The present invention relates to synergistic insecticidal compositions. Particularly, the present invention relates to a synergistic insecticidal composition comprising Pymetrozine, Diafenthiuron and one or more compounds having insecticidal, acaricidal or nematicidal activity.
BACKGROUND OF THE INVENTION
Insecticide compositions that can be applied at as low a dose as possible and be effective in controlling pest species of insects while causing as little harm as possible to beneficial insects and minimal disturbance in the environment are in demand by the farming community. Insects are very destructive to crop plants and can result in significant loss of crop yield and quality, which results in economic loss to the grower and increased costs to the consumer. Combinations of insecticides are typically used to broaden the spectrum of insect control or enhance the level of control of any given species through additive effect. Certain rare combinations surprisingly give a greater-than-additive or synergistic effect. There is a need to provide synergistic compositions as they afford various advantages like improved pest control, a greater spectrum of pests controlled, reduced cost and reduced residue problems. Hitherto, no attempts have been made to formulate a combination of Pymetrozine, Diafenthiuron and one or more compounds having insecticidal, acaricidal or nematicidal activity.
Swiss Patent CH689326 (A5) discloses a pesticidal composition containing (a) pymetrozine or one of its salts; and (b) a thiourea, benzoylurea, carbamoyl oxime, halocarboxylic acid, organophosphate, organochlorine derivative, nitroenamine, nitroguanidine, cyanoguanidine, carbamate, thiocarbamate, carbodiimide, formamidine, benzilic acid, dioxolane, thiadiazine, triazine, pyridazinone, pyrrole,

phenoxyphenyl ether, sulphonamide, Bacillus thuringiensis preparation, milbemycin, avermectin or pyrethroid.
European Patent Application EP96810173.3 discloses the combinations of diafenthiuron with other insecticides.
Combinations of Pymetrozine, Diafenthiuron and one or more compounds having insecticidal, acaricidal or nematicidal activity have now been found to provide control of insects which is substantially and surprisingly enhanced over the expected simply additive control by said components.
There is no mention in the prior art that combining Pymetrozine and Diafenthiuron with one or more compounds having insecticidal, acaricidal or nematicidal activity produces a pronounced insecticidal effect in controlling a wide range of insect pests and improved performance in the field.
OBJECTS OF THE INVENTION
The main object of the invention is to provide a synergistic insecticidal composition.
Another object of the present invention is to provide a synergistic insecticidal composition comprising Pymetrozine, Diafenthiuron and one or more compounds having insecticidal, acaricidal or nematicidal activity, which is effective against broad spectrum of insects and also helps in resistance management.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a synergistic insecticidal composition comprising: a) pymetrozine; b) diafenthiuron; c) at least one insecticide selected from the group comprising thiamethoxam, imidacloprid, acephate, lambda cyhalothrin, chlorpyrifos, acetamiprid and clothianidin; and d) excipients.

In an embodiment the synergistic insecticidal composition comprises pymetrozine, diafenthiuron, clothianidin and excipients.
In another embodiment the synergistic insecticidal composition comprises pymetrozine, diafenthiuron and clothianidin in a weight ratio in the range from about 1:5:0.1 to 30:50:10.
In yet another embodiment, pymetrozine is present in an amount in the range from about 1 to 30% w/w, diafenthiuron is present in an amount in the range from about 5 to 50% w/w, and clothianidin is present in an amount in the range from about 0.1 to 10% w/w.
In one another embodiment, the synergistic insecticidal composition comprises excipient selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, disintegration agent, thickener, filler.
In another embodiment, the composition is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) 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).

In another embodiment, the synergistic insecticidal composition is formulated as suspension concentrate or water-dispersible granule.
In one another embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, thickener, and wherein the formulation is a suspension concentrate.
In yet another embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, disintegration agent, defoamer, filler, and wherein the formulation is water dispersible granule.
In an embodiment, the synergistic insecticidal composition comprises dispersing agent selected from the group comprising amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, naphthalene sulphonate of formaldehyde condensate, lignin based sulphonate and combinations thereof, and present in an amount in the range from 2 to 10% w/w.
In another embodiment, the synergistic insecticidal composition comprises a wetting agent selected from the group consisting of ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate and combinations thereof, and present in an amount in the range from 1 to 5% w/w.
In yet another embodiment, the synergistic insecticidal composition comprises an anti-freezing agent selected from the group consisting of propylene glycol, diethylene glycol, monoethylene glycol and combinations thereof, and present in an amount in the range from 2 to 10% w/w.
In one another embodiment, the synergistic insecticidal composition comprises a defoamer which is dimethyl polysiloxane emulsion and present in an amount in the range from 0.01 to 1% w/w.

