DESC:FIELD OF THE INVENTION

The present invention relates to a synergistic pesticidal composition comprising of a neonicotinoid and an azole fungicide. Particularly, the present invention relates to synergistic pesticidal composition of nitenpyram and cyproconazole with one or more agrochemical additives in synergistically effective amounts and a process thereof.

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 applies 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.

Nitenpyram is an insecticide used to control various insect pests. It belongs to the class of neonicotinoid insecticides. Nitenpyram acts as an agonist of the nicotinic acetylcholine receptor, affecting cholinergic transmissions in the insect central nervous system. It is a systemic insecticide with translaminar activity. It provides control of aphids, thrips, leafhoppers, whiteflies and other sucking insects in rice and other crops.
Nitenpyram chemically known as (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N'-methyl-2-nitrovinylidenediamine. The structure of nitenpyram is,

Cyproconazole is an agricultural fungicide of the class of azoles, used on cereal crops, coffee, sugar beet, fruit trees and grapes, on sod farms and golf courses and on wood as a preservative. It was introduced to the market by Sandoz in 1994 (now Syngenta as of 2000).

Cyproconazole chemically known as 2-(4-Chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl) butan-2-ol. The structure of cyproconazole is,

In an embodiment of the invention, the present invention provides a synergistic pesticidal composition of an insecticide, and a fungicide.

The mixing of insecticides with fungicides results in incompatibility of physical nature and 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. Inventors of the present invention have surprisingly found the novel synergistic composition of neonicotinoid insecticide nitenpyram, and an azole fungicide cyproconazole with one or more agrochemical additives which allows for broader disease control spectrum.

None of the literature reference discloses a pesticidal combination of neonicotinoid insecticide and an azole fungicide.

SUMMARY OF THE INVENTION

One aspect of the present invention is to provide a synergistic pesticidal composition of an insecticide, and a fungicide.

Another aspect of the present invention is to provide a pesticidal combination of a neonicotinoid insecticide, and an azole fungicide with one or more agrochemical additives.

Yet another aspect of the present invention is to provide an improved stable and ready to use pesticidal composition, having superior bio-efficacy compared to the individual formulations or mixtures.

Yet another aspect of the present invention is to provide a pesticidal composition comprising combination of nitenpyram and cyproconazole with one or more agrochemical additives.
Yet another aspect of the present invention is to provide a pesticidal composition comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w), and
c. agrochemical additives in the range of 10 to 70% (w/w).

Yet another aspect of the present invention is to provide a pesticidal soluble liquid (SL) composition comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. emulsifiers in the range of 10% to 50%,
d. solvent in the range of 30% to 40% (w/w), and
e. co-solvent in the range of 10% to 20% (w/w).
wherein, nitenpyram and cyproconazole are in the weight ratios of 1:0.84.

Yet another aspect of the present invention is to provide a pesticidal soluble liquid (SL) composition comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. castor oil ethoxylate with 36 mole EO in the range of 10% to 30% (w/w),
d. polysorbate in the range of 10% to 20% (w/w),
e. dimethyl amide in the range of 30% to 40% (w/w), and
f. N-methyl-2-pyrrolidone in the range of 10% to 20% (w/w)
wherein, nitenpyram and cyproconazole are in the weight ratios of 1:0.84.
Yet another aspect of the present invention provides a process for preparing soluble liquid (SL) composition of nitenpyram and cyproconazole comprising the steps of:
a. dissolving nitenpyram and cyproconazole in a solvent and co-solvent mixture,
b. adding castor oil ethoxylate, polyoxyethylene sorbitol ester as emulsifiers to obtain a homogenous mixture,
c. passing through filter cloth, and
d. packing the obtained soluble liquid material.

In yet another aspect the present invention provides a pesticidal composition comprising nitenpyram and cyproconazole in form of a wettable powder (WP), or a water-dispersible granule (WDG), or a suspension concentrate (SC), or a suspoemulsion (SE).
The present invention relates to a pesticidal composition with synergistic activity. The composition contains two components that mutually complement each other when used together and exhibit activity that is greater than the activities of individual components when used alone.

