreads in rain splash, surface water, in water within the soil, and in soil on machinery and shoes over long distances.
The field trial was conducted to evaluate the efficacy of innovative mixtures of Fipronil and Metalaxyl against phytophthora root rot fungus in tomato crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Tomato crop was raised with all standard agronomic practices. Seed treatment was done with slurry method by preparing 10 ml slurry volume of chemical at the time of sowing and transplanting.
The visual observations were recorded for % disease control from ten plants per plot. The observations were recorded at 07 DAA (Days after application) and 14 DAA (Days after application).

Table 1: % Root rot disease control in Tomato:
Compositions Dose (gram active per hectare) Percent disease control – Phytophthora Spp.
07 DAA 14 DAA
Fipronil 40% + Metalaxyl 40% (WS) 8 85 80
Metalaxyl 4 75 60
Fipronil 4 00 00
WS – Water-dispersible powders for slurry seed treatment and DAA - Days after application.

The trial results show excellent efficacy of Fipronil 40% + Metalaxyl 40% (WS) against root rot disease of tomato. The solo application of two active ingredients tested here, were not able to provide satisfactory control of root rot disease. The combination of Fipronil + Metalaxyl found very promising against tomato root rot in terms of efficacy as well as residual control.

Table 2: Percent late blight disease control at 14 DAA:
Compositions Dose
(g or ml/ha) % Late blight disease control
Actual
Metalaxyl 4 60
Fipronil 4 50
Fipronil 40% + Metalaxyl 40% (WS) 8 80
Ratio of O/E 1.33

The results in table 2 clearly demonstrates synergy between Fipronil and Metalaxyl in controlling root rot disease in tomato. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.

Trial 2: Bio-efficacy against tomato leaf minor:
The tomato leaf miner (Tuta absoluta), a major pest of field- and greenhouse-grown tomatoes, belongs to the family of Gelechiidae. It is oligophagous, feeding mainly on Solanaceae species. The main host is tomato, but it also feeds on other solanaceous crop plants including potato, eggplant, capsicum pepper and tobacco as well as weeds such as Datura stramonium, Lycium chilense, and Solanum nigrum.
The most distinctive symptoms of damage done by the tomato leaf miner (Tuta absoluta) are the blotch-shaped mines in the leaves. Caterpillars prefer leaves and stems, but they may also occur underneath the crown of the fruit and even inside the fruit itself. On leaves, the larvae only feed on mesophyll tissues, leaving the epidermis intact. Fruits can be attacked as soon as they are formed but the larvae only feed on green fruits. In case of serious infection, leaves die off completely. Mining by the caterpillar causes malformations.
Damage to fruit allows fungal diseases to enter, leading to rotting fruit before or after harvest.
The field trial was conducted to evaluate the efficacy of innovative mixtures of metalaxyl and Fipronil against leaf miner in Tomato crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Tomato crop was raised with all standard agronomic practices. Seed treatment was done with slurry method by preparing 10 ml slurry volume of chemical at the time of sowing and transplanting.

The visual observations were recorded for % pest damage from ten plants per plot. The observations were recorded at before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 3: % leaf minor control in Tomato:
Compositions Dose
(g AI/ha) % Control – Tomato pod borer
07 DAA 14 DAA
Fipronil 40% + Metalaxyl 40% (WS) 8 85 80
Metalaxyl 4 72 64
Fipronil 4 75 65
WS – Water-dispersible powders for slurry seed treatment, and DAA - Days after application.

The trial results show excellent efficacy of Fipronil 40% and Metalaxyl 40% (WS) against leaf minor of Tomato. The solo application of two active ingredients tested here were also not able to provide satisfactory control of Tomato leaf minor. The combination of Fipronil and Metalaxyl found very promising against Tomato leaf minor in terms of efficacy as well as residual control.

Table 4: Percent leaf minor control at 14 DAA:
Compositions Dose
(g or ml/ha) % Late blight disease control
Actual
Metalaxyl 4 50
Fipronil 4 65
Fipronil 40% + Metalaxyl 40% (WS) 8 85
Ratio of O/E 1.23

The results in table 4 clearly demonstrates synergy between Fipronil and Metalaxyl in controlling Tomato Thrips. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.

Trial 3: Bio-efficacy against tomato fruit borer:

The tomato fruit borer (Helicoverpa armigera), Fruit borer is one of the serious pests of tomato. It is polyphagous pest. The moth of this insect is of medium size yellowish brown in colour. The caterpillars are light yellow in colour & there are light yellow stripes on both sides on the dorsal part of the body.