In still another embodiment, the synergistic insecticidal composition comprises a disintegration agent selected from citric acid and sodium bicarbonate and present in an amount in the range from 1 to 2% w/w.
In an embodiment, the synergistic insecticidal composition comprises a biocide selected from the group consisting of 20% aqueous dipropylene glycol solution of l,2-benzisothiazolin-3-one, formaldehyde and combinations thereof and present in an amount in the range from 0.01 to 0.50% w/w.
In another embodiment, the synergistic insecticidal composition comprises a thickener which is xanthan gum and present in an amount in the range from 0.01 to 0.50% w/w.
In one another embodiment, the synergistic insecticidal composition comprises a filler selected from group comprising of bentonite clay, china clay, silica, kaolin and diatomaceous earth.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1. is a flowchart for preparing a synergistic insecticidal composition in the form of suspension concentrate.
Figure 2. is a flowchart for preparing a synergistic insecticidal composition in the form of water-dispersible granule.
DETAILED DESCRIPTION OF THE INVENTION
Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods. The illustrative examples are described in this section in connection with the embodiments and methods provided. The invention according to its various aspects is particularly pointed out and distinctly claimed in the appended claims read in view of this specification and appropriate equivalents.
It is to be noted that, as used in the specification and the appended claims, 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.
The expression of various quantities in terms of "% w/w" or "%" means the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified.
The term "active ingredient" (A. I.) or "active agent" used herein refers to that component of the composition responsible for control of insects or pests.
The present invention provides a synergistic insecticidal composition comprising a) pymetrozine b) diafenthiuron c) at least one insecticide selected from the group comprising thiamethoxam, imidacloprid, acephate, lambda cyhalothrin, chlorpyrifos, acetamiprid and clothianidin; and d) excipients.
Pymetrozine is a pyridine azomethine insecticide suitable for use in integrated crop management to control aphids and other plant sucking insect pests. It belongs to the class of anti-feedants. Pymetrozine is represented by following structural formula
H3CX ^NN ^H
N


%N' 0
\/H
IUPAC: (E)-4,5-dihydro-6-methyl-4-(3-pyridinylmethyleneamino)-l,2,4-triazin-3(2H)-one

Pymetrozine has novel unidentified biochemistry. Pymetrozine is selective against Homoptera, by acting as feeding inhibitors leading to high mortality due to starvation due to cessation of feeding. It provides efficient control of both juvenile and adult stages of aphids and whiteflies in vegetables, ornamental, cotton, deciduous and citrus fruits, tobacco and hops. It also provides effective control of plant hoppers in rice.
In view of the close relationship between pymetrozine in free form and its agriculturally suitable salts, including their equilibration under physiological and environmental conditions, hereinbefore and hereinafter any reference to pymetrozine is to be understood as including both free pymetrozine and its agriculturally suitable salts, where appropriate and expedient.
Diafenthiuron is an insecticide and acaricide effective against phytophagous mites and other sucking pests. It belongs to the class of thiourea insecticide/acaricide.
Diafenthiuron is represented by following structural formula-
CH3
CH3—CH S
II CH,

K TJ—C—CH3
^v°A/-|
H H CH3
CH3—CH
CH3

IUPAC: 1 -tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea
Diafenthiuron is rapidly desulphurated abiotically to the pesticidal carbodiimide (inhibitor of mitochondrial respiration) in the presence of sunlight and singlet oxygen. Diafenthiuron is a potent in vivo inhibitor of mitochondrial respiration. It is an insecticide/acaricide which kills larvae, nymphs and adults by contact and/or stomach action and also shows some ovicidal action. It is effective against