The present invention discloses a co-formulation of nitenpyram with cyproconazole which results in synergistic mixture that is more effective than the individual compounds at the considered doses.

DESCRIPTION OF THE INVENTION

The terms "comprise", "comprises", and "comprising" are to be interpreted inclusively rather than exclusively. Likewise, the terms "include", "including", and "or" should all be construed to be inclusive, unless such a construction is clearly prohibited from the context. However, the embodiments provided by the present disclosure may lack any element that is not specifically disclosed herein. Thus, a disclosure of an embodiment defined using the term "comprising" is also a disclosure of embodiments "consisting essentially of” and "consisting of” the disclosed components. Where used herein, the term "example," particularly when followed by a listing of terms, is merely exemplary and illustrative, and should not be deemed to be exclusive or comprehensive. Any embodiment disclosed herein can be combined with any other embodiment disclosed herein unless explicitly indicated 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.

One embodiment of the present invention is to provide a pesticidal composition comprising combination of a neonicotinoid insecticide, and an azole fungicide with one or more agrochemical additives.

Another embodiment of the present invention is to provide a pesticidal composition comprising combination of nitenpyram and cyproconazole with one or more agrochemical additives.

Yet another embodiment of the present invention is to provide a pesticidal composition comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w), and
c. agrochemical additives in the range of 10 to 70% (w/w).

Yet another embodiment of the present invention is to provide a pesticidal soluble liquid (SL) composition comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. emulsifiers in the range of 10% to 50%,
d. solvent in the range of 30% to 40% (w/w), and
e. co-solvent in the range of 10% to 20% (w/w)
wherein, nitenpyram and cyproconazole are in the weight ratios of 1:0.84.
Yet another embodiment of the present invention is to provide a pesticidal soluble liquid (SL) composition comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. castor oil ethoxylate with 36 mole EO in the range of 10% to 30% (w/w),
d. polysorbate in the range of 10% to 20% (w/w),
e. dimethyl amide in the range of 30% to 40% (w/w), and
f. N-methyl-2-pyrrolidone in the range of 10% to 20% (w/w)
wherein, nitenpyram and cyproconazole are in the weight ratios of 1:0.84.
In yet another embodiment the present invention provides a pesticidal composition comprising nitenpyram and cyproconazole in the form of a wettable powder (WP), or a water-dispersible granule (WDG), or a suspension concentrates (SC), or a suspoemulsion (SE).
According to the present invention a wettable powder (WP), or a water dispersible granule (WDG) formulation comprises one or more agrochemical acceptable additives selected from a wetting agent, a dispersing agent, a rheology modifier, and a filler.

According to the present invention a suspension concentrate (SC), or a suspoemulsion (SE) formulations comprises one or more agrochemical acceptable additives selected from a wetting agent, a dispersing agent, an anti-freezing agent, a biocide, a defoamer, a viscosity modifier, an emulsifier, and a base.

The present invention provides a synergistic pesticidal composition comprising a neonicotinoid insecticide, and an azole fungicide with one or more agrochemical additives. One embodiment of the present invention provides the synergistic pesticidal composition comprising nitenpyram and cyproconazole in the weight ratio of 1:1, more preferably in the ratio of 1:0.84. However, variables of the ratio 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.

According to the present invention the emulsifier plays an important role in maintaining the transparency of the composition. The emulsifiers used in the composition allow the active ingredient to keep the suspension in transparency.

