FIELD OF THE INVENTION:
The present invention relates to the field of agrochemicals. The invention in particular relates to pesticidal combination, process for simultaneous control of insects and fungal pests in agricultural crops.
BACKGROUND OF THE INVENTION:
Damage to economically important plants and crops caused by various pests including insects, weeds, fungus, bacteria, virus, rodents, nematodes and other pests greatly impair the productivity and at some instances destroy the crop completely. At certain instances, plants also may suffer from simultaneous or subsequent attack by various kinds of pests for instance an insect pest and a plant disease. Since each pest has its unique mechanism of damaging the plant crop, specific active ingredient may be required to control a target pest especially under the circumstances of concurrent attack by the different kind of pests.
Few prior arts disclose certain pesticidal compositions comprising insecticidal active ingredient and fungicidal active ingredient. For instance, WO2008003738A1 discloses a pesticidal composition comprising a pyridylethylbenzamide derivative, insecticidal compounds and fungicidal compounds. But WO2008003738A1 fails to disclose synergistic effect of particular combination of pyridylethylbenzamide derivative, insecticidal compounds and fungicidal compounds.
WO2008135480 discloses a method for controlling specific fungal pathogen in soybeans by employing benodanil. It discloses a laundry list of fungicides comprising azacona-zole, bitertanol, bromuconazole, cypro-conazole, difenoconazole, diniconazole, diniconazole-M, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tri-adimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole and oxpoconazol. However, WO2008135480 fails to disclose the effective concentration and specific combination of insecticidal and fungicidal active ingredients.

None of the prior art documents therefore disclose a combination comprising the insecticidal-fungicidal mix aimed at delivering the simultaneous and effective control of both fungus and insect pests in agricultural crops. Therefore, there arises a need to develop a pesticidal combination that delivers a simultaneous and enhanced control of both the insect and fungal pests attacking the economically important crops.
OBJECT OF THE INVENTION
An object of the present invention is to provide novel and synergistic pesticidal combination that provides simultaneous control of a specific insect and a specific fungal pest in agricultural crops.
SUMMARY OF THE INVENTION
The present invention provides a novel and synergistic pesticidal combination that provides simultaneous control of insect and fungal pests in agricultural crops. The combination of the present invention may comprise insecticides in combination with fungicides which provides a multipronged approach for management of crop infestations. The present invention also discloses compositions comprising the combination of the present invention and agricultural use of the combination and composition of the present invention
DETAILED DESCRIPTION OF THE INVENTION:
Those skilled in the art will be aware that the invention described herein is subject to variations and modifications other than those specifically described. It is to be understood that the invention described herein includes all such variations and modifications. The invention also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of any two or more of said steps or features.
In an embodiment, the present invention discloses a pesticidal combination comprising at least two insecticidal active ingredients and at least one fungicidal active ingredient.
The present invention discloses a synergistic pesticidal combination wherein said combination comprises:

a) At least one insecticide belonging to the group of neonicotinoids;
b) At least one insecticide belonging to the group of pyridines azomethines;
c) At least one fungicide belonging to the group of triazole fungicides.
The insecticidal active ingredients of present invention may be selected from a group comprising neonicotinoids including but not limited to Acetamiprid, Clothianidin, Imidacloprid, Nitenpyram, Nithiazine, Dinotefuran, Thiacloprid and Thiamethoxam. Preferably the insecticide active ingredients are Nitenpyram.
Nitenpyram, known by its CAS NUMBER: 150824-47-8 and IUPAC name (lE)-N-((6-chloro-3-pyridinyl) methyl)-N-ethyl-N-methyl-2-nitro-1,1- ethenediamine is represented by the chemical structure below.
Nitenpyram is a pale yellow crystalline solid in its solid form. It is a systemic insecticide that belongs to the chemical class of neonicotinoids. It acts as primarily against hemipteran but also with some activity against thysanoptera. As other neonicotinoids, Nitenpyram is an agonist of the nicotinic acetylcholine receptors it has systemic mode of action with trans- laminar activity. It possesses stomach and contact action affecting the insect nervous system.
It however does not show any long-term activity. It is largely used to kill external parasites in livestock and domestic pets but also used to control sucking insects on rice and in greenhouse crops. Example of pests controlled by this chemical include aphids, thrips, whitefly, fleas and ticks.
The insecticidal active ingredients of present invention may be selected from a group comprising at-least one insecticide belonging to the group of pyridines azomethines, preferably the compound is pymetrozine.