phytophagous mites (Tetranychidae, Tarsonemidae), Aleyrodidae, Aphididae and Jassidae on cotton, various field and fruit crops, ornamental plants and vegetables. It also controls some leaf-feeding pests in cole crops {Plutella xylostella), soybeans (Anticarsia gemmatalis) and cotton (Alabama argillacea). It is safe on adults of all beneficial groups (Anthocoridae, Coccinellidae, Miridae) and on adults and immature stages of predatory mites (Amblyseius andersoni, Typhlodromus pyri), spiders (Erigonidae, Lycosidae), and Chrysopa cornea. It is non-selective to immature stages of Heteroptera (Anthocoridae, Miridae) and is compatible with the biological control of Aleyrodidae and mites in glasshouses.
The at least one insecticides used along with pymetrozine and diafenthiuron in the synergistic composition of the present invention can be selected from, but not limited to chloronicotinyl compounds, carbamate compounds, pyrethroid compounds, macrolide compounds, phosphorus compounds, diamide compounds, isoxazoline compounds and the like. Examples thereof include the following compounds indicated by their common names, however, the present invention is by no means limited to acetamiprid, acephate, carbaryl, methomyl, cartap, cyhalothrin, triazophos, ethofenprox, teflubenzuron, flufenoxuron, tebufenozide, fenpyroximate, pyridaben, imidacloprid, buprofezin, BPMC (fenobucarb), malathion, pirimicarb, permethrin, cypermethrin, bifenthrin, silafluofen, nitenpyram, chlorfluazuron, methoxyfenozide, tebufenpyrad, pyrimidifen, propargite, hexythiazox, spinosad, spirotetramat, milbemectin, BT (Bacillus thuringiensis), indoxacarb, chlorfenapyr, fipronil, etoxazole, acequinocyl, pirimiphos-methyl, chlorpyrifos, avermectin, abamectin, emamectin-benzoate, fenbutatin oxide, terbufos, ethoprophos, fosthiazate, oxamyl, benfuracarb, spirodiclofen, methiocarb, cyfluthrin, beta-cyfluthrin, spiromesifen, amitraz, ethiprole, broflanilide, chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyhalodiamide, flubendiamide, tetrachlorantraniliprole, tetraniliprole, afoxolaner, fluralaner, fluxametamide and the like.
Further, the insecticides, can be selected from compounds ethion, dichlorvos, monocrotophos, dimethoate, profenos, chlorpyrifos-methyl, pyrethrins, allethrin,

prailethrin, resmethrin, permethrin, tefluthrin, alpha-cypermethrin, lambda-cyhalothrin, deltamethrin, fenvalerate, esfenvalerate, flucythrinate, fluvalinate, thiodicarb, propoxur, fenoxycarb, fenothiocarb, bifenazate, carbofuran, carbosulfan, furathiocarb, diflubenzuron, hexafiumuron, novaluron, lufenuron, chlorfluazuron, amitraz, chromafenozide, tolfenpyrad, thiacloprid, thiamethoxam, clothianidin, dinotefuran, pyriproxyfen, cyromazine, thiocyclam, fenazaquin, azadirachtin, rotenone, pyridalyl, metafiumizone or its isomers, pyrifluquinazon, triazamate, isoprothiolane, flupyradifuron, flonicamid, afidopyropen.
Preferred insecticide used along with pymetrozine and diafenthiuron in the synergistic composition of the present invention can be selected from thiamethoxam, imidacloprid, acephate, lambda cyhalothrin, chlorpyrifos, acetamiprid and clothianidin. More preferably, the insecticide is clothianidin.
In an embodiment the synergistic insecticidal composition comprises pymetrozine, diafenthiuron and clothianidin in a weight ratio in the range from about 1:5:0.1 to 30:50:10.
In another embodiment, pymetrozine is present in an amount in the range from about 1 to 30% w/w, diafenthiuron is present in an amount in the range from about 5 to 50% w/w, and clothianidin is present in an amount in the range from about 0.1 to 10% w/w.
The synergistic insecticidal composition comprises excipient selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, disintegration agent, thickener and filler.
The synergistic composition of the present invention may be formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD),

Oil miscible fiowable 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). The abbreviations provided for various formulations are the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations).
Preferably, the composition of the present invention is formulated as suspension concentrate and water dispersible granule.
In an embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, thickener, and the composition is in the form of a suspension concentrate (SC). The term "suspension concentrate" used herein refers to a suspension of the active insecticide and excipients in a small quantity of liquid, usually water.
In another embodiment, the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, disintegration agent, defoamer, filler, and wherein the formulation is water dispersible granule. The term "water dispersible granules" used herein refers to granules that are obtained by blending and agglomerating a ground solid active ingredient together with excipients.
It is generally observed that solid particles in a liquid undergo spontaneous aggregation to form lumps. Hence it is recommended to add a dispersing agent which prevents agglomeration of solid particles and keep them suspended in fluid.