Emulsifiers as used herein includes but are not limited to nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers, aliphatic amine alkoxylates, polyoxy ethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty acid amide alkoxylates, fatty acid poly diethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isoforms tridecyl alcohol, fatty acid amides, alkyl poly glycosides, non-ionic surfactant blend (ATLOX 309F), polyoxyethylene (40) sorbitol hexaoleate (ATLOX G-1086), polyacrylate graft copolymer (DISPERSOGEN PSL 100), Castor oil ethoxylate with 36 mole EO (EMULSOGEN 360), Tri-sec-butylphenol polyglycol ether with 4 EO (SAPOGENAT T 040), Ethoxylate of alkyl polyethylene glycol ether (LUTENSOL TO 5), EO/PO butyl ether (Ethylene 500 LQ), polyoxyethylene sorbitol ester (Tween 20) or its combinations thereof.

According to the present invention, the emulsifier used for the present invention can also perform as a surfactant, a dispersant, a foaming agent, or a detergent.

According to the present invention, the solvent may be selected from dimethyl amide, N, N-dimethyl decanamide or N, N-dimethyl octanamide.

According to the present invention, the co-solvent may be selected from N-methyl-2-pyrrolidone (NMP), N, N-dimethyl acetamide (DMAc), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

According to the present invention, the wetting agent may be selected from Sodium isopropyl naphthalene sulfonate (MORWET IP), and fatty alcohol ethoxylate (ATLOX 4894).

According to the present invention, the dispersing agent may be selected from alkyl naphthalene sulfonate condensate (MORWET D-425), Sodium lignosulphonate, polymethyl methacrylate-polyethylene glycol graft copolymer (ATLOX 4913), Alcohols, C12-16, ethoxylated (TERSPERSE 4894), Dispersant emulsifier blend (TERSPERSE 2288), Sodium naphthalene condensate formaldehyde (BORRESPERSE NA) or its combinations thereof.

According to the present invention, the rheology modifier is silicon dioxide, and the filler is maize starch.

According to the present invention, the biocide may be selected from 1,2-Benzisothiazol-3(2H)-one (NIPACIDE BIT 20), and Benzisothiazolin3-one (PROXEL GXL).

According to the present invention, the defoamer is polydimethylsiloxane (SAG 1572), the viscosity modifier is xanthan gum (AGRHOPOL 23W), and the base is water.

A person skilled in art can easily determine the amount of agrochemical additives depending on the composition formulation without any undue experimentation.

In yet another embodiment the present invention provides a process for preparing soluble liquid (SL) composition comprising the steps of:
a. dissolving nitenpyram and cyproconazole in solvent and co-solvent mixture,
b. adding castor oil ethoxylate, polyoxyethylene sorbitol ester as emulsifiers to obtain a homogenous mixture,
c. passing through filter cloth, and
d. packing the material.

Nitenpyram and cyproconazole may be present in the composition or applied in any amounts relative to each other, to provide enhanced or synergistic effect of the mixture.

The pesticidal composition of the present invention may be in different types of formulations. Formulation includes water soluble liquid (SL), an emulsifiable concentrate (EC), an emulsion (EW), a microemulsion (ME), a suspension concentrate (SC), an oil-based dispersion (OD), a flowable suspension (FS), a water soluble powder (WS), a water-dispersible granule (WDG), a water-soluble granule (SG), a water-dispersible powder or wettable powder (WP), a water soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), an aqueous suspoemulsion (SE), a capsule suspension (CS) and a microgranule (MG). Preferably, the synergistic pesticidal composition can be formulated as soluble liquid (SL).

The present invention provides a synergistic pesticidal composition of a neonicotinoid nitenpyram and an azole fungicide cyproconazole possessing an enhanced efficacy over the individual active compound used in isolation.
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 following examples describe 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, which have been particularly effective on bench scale.

EXAMPLES:
Example-1: Composition of nitenpyram 12% and cyproconazole 10% water soluble liquid (SL)

S. No. Ingredients Function Quantity
(in %w/w)
1. Nitenpyram @ 98% (b) 12 % Active Ingredient 12.24
2. Cyproconazole @98 % (b) 10% Active Ingredient 10.2
3. Dimethyl amide Solvent 32.56
4. Emulsogen EL 360
(Castor oil ethoxylate with 36 mole EO) Emulsifier-1 20
5. Tween 20 (polyoxyethylene sorbitol ester) Emulsifier-2 10
6. N-Methyl-2-pyrrolidone Co-solvent 15
Total 100

Manufacturing process:

Nitenpyram and cyproconazole were dissolved in dimethyl amide and N-methyl-2-pyrrolidone solvents. To this clear solution emulsifiers castor oil ethoxylate with 36 mole EO polyoxyethylene sorbitol ester and Tween 20 were added and were mixed in a homogenizer for 60 minutes. The mixture was passed through filter cloth and the material was collected and packed.