Pymetrozine, having the CAS NUMBER: 123312-89-0 also known as 6-methyl-4-[(E)-pyridin-3-ylmethylideneamino]-2,5-dihydro-l,2,4-triazin-3-one and represented by the figure below is a relatively new insecticide.
It is highly active and specific against sucking insect pests. Pymetrozine is the only representative of the pyridine azomethines, a comparatively new class of insecticides, and is being developed worldwide for control of aphids and whiteflies in field crops, vegetables, ornamentals, cotton, hop, deciduous fruit, and citrus, and for the control of plant hoppers in rice. Pymetrozine technical is a crystalline granular in its solid state with a melting point of 217°C (decomp.). The mode of action of pymetrozine in insects has not been precisely determined biochemically, but it may involve effects on neuro-regulation or nerve-muscle interaction. Physiologically, it appears to act by preventing these insects from inserting their stylus into plant tissue, thus inhibiting the insects to feed themselves.
The fungicidal active ingredients may be selected from triazole compound including but not
limited to azaconazole, bromuconazole, cyproconazole, diclobutrazol, difenoconazole,
diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol,
furconazole, hexaconazole, imibenconazole, Ipconazole, ipfentrifluconazole,
mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, uniconazole, triticonazole. Preferably the fungicidal active ingredients are tebuconazole
Tebuconazole, with CAS No 107534-96-3 also represented as l//-l,2,4-Triazole-l-ethanol, a-[2-(4-chlorophenyl)ethyl]-a-(l,l-dimethylethyl)-is a fungicide of the triazole . Its chemical structure is as below:

Tebuconazole is a triazole fungicide used agriculturally to treat plant pathogenic fungi. It acts as a systemic fungicide. It acts as a Demethylase inhibitor (DMI) - by interfering in the process of building the structure of the fungal cell wall. Finally, it inhibits the reproduction and further growth of the fungus. It offers an effective and reliable solution against a wide spectrum of diseases in many crops by protective, curative and eradicative action.
The pesticidal combination of the present invention may comprise insecticidal active ingredients in the range 1-100% and fungicidal active ingredient in the range of 1-75% w/w.
The pesticidal combination of the present invention preferably comprise
(a) Nitenpyram in the range of 1-30%, w/w of the total weight, preferably l-28%w/w, more preferably 1-25% w/w of the combination,
(b) Pymetrozine is in the range of 1-60% w/w, preferably 1-58% w/w, more preferably 1-55% w/w, of the total weight of the combination.
(c) Tebuconazole is in the range of 1-75% w/w, preferably 1-50% w/w, more preferably 1-45% w/w, of the total weight of the combination. The synergistic pesticidal combination may be present in the ratio 1:1:1 to 1:3:3
In another embodiment, the present invention discloses a composition comprising the combination of the present invention along with agriculturally acceptable excipients selected from the group comprising suspension concentrates, highly concentrated aqueous suspensions, wet dispersible powders, water dispersible granules, dispersions and aqueous solutions.
The composition of the present invention may be any suitable composition such as wet dispersible granules, suspensions, emulsions, preferably suspension concentrates.

The pesticidal composition of the present invention may be formulated as suspension, highly concentrated aqueous suspensions, wet dispersible powders, water dispersible granule, dispersions or aqueous solution.
The suspension concentrate of the present invention comprises an anti-freeze agent, a dispersing agent, a wetting agent, a defoaming agent, a thickener, an antibacterial agent and demineralized water.
The present composition comprises one or more anti-freeze agent selected from the group comprising ethylene glycol, propylene glycol or glycerol. Preferably the anti - freeze agent is Propylene glycol. The anti-freezing agent may be present in an amount ranging from 5-10% w/w of the composition. Preferably, the amount of anti-freezing agent is 6% w/w of the composition.
The dispersing agent may be selected from the group comprising sodium lignosulphonates, sodium naphthalene sulphonate- formaldehyde condensates, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylates and esters, ethylene oxide/propylene oxide block copolymers. Preferably, the dispersing agent is tri steryl phenol ethoxylate potassium salt, amine salt of poly aryl phenyl ether phosphate or combinations thereof. The dispersing agent may be present in an amount ranging from 4-8% w/w of the composition. Preferably, the amount of dispersing agent is 5% w/w of the composition.
The defoamer or an antifoaming agent may be selected from the group comprising silicone emulsions, long-chain alcohols, fatty acids, organ fluorine compounds. Preferably, the defoamer or the antifoaming agent is silicon based. The said defoamer or antifoaming agent may be present in an amount ranging from 0.2-1 % w/w of the composition. Preferably, the amount of deformer or the antifoaming agent is 0.5% w/w of the composition.
The present composition comprises one or more thickeners. Preferably, the thickener is Xanthan gum. Said thickener is added as per the specific requirements in the composition.
The present composition comprises one or more anti-bacterials orbiocides. The antibacterial or the biocide may be present in an amount ranging from 0.1-0.5%) of the composition. Preferable, the amount of anti-bacterial or biocide is 0.2% w/w of the composition.
In another embodiment the present invention disclosed a process of preparing a suspension concentrate of the present invention.