Accordingly, the composition of the present invention contains dispersing agents such as amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, naphthalene sulphonate of formaldehyde condensate, lignin based sulphonate. One or more dispersing agents may be used in the synergistic composition of the present invention. The dispersing agent is present in an amount in the range from 2 to 10% w/w.
Wetting is the first stage of dispersion, in which air surrounding the granular composition is substituted with water. Wetting of the composition with water cannot occur if the surface tension of the liquid is very high. Hence, it is recommended to add a wetting agent to the composition to facilitate the process of dispersion of the granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate, each of which can be used individually or in combination, in an amount in the range from 1% to 5% w/w.
An anti-freezing agent is generally added to insecticidal composition, to prevent the aqueous compositions from freezing. Suitable anti-freezing agents useful herein, but not limited to, include propylene glycol, diethylene glycol, monoethylene glycol and combinations thereof. Preferably, the anti-freezing agent is present in an amount in the range from 2 to 10% w/w.
A defoamer, also called as anti-foam, is generally added to an insecticidal composition as foam formation prevents the efficient filling of a container. Preferably, the defoamer is polydimethyl siloxane emulsion. In the insecticidal composition the defoamer is present in an amount in the range from 0.01 to 1%
w/w.
The disintegration agent is selected from citric acid and sodium bicarbonate and present in an amount in the range from 1 to 2% w/w.

The synergistic insecticidal composition comprises a biocide selected from the group consisting of 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3-one, formaldehyde and combinations thereof, and present in an amount in the range from 0.01-0.50% w/w. The biocide is added to the composition of the present invention for its preservation against spoilage from bacteria, yeasts and fungi.
It is necessary to add a thickener to an insecticidal composition to reduce the tendency of the insecticide composition to disperse when sprayed, and decrease the likelihood of it being rinsed off from the crops. Preferably, the synergistic insecticidal composition comprises xanthan gum as thickener in an amount in the range from 0.10-0.50% w/w.
A filler is added to the composition to improve the handling and storage characteristics of the composition. Fillers also add mass and/or volume to the active ingredient in order to facilitate precise measurement of the doses. Suitable fillers that may be used in the composition of the present invention include, but not limited to, bentonite clay, china clay, silica, kaolin and diatomaceous earth.
The present invention also relates to a process of preparation of synergistic insecticidal compositions comprising pymetrozine, diafenthiuron, at least one insecticide selected from the group comprising thiamethoxam, imidacloprid, acephate, lambda cyhalothrin, chlorpyrifos, acetamiprid and clothianidin, and excipients.
The present invention also provides a method of controlling insects by applying an effective amount of the synergistic insecticidal composition to the above ground portions of the plant. The present invention provides an improved method of combating homopterous insects in field, vegetable, greenhouse and orchard crops.

The composition of the present invention provides effective control of insects
belonging to the order Hemiptera and Thysanoptera. These insects
include Brevicoryne brassicae, Hydaphis pseudobrassicae, Acyrthosiphon
pisum, Aphis craccivora, Aphis fabae, Macrosiphum rosae, Macrosiphum
euphorbiae, Hyalopterus amygdali, Brachycaudus persicaecola, Aphis
pomi, Sappaphis piricola, Aphis citricola, Nasonovia ribisnigri, Eriosoma
lanigerum, Megoura viciae, Pemphigus sp., Toxoptera spp, Phorodon
humuli, Diuraphis noxia, Lipaphis erysimi, Metopolophium
dirhodium, Therioaphis spp., Schizaphis graminum, Sitobion
avenae, Rhopalosiphum spp., Aphis gossypii, Myzus nicotianae and
particularly Myzus persicae. The insects also include Bemisia tabaci, Trialeurodes
vaporariorum, Nilaparvata lugens, Nephotettix spp., Philaenus
spumarius, Empoasca spp., Spissistilus festinus, Laodelphax
striatellus, Erythroneura sp., Typhlocyba pomaria, Adelges abietis, Icerya purchasi, Aonidiella aurantii, Quadraspidiotus perniciosus, Gossyparia spuria, Planococcus
citri, Phenacoccus spp., Pseudococcus spp., Centrococcus sp., Eriococcus
Azaleae, Oebalus pugnax, Nezara viridula, Lygus spp., Euschistus
spp., Chlorochroa spp., Pachypsylla celtidismama, Paratrioza
cockerelli, Cacopsylla pyricola, Pseudatomoscelis seriatus,
Thrips spp., Frankliniella occidentalis, Pineus strobi and other genera and species closely related to these insects.
The present invention provides effective control of a broad spectrum of insect pests of ornamental, vegetable, field, cereal, greenhouse, fruit, vine crops and cotton.
It has been surprisingly found that the synergistic insecticidal composition of present invention provides a wide spectrum control of insects, delaying the emergence of the resistant strains of the insects, and achieving effective and economical control of undesired insects.