Example-2: Composition of nitenpyram 12% and cyproconazole 10% Wettable Powder (WP)

S. No. Ingredients Function Quantity
(in %w/w)
1. Nitenpyram @ 98% (b) 12 % Active Ingredient 12.37
2. Cyproconazole @98 % (b) 10% Active Ingredient 10.41
3. Morwet IP
(Sodium isopropyl naphthalene sulfonate) Wetting agent 2.5
4. Morwet D-425
(Alkyl naphthalene sulfonate condensate) Dispersing agent 5
5. Sodium lignosulphonate Dispersing agent 4
6. Silicon dioxide Rheology modifier 1
7. Maize starch Filler 64.72
Total 100

Manufacturing process:
Nitenpyram, cyproconazole, sodium isopropyl naphthalene sulfonate (Morwet IP), alkyl naphthalene sulfonate condensate (Morwet D-425), sodium lignosulphonate, silicon dioxide and maize starch were blended in a ribbon blender for 15 minutes. This was followed by milling the sample through air jet milling instrument (Inlet pressure - 4kg/cm2 and Grinding pressure - 6kg/ cm2 for milling the sample) and collecting the material and packing (the particle size distribution (PSD) of the milled material should be <10 µ).

Example-3: Composition of nitenpyram 12% and cyproconazole 10% Water dispersible granules (WDG)

S. No. Ingredients Function Quantity (in %w/w)
1. Nitenpyram @ 98% (b) 12 % Active Ingredient 12.37
2. Cyproconazole @98 % (b) 10% Active Ingredient 10.41
3. Morwet IP
(Sodium isopropyl naphthalene sulfonate) Wetting agent 2.5
4. Morwet D-425
(Alkyl naphthalene sulfonate condensate) Dispersing agent 5
5. Sodium lignosulphonate Dispersing agent 4
6. Ammonium sulphate Disintegrating agent 1
7. Maize starch Filler 64.72
Total 100

Manufacturing process:
Nitenpyram, cyproconazole, sodium isopropyl naphthalene sulfonate (Morwet IP), alkyl naphthalene sulfonate condensate (Morwet D-425), sodium lignosulphonate, ammonium sulphate and maize starch were blended in a pre-blender and mixed for 1 hr. This is followed by milling the sample through air jet mill instrument at Inlet pressure 2-3 kg/cm2 and grinding pressure 6 kg/ cm2 and checking the particle size < 12 micron. The milled material was collected and post blended for 1 hr. This was followed by extruding the granules at 35 rpm (1.0 mesh). The granules were collected and dried at 45°C for 30 min. The sample was checked for quality analysis and formulated in suitable packaging.

Example-4: Composition of nitenpyram 12% and cyproconazole 10% Suspension concentrate (SC)

S. No. Ingredients Function Quantity (in %w/w)
1. Nitenpyram @ 98% (b) 12 % Active Ingredient 12.37
2. Cyproconazole @98 % (b) 10% Active Ingredient 10.41
3. Atlox 4894 (Fatty Alcohol Ethoxylate) Wetting agent 1.5
4. Atlox 4913 (polymethyl methacrylate-polyethylene glycol graft copolymer) Dispersing agent 2
5. Propylene Glycol Antifreezing agent 10
6. Nipacide Bit 20
(1,2-Benzisothiazol-3(2H)-one) Biocide 0.1
7. Sag 1572
(Polydimethylsiloxane antifoam emulsion) Defoamer 0.5
8. Xanthan gum Viscosity Modifier 10
9. Water Base 53.12
Total 100