The process of preparing the suspension concentrate comprises the following steps:
i. Diluting and solubilising a mixture surfactants and antifreeze agents in water to obtain a solution,
ii. Addition of defoaming agent to the solution of step (i) followed by addition of Pymetrozine technical to obtain a homogenous mixture; iii. Addition of Nitenpyram technical and Tebuconazole technical and adjuvants to obtain a homogenous mass;
iv. Size reduction of the homogenous mass of step (iii) to obtain mean particle size of less than 5 micron;
v. Preparation of an aqueous gum solution of 2% gum solution; optionally containing formaldehyde;
vi. Addition of the aqueous gum solution of step (v) to the homogenous mass of step (iii) to obtain a suspension concentrate. It has been observed that the composition of the present invention is synergistic and possesses enhanced agricultural effect as suspension concentrate.
In another embodiment the pesticidal combination and composition of present invention discloses a simultaneous, effective control of brown plant hopper (BPH) and brown spot disease in paddy crops.
Plant hoppers are important pest of agricultural crops. For instances, brown plant hopper (BPH), Nilaparvata lugens (Hemiptera: Delphacidae) is a plant hopper species that feeds on rice plants {Oryza sativa L). BPH are among the most important pests of rice, and rice is the major staple crop for about half the world's population. They damage rice directly through feeding and also by transmitting two viruses, rice ragged stunt virus and rice grassy stunt virus. Up to 60% yield loss is common in susceptible rice cultivars attacked by BPH.
BPH infest the rice crop at all stages of plant growth. As a result of feeding by both nymphs and adults at the base of the tillers, plants turn yellow and dry up rapidly. At early infestation, round, yellow patches appear, which soon turn brownish due to the drying up of the plants.
Brown spot a largely ignored fungal disease is one of the most common and most damaging rice diseases. It infects the coleoptile, leaves, leaf sheath, panicle branches, glumes and spikelets. Its most observable damage is the numerous big yellowish-brownish spots on the leaves

which can kill the whole leaf. Brown spot can occur at all crop stages, but the infection is most critical during maximum tillering up to the ripening stages of the crop. It causes both quality and quantity losses. The disease easily develops in areas with high relative humidity (86-100%) and a temperature between 16 and 36°C.
Unfortunately, similar weather conditions favour the development of both the spot disease and plant hopper insect attack. Humid conditions are especially congenial for the insect pests like Brown plant hopper and infestation by fungi and development of brown spot disease. The present invention therefore is useful in such condition, where there is simultaneous spot disease and plant hopper insect attack.
EXAMPLES:
The examples below are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Example 1 (a): Preparation of the combination of present invention
The present combination was prepared in the form of a wettable powder by undertaking the following steps:
1) All raw materials such as wetting agent, dispersant, dispersing agent, silica, china clay and Pymetrozine technical were mixed in the given proportion.
2) The above mass was mixed with blender and ground in jet mill.
3) Grinding was carried out until a mean particle size of below 10 microns was obtained.
4) After grinding, the resultant mix was mixed homogenously by blender followed by addition of Nitenpyram & Tebuconazole technical to obtain a homogenous mass.
5) Quality parameters of the final mix were checked.

Table 1: Composition of Nitenpyram 8% +Pymetrozine 17% + Tebuconazole 22% WP)
Table 2: Test parameters
Example 1 (b): Preparation of the combination of present invention
The present combination was prepared in the form of wettable dispersible granule (WDG) by undertaking the following steps:

1) All the raw materials such as wetting agent, dispersing agent, filler and technical were mixed in the given proportion.
2) The above mass was mixed in blender and ground by jet mill.
3) Grinding was carried out until a mean particle size of below lOmicron was obtained.
4) After grinding, the resultant mix was mixed homogenously using blender and a dough was prepared by dough mixer and granules were prepared through the extruder.
5) Granules as prepared above were dried using hot air or oven
6) Quality parameters of the final dry granules were checked
Table 3: Chemical combination of the (Pvmetrozine 17% + Nitenpyram 8% +
Tebuconazole 22% WPG)