This pest damages the tomato crop from fruit formation till the last harvest. Fruit borer of tomato can attack the crop anytime throughout the year. The caterpillar of this pest pierces the fruit and eats the pulp of the fruit. These caterpillars are seen hanging halfway out of the fruit. The holes made on the fruits are round and only the upper part inside the hole is eaten by these pests. One larva can damage many fruits. These caterpillars damage the leaves as well as the fruits. The fruit on which this caterpillar bores, there is an outbreak of mildew on it and the fruit rots completely. Such damaged tomatoes are not edible.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Fipronil and Metalaxyl against fruit borer in Tomato crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Tomato crop was raised with all standard agronomic practices. Seed treatment was done with slurry method by preparing 10 ml slurry volume of chemical at the time of sowing and transplanting.

The visual observations were recorded for % pest damage from ten plants per plot. The observations were recorded at before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 5: % leaf minor control in Tomato:
Compositions Dose
(g AI/ha) % Control – Tomato pod borer
07 DAA 14 DAA
Metalaxyl 40% + Fipronil 40% (WS) 8 90 80
Metalaxyl 4 75 69
Fipronil 4 80 70
WS - Water-dispersible powders for slurry seed treatment, and DAA - Days after application.

The trial results show excellent efficacy of Fipronil 40% and Metalaxyl 40% (WS) against fruit borer of Tomato. The solo application of two active ingredients tested here were also not able to provide satisfactory control of Tomato leaf minor. The combination of Fipronil and Metalaxyl found very promising against Tomato fruit borer in terms of efficacy as well as residual control.

Table 6: Percent fruit borer control at 14 DAA:
Compositions Dose (g or ml/ha) % Late blight disease control
Actual
Metalaxyl 4 54
Fipronil 4 70
Metalaxyl 40% + Fipronil 40% (WS) 8 83
Ratio of O/E 1.14

The results in table 6 clearly demonstrates synergy between Fipronil and Metalaxyl in controlling Tomato fruit borer. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.
The pesticide combination of Fipronil + Metalaxyl provided excellent control of Tomato Phytophthora root rot, leaf minor and fruit rot disease and pests. The same combination had shown synergistic effect on insect and disease control in Tomato. ,CLAIMS:WE CLAIM:
1. A pesticidal composition comprising a combination of broad-spectrum insecticide Fipronil, and an acylalanine fungicide Metalaxyl with one or more agrochemical additives.

2. The composition as claimed in claim 1, wherein the agrochemical additives selected from a wetting agent, dispersing agent, a pigment, a rheology modifier, an adjuvant and a filler.

3. The composition as claimed in claim 1, wherein the composition is formulated as a water dispersible powder for slurry seed treatment (WS) form.

4. The composition as claimed in claims 1-3, wherein water dispersible powder for slurry seed treatment (WS) composition comprising of:
a) Fipronil present in a range from 10% to 50% (w/w),
b) Metalaxyl present in a range from 10% to 50% (w/w),
c) wetting agent present in a range from 1% to 5% (w/w),
d) dispersing agent present in a range from 1% to 5% (w/w),
e) pigment present in a range from 0.5 % to 3% (w/w),
f) adjuvant or rheology modifier present in a range from 1% to 3% (w/w) and
g) filler present in a range from 1% to 75% (w/w).

5. The pesticidal composition as claimed in claim 4, wherein the wetting agent is selected from alkylnaphthalene sulfonate condensate (ANS) blend, dialkyl naphthalene sulphonate sodium salt, linear alcohol derivative, and polyethylene glycol nonyl phenyl ether ammonium sulfate.

6. The pesticidal composition as claimed in claim 4, wherein the dispersing agent is selected from sodium poly alkyl naphthalene sulphonate, phenol sulfonic acid-formaldehyde, phenol sulfonic acid-formaldehyde polycondensation as sodium salt, acrylic copolymer, sodium salt of methyl naphthalene sulfonate, sodium polycarboxylate, sodium methyl oleoyl taurate, sodium ligno sulphonate and sodium lauryl sulphate or combination thereof.

7. The pesticidal composition as claimed in claim 4, wherein the pigment is Permanent Rubin L5-B-01.

8. The pesticidal composition as claimed in claim 4, wherein the rheology modifier is silicon dioxide.

9. The composition as claimed in claim 4, wherein the filler is china clay.

10. The process for preparation of composition as claimed in claim 4, wherein the process comprising steps of:
a) weighing and mixing all the raw material in a pre-blender and mix it for 1 hour,
b) milling the sample through air jet mill instrument (Inlet pressure 2-3 kg/cm2) and grinding (pressure 6 kg/ cm2) to get the desired particle size < 15 micron,
c) collecting the Milled material, and post blending it for 1 hour,
d) packing the formulated material in a TLP (Triple laminated pouch).

Dated this Eleventh (11th) day of March, 2023

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