Manufacturing process:

In a pre-mixer, vessel no.1 the fatty alcohol ethoxylate (Atlox 4894), polymethyl methacrylate-polyethylene glycol graft copolymer (Atlox 4913) was added. After 15 min 0.1 parts by weight of Nipacide BIT-20 followed by 0.5 parts of SAG 1572 were added. The mixture was stirred for 15 mins by adding water followed by the addition of Nitenpyram and cyproconazole. The mixture was stirred for homogenization. The wet slurry from the above vessel was passed through dyno-mill at a temperature below 30°C and material was collected in another vessel no.2 (post mixer). Continuous stirring was maintained in both the vessels to avoid sedimentation. The particle size distribution 10 (PSD) of the sample was checked. The PSD of the material should be d90 < 15 µ. If the d90 is higher than > 15 µ then the mixture was grinded till the PSD value complies with the specification. The required quantity of xanthan gum was added to the wet slurry in vessel no.2 and stirred for 3 hrs. for homogenization. The sample was checked for complete analysis and packed in designated bottles.

Example-5: Composition of nitenpyram 12% and cyproconazole 10% Suspoemulsion (SE)

S. No. Ingredients Function Quantity
(in %w/w)
1. Nitenpyram @ 98% (b) 12 % Active Ingredient 12.37
2. Cyproconazole @98 % (b) 10% Active Ingredient 10.41
3. Propylene Glycol Antifreezing agent 6
4. Tersperse 4894 (Alcohols, C12-16, ethoxylated) Dispersing agent 2
5. Tersperse 2288 (Dispersant emulsifier blend) Dispersing agent 2
6. Proxel GXL (Benzisothiazolin3-one) Biocide 0.1
7. SAG 1572 (Polydimethylsiloxane) Defoamer 0.5
8. Borresperse NA (Sodium naphthalene condensate formaldehyde) Dispersing agent 2
9. Emulsogen TS 160 (Tristyryl phenol-polyethylene glycol ether) Emulsifier 2
10. Agrhopol 23W (Xanthan gum) Viscosity Modifier 4
11. Water Base 58.62
Total 100

Manufacturing process:

Propylene glycol and Borresperse NA (sodium naphthalene condensate formaldehyde), alcohols C12-16, ethoxylated (Tersperse 4894), water and 1,2- benzisothiazolin-3-one (Proxel GXL), and polydimethylsiloxane (SAG 1572) were added by stirring. The mixture was stirred for 15 minutes and cyproconazole and Tersperse 2288 was added. The mixture was homogenized. The organic phase was prepared by adding sodium naphthalene condensate formaldehyde, Borresperse NA and heated in a vessel to 40°C and adding nitenpyram by slow stirring. Tristyryl phenol-polyethylene glycol ether (Emulsogen TS 160) was added and stirred for 30 mins. Both the aqueous and organic phases were mixed with stirring. Wet slurry was passed through dyno-mill at temperature less than 35° C and collected in separate vessel. Continuous stirring was maintained in vessels to avoid sedimentation. Sample was analyzed to check the Particle Size distribution (PSD). Milling process was repeated till desired particle size was obtained (i.e d90 < 15 µ). In the next step Agrhopol 23W added in propylene glycol then benzisothiazolin-3-one (Proxel GXL) was added to this slurry into distilled water and stirred the mixture until it gets lumps free homogeneous mixture. This gel was kept for 4-5 hours to get a translucent homogeneous gel. The required quantity of gel was added to the wet slurry prepared above and stirred the mixture for ~3 h for homogenization. Material was packed in a suitable bottle.