Table 4: Test parameters
Example 1 (c): Preparation of the combination of present invention
The present combination was prepared in the form of a Suspension Concentrate by undertaking the following steps:
1) The mixture of surfactants & anti freezing agents were first diluted in deminerali sed water, and solubihsed by high speed mixer, defoamer was then added followed by addition of the Pymetrozine technical, this was mixed to obtain a homogenous mixture and then Nitenpyram technical was added, and then Tebuconazole technical was added and rest of the adjuvants were mixed to obtain a homogenous mass.
2) The above mixed mass was ground in a sand mill. Grinding was carried out until a mean particle size of <5 micron was obtained.
3) 2% gum solution was prepared by taking 10 gm DM water, adding 0.5 gm of formaldehyde sol. then adding0.20gm of xanthan gum under slow stirring.
4) The 2% solution of xanthan gum obtained above was added to the homogenous mass obtained in step 2 under slow stirring.
5) Quality parameters of the final mix were checked.

Example 2: Composition of the present invention:
An exemplification of the composition of the present invention is at Table (5(a) and Table 2(b). various parameter of the composition containing the combination of the present invention are tested by standard methods and set out at Table 5(c).
Table 5(a): Chemical combination (Pymetrozine 17% + Nitenpyram 8% +
Tebuconazole 22% SO
Table 5(b): Chemical combination (Pymetrozine 17% + Nitenpyram 8% +
Tebuconazole 22% SO

Table 5(c): Test parameters
Example 3: Bioefficacy tests of the present combination:
The bioefficacy of the present insecticidal-fungicidal combination was tested against the insect pest -BPH (Brown plant hopper) and brown spot disease in Paddy crop. The field trials were conducted during the Kharif season 2017-18 in karnal, Haryana of India. The trials were conducted in random block design (RBD) in a plot size of 30 sq. m. at a temperature of 37.5°C and at a relative humidity of 75%. A total of twenty-two treatments in three replications were performed following the foliar over the top application of the formulation.
Measured quantity of the chemical was added to the required volume of water @150 lit. /ac for spraying. The spray tank was filled with half the quantity of clean required volume of water and

then the measured chemical (according to the dose) was added followed by the rest half quantity of water. The solution was stirred well, and thorough coverage were ensured.
Table 6 below provides the treatment details of the trials conducted on paddy with the
present formulation

3(a) Evaluation of bioefficacy:
(i) Target insect pest: Brown plant hopper (BPH) in paddy:
The number of live BPH were counted from 10 randomly selected hills/replication before application (pre-count) and at 1, 3, 5, 7, 10 and at 5 days interval thereafter till re-infestation. Percent control of BPH Population was calculated based on no. of live BPH population. Formula are given below.
C-T
Percent control = x 100
C
Where C = No. of BPH (Both Nymph & Adult) population in control plot T = No. of BPH (Both Nymph & Adult) population in treated plot
(ii) Target fungal pest: Helminthosporium oryzae (Brown spot of rice):
Observation of disease symptoms were taken before every spray and 15 days after last application. Disease assessment was done as per the rating scale of 0 to 9 given by Mayee & Datar (Phyto Pathometery, 1986) on the basis of affected leaf area. The rating scale is shown below:

1 No Incidence
2 Less than 1%
3 1-3%
4 4-5%
5 11-15%
6 16-25%
7 26-50%
8 51-75%
9 76-100%

The disease index was calculated as per the formula below:
Sum of all the numerical disease rating X 100
% Disease Index =
(PDI) Total No. of plants (10) X Maximum disease grade in scale (9)
Example 3(b): Evaluation of phytotoxicity:
Visual observations were recorded at 3, 7 and 10 days after application. The parameters observed were leaf injury on tip/surface, necrosis, vein clearing, epinasty, hyponasty and wilting. For the rating on phytotoxicity the core Scale of 0 - 10 was followed for leaf injury on tips/surface.
Table 7: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface

Table 8: Bioefficacy of Trimix of Novel insecticide Nitenpyram +Pymetrozine + Tebuconazole against BPH (After First
Application)

Table 9: Bioefficacy of Trimix of Novel insecticide Nitenpyram + Pymetrozine + Tebuconazole against BPH (After Second
Application)

RESULT:
Table-8 & Table-9 indicated that maximum percent control of BPH population and minimum percent disease index as shown in Table-10 was observed with CCP-81722 SC @ 325-350 ml per acre.
No phytotoxicity symptoms as shown in (Table-11 & 12) were observed in paddy crop.
The applicant would like to state that the pesticidal combination of the present invention is undergoing field trials and hence the amount of ingredients may vary from the above as the applicant is under the process of determining the best possible embodiments and results.
The combination of the present invention is expected to show activity against numerous insect pests including but not limited to Green Leaf hopper {Nephotettix virescens, Nephotettix malayanus), Brown Plant hopper (Nilaparrata lugens), White backed plant hopper ( Sogatella furcifera) and other rice diseases (for instance, False smut, sheath rot).
Advantages
The present invention ensures uniform and homogeneous distribution of active ingredients and can be easily sprayed on paddy crops for effective control of brown plant hopper (BPH) and brown spot disease in paddy crops.

We claim:
1. A synergistic pesticidal combination wherein said combination comprises:
a. At least one insecticide belonging to the group of neonicotinoids;
b. At least one insecticide belonging to the group of pyridines azomethines;
c. At least one fungicide belonging to the group of Triazoles.
2. The synergistic pesticidal combination as claimed in claim 1, wherein the neonicotinoid is selected from the group comprising Acetamiprid, Clothianidin, Imidacloprid, Nitenpyram, Nithiazine, Dinotefuran, Thiacloprid, Thiamethoxam, preferably the insecticide is Nitenpyram.
3. The synergistic pesticidal combination as claimed in claim 1, wherein the pyridine azomethine is pymetrozine.
4. The synergistic pesticidal combination as claimed in claim 1, wherein the Triazoles is selected from the group comprising azaconazole, bromuconazole, cyproconazole, difenoconazole, hexaconazole, Ipconazole, furconazole, tebuconazole, etaconazole, more preferably tebuconazole.
5. The synergistic pesticidal combination as claimed in claim 1, wherein said combination comprises:
a. Nitenpyram in the range of 1-30% w/w, preferably l-28%w/w, more
preferably 1-25% w/w of the combination of the total weight of the
combination.
b. Pymetrozine in the range of 1-60% w/w, preferably 1-58% w/w, more
preferably 1-55% w/w of the total weight of the combination.
c. Tebuconazole in the range of 1-75% w/w, preferably 1-50% w/w, more
preferably 1-45% w/w, of the total weight of the combination.
6. The synergistic pesticidal combination as claimed in claim 1, wherein the ratio
of combination is 1:1:1 to 1:3:3.
7. A pesticidal composition comprising the combination as claimed in claim 1,
along with agriculturally acceptable excipients.
8. The pesticidal composition as claimed in claim 7, wherein said composition is
formulated in a form selected from the group comprising suspension concentrates,
highly concentrated aqueous suspensions, wet dispersible powders, water dispersible
granules, dispersions and aqueous solutions, preferably a suspension concentrate.
9. The pesticidal composition as claimed in claim 7, wherein the agriculturally
acceptable excipients are selected from the group comprising anti-freezing agent,

dispersing agent, wetting agent, defoamer, antibacterial or biocide, thickener and demineralized water.
10. The pesticidal composition as claimed in claim 9, wherein said antifreeze agent is selected from the group comprising ethylene glycol, propylene glycol and glycerol.
11. The pesticidal composition as claimed in claim 9, wherein said dispersing agent is selected from the group comprising sodium hgnosulphonates, sodium naphthalene sulphonate- formaldehyde condensates, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylates and esters and ethylene oxide/propylene oxide block copolymers.
12. The pesticidal composition as claimed in claim 9, wherein said antifoaming agent is selected from the group comprising silicone emulsions, long-chain alcohols, fatty acids, organ fluorine compounds.
13. The pesticidal composition as claimed in claim 9, wherein said thickener is Xanthan gum.
14. A process for preparing the synergistic pesticidal combination as claimed in claim 1, wherein said process comprises the following steps:
i. Diluting and solubilising a mixture of surfactants and antifreeze agents in
water to obtain a solution, ii. Addition of antifoaming agent to the solution of step (i) followed by
addition of Pymetrozine technical to obtain a homogenous mixture; iii. Addition of Nitenpyram technical and Tebuconazole technical and adjuvants
to obtain a homogenous mass; iv. Size reduction of the homogenous mass of step (iii) to obtain mean particle
size of less than 5 micron; v. Preparation of an aqueous gum solution of 2% gum solution; optionally
containing formaldehyde; vi. Addition of the aqueous gum solution of step (v) to the homogenous mass of step (iii) to obtain a suspension concentrate. 15. The combination and composition as claimed in claim 1 and 7 for simultaneous, effective control of brown plant hopper (BPH) and brown spot disease in paddy crops.