Example-6: Composition of nitenpyram 12% and cyproconazole 10% water soluble liquid (SL)

S. No. Ingredients Function Quantity
(in %w/w)
1. Nitenpyram @ 98% (b) 12 % Active Ingredient 12.37
2. Cyproconazole @98 % (b) 10% Active Ingredient 10.41
3. N, N-dimethyl decanamide Solvent 32.22
4. N-methyl-2-pyrrolidinone Co-solvent 15.0
5. 36 mole castor oil ethoxylate Emulsifier-1 20.0
6. Polysorbate 20 (polyoxyethylene (20) sorbitan esters) Emulsifier-2 10.0
Total 100

Manufacturing process:

Nitenpyram and cyproconazole were dissolved in N, N-dimethyl decanamide and N-methyl-2-pyrrolidone solvents. To this clear solution emulsifiers castor oil ethoxylate with 36 mole EO polyoxyethylene sorbitol ester were added and were mixed in a homogenizer for 60 minutes. The mixture was passed through filter cloth and the material was collected and packed.

Example-7: Efficacy study for combination of Cyproconazole 10% + Nitenpyram 12% SL in Rice Sheath blight, and BPH

There is always a co-occurrence of insects and diseases in rice crops. Hence farmers usually do tank-mix insecticide and fungicide. The improper tank mixing sequence of chemicals may lead to incompatibility which adversely affects crop safety and pest control.
Trial 1: Bio-efficacy against rice sheath blight and BPH:
The sheath blight is caused by the fungal pathogen Rhizoctonia solani. This potentially devasting disease can infect rice foliage at any stage of crop development. It is a 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 requires 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 favorable conditions such as warm temperature (28 to 32°C), high humidity (95% or above), and dense stands with a heavily developed canopy.
Two species of planthopper infest rice. These are the brown planthopper (BPH), Nilaparvata lugens (Stal); and the white backed planthopper (WBPH), Sogatella furcifera (Horvath). High population of planthoppers cause leaves to initially turn orange yellow before becoming brown and dry and this is a condition called hopper burn that kills the plant. BPH can also transmit Rice Ragged Stunt and Rice Grassy Stunt diseases. Neither disease can be cured. Planthoppers can be a problem in rainfed and in irrigated wetland environments. It also occurs in areas with continuous submerged conditions in the field, high shade, and humidity. Closed canopy of the rice plants, densely seeded crops, excessive use of nitrogen, and early season insecticide spraying also favors insect development.
Hopper burn is like the feeding damage or "bug burn" caused by the rice black bug. To confirm hopper burn caused by planthoppers, the presence of sooty molds at the base of the plant is checked. The feeding damage caused by planthoppers results in the yellowing of the plants. At high population density, hopper burns, or complete drying of the plants is observed. At this level, crop loss may be 100%.
The field trial was conducted to evaluate the efficacy of innovative mixtures of Cyproconazole and Nitenpyram against sheath blight and BPH in rice crop. The trial was conducted with randomized block design with net plot size of 5m x 6m. Rice crops were 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 and insect 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: Percent Sheath blight disease control in rice:
Compositions Dose
(g AI/ha) Percent disease control – rice sheath blight
07 DAA 14 DAA
Cyproconazole 10% + Nitenpyram 12% SL 220 95 90
Cyproconazole 10% SL 100 90 80
Nitenpyram 25% SP 120 85 70
SL – soluble liquid, SP-soluble powder, and DAA - Days after application.

The trial results in Table 1 shows that excellent efficacy of premix sample of Cyproconazole 10% + Nitenpyram 12% observed against sheath blight disease of rice as compared to solo treatments.

Table 2: Percent BPH control in rice:
Compositions Dose
(g AI/ha) % Control – rice BPH
07 DAA 14 DAA
Cyproconazole 10% + Nitenpyram 12% SL 220 95 90
Cyproconazole 10% SL 100 45 25
Nitenpyram 25% SP 120 85 75
SL – soluble liquid, SP-soluble powder, and DAA - Days after application.

The trial results in Table 2 shows that excellent efficacy of premix sample of Cyproconazole 10% and Nitenpyram 12% observed against BPH in rice as compared to solo treatments.

SYNERGY STUDIES:

After calculating % disease & insect control, the synergism was calculated.

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 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

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.)

Table 3: Percent sheath blight disease control at 14 DAA

Compositions Dose
(g or ml/ha) % Sheath blight disease control
Actual
Cyproconazole 10% SL 100 80
Nitenpyram 25% SP 120 70
Cyproconazole 10% + Nitenpyram 12% SL 220 90
Ratio of O/E 1.13

SL – soluble liquid, SP-soluble powder, and DAA - Days after application.

Table 4: Percent BPH control at 14 DAA

Compositions Dose
(g AI/ha) % Control – rice BPH
Actual
Cyproconazole 10% SL 100 25
Nitenpyram 25% SP 120 75
Cyproconazole 10% + Nitenpyram 12% SL 220 90
Ratio of O/E 1.2
SL – soluble liquid, SP-soluble powder, and DAA - Days after application.

The results in tables 3 & 4 clearly demonstrate that premix sample of Cyproconazole 10% and Nitenpyram 12% SL helps in controlling both rice sheath blight disease and BPH in rice. The large O/E difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.

The above description is for the purpose of illustrating and not limiting the present invention and teaching the person of ordinary skill in the art how to practice the invention. It is not intended to detail all those obvious modifications and variations of it which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention as defined in the appended claims. The claims are meant to cover the claimed components and steps in any sequence which is effective to meet the objectives there intended unless the context specifically indicates the contrary. ,CLAIMS:We claim:

1. A pesticidal synergistic composition comprising neonicotinoid insecticide, and an azole fungicide with one or more agrochemical additives.
2. The pesticidal composition as claimed in claim 1, wherein the neonicotinoid insecticide is nitenpyram and azole fungicide is cyproconazole.
3. The pesticidal composition as claimed in claim 1 and claim 2, wherein the nitenpyram is present in a range from 10% to 15% (w/w), cyproconazole is present in a range from 10% to 20% (w/w) and agrochemical additives present in the range from 10% to 70% (w/w).
4. The pesticidal composition as claimed in claim 1, wherein the agrochemical additives are selected from a wetting agent, a dispersing agent, a rheology modifier, an antifreezing agent, a biocide, a defoamer, a viscosity modifier, a emulsifier, a solvent, a co-solvent, a filler, and base.
5. The pesticidal composition as claimed in claim 1, wherein the composition formulation is selected from water soluble liquid (SL), wettable powder (WP), water-dispersible granule (WDG), suspension concentrates (SC), and suspoemulsion (SE).
6. The pesticidal composition as claimed in claim 3, wherein the composition formulation is a water-soluble liquid (SL) comprising:
a. nitenpyram in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w), and
c. emulsifiers in the range of 10% to 50% (w/w),
d. solvent in the range of 30% to 40% (w/w), and
e. co-solvent in the range of 10% to 20% (w/w).
wherein, nitenpyram and cyproconazole are in the weight ratios of 1:0.84.
7. The pesticidal composition as claimed in claim 6, wherein the emulsifier is selected from the group comprising castor oil ethoxylate with 36 mole EO (Emulsogen EL 360), polyoxyethylene (20) sorbitan esters (Polysorbate 20), polyoxyethylene sorbitol ester (Tween 20) or its combinations thereof.
8. The pesticidal composition as claimed in claim 6, wherein the solvent is selected form dimethyl amide, N, N-dimethyl decanamide or N, N-dimethyl octanamide.
9. The pesticidal composition as claimed in claim 6, wherein the co-solvent is selected from N-methyl-2-pyrrolidone (NMP), N, N-dimethyl acetamide (DMAc), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).
10. A process for preparing pesticidal composition as claimed in claim 6, wherein preparing soluble liquid (SL) composition comprising the steps of:
a. dissolving nitenpyram and cyproconazole in a solvent and co-solvent mixture,
b. adding castor oil ethoxylate, polyoxyethylene sorbitol ester as emulsifiers to obtain a homogenous mixture,
c. passing through filter cloth, and
d. packing the material.