The synergism manifested by the composition of the present invention comprising pymetrozine, diafenthiuron, at least one insecticide selected from the group comprising thiamethoxam, imidacloprid, acephate, lambda cyhalothrin, chlorpyrifos, acetamiprid and clothianidin, allows a substantial reduction in the application rates of each of these active ingredients, while maintaining good insecticidal efficacy. Decreasing application rates reduces treatment cost to the farmer and also eases the burden on the environment both from manufacturing waste and crop protection chemical residues.
The embodiments of the present invention are more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those of skill in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are on a weight basis and all reagents used in the examples were obtained or are available from the chemical suppliers.
EXAMPLES
Examples 1-4
The synergistic insecticidal composition of the present invention comprising pymetrozine, diafenthiuron and clothianidin in the form of water dispersible granules are provided in Examples 1-3 (Table 1). The unit of each component of the composition are expressed in "% w/w" i.e. the percentage by weight, relative to the weight of the total solution or composition.
The excipients used in Examples 1-3 for preparing the synergistic composition of the present invention in water dispersible granule form are dispersing agent, wetting agent, disintegration agent, defoamer and filler.

Table 1: Synergistic insecticidal composition formulated as water dispersible granules

S.No. Component Function Example 1 Example 2 Example 3
1 Pymetrozine Active ingredient 15.00 15.00 15.00
2 Diafenthiuron Active ingredient 30.00 30.00 30.00
3 Clothianidin Active ingredient 1.5 2.0 2.5
4 Naphthalene sulphonate of formaldehyde condensate Dispersing agent 02.00 -10.00
5 Naphthalene alkyl aryl sulphonate Wetting agent 01.00-05.00
6 Citric acid Disintegration agent 01.00-02.00
7 Dimethyl
Polysiloxane
emulsion Defoamer 00.10-01.00
8 China clay Filler Q.S. to make 100
Table 2 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in WG form. The active ingredients, pymetrozine, diafenthiuron and clothianidin are in technical grade. The entries for active ingredients, pymetrozine, diafenthiuron and clothianidin, in table 2 varies from that of table 1, as the entries in table 1 are for 100% pure compounds whereas the entries in Table 2 are for technical ones with certain percentage of impurities. Hence, example 1 of table 1 for pymetrozine 15% w/w, diafenthiuron 30% w/w and clothianidin 1.5% w/w of 100% purity corresponds to example 4 of table 2 for pymetrozine 15.31 kg, diafenthiuron

31.25 kg and clothianidin 1.54 kg of 98%, 96% and 98% purity respectively. Likewise, example 2, 3 corresponds to examples 5, 6 of table 2.
Table 2: Quantities of active ingredients and raw material charged

Sr. No. Components Weight (Kg)

Example 4 Example 5 Example 6
1 Pymetrozine (Basis of 98.0%) 15.31 15.31 15.31
2 Diafenthiuron (Basis of 96.0%) 31.25 31.25 31.25
3 Clothianidin (Basis of 98.0%) 1.54 2.08 2.56
4 Naphthalene sulphonate derivative 04.00 04.00 04.00
5 Naphthalene alkyl aryl sulphonate 02.00 02.00 02.00
6 Acrylic graft copolymer 02.00 02.00 02.00
7 Citric acid 00.50 00.50 00.50
8 China clay 43.40 42.86 42.38
Example 7: Process for the preparation of synergistic insecticidal composition of pymetrozine, diafenthiuron and clothianidin in water dispersible granule form
All the components were weighed as per example 4 and mixed well using proper ribbon blender type mixer to obtain a mixture. The mixture was milled with suitable air jet mill. The milling chamber was kept at 6 kg per cm2 and at feeding pressure of 2 kg per cm . The mixture was milled to achieve a particle size below 10 microns and then mixed properly in a post blender. A dough was prepared

using the milled mixture and 10% to 20% water in suitable dough-mixer. The dough was then extruded using proper extruder having suitable screen while maintaining the temperature of the screen below 45°C to obtain extruded granules. The extruded granules were dried using a fluid bed dryer. The air flow was kept at 75% and the temperature of the air was maintained at 47°C.
Table 3 provides synergistic insecticidal composition of the present invention comprising pymetrozine, diafenthiuron and clothianidin in the form of suspension concentrate (SC). The unit of each component of the composition are expressed in "% w/w" i.e. the percentage by weight, relative to the weight of the total solution or composition.
Table 3: Synergistic insecticidal composition formulated as suspension concentrate (SC)

S.No. Component Function Example 8 Example 9 Example 10
1 Pymetrozine Active ingredient 15.00 15.00 15.00
2 Diafenthiuron Active ingredient 30.00 30.00 30.00
3 Clothianidin Active ingredient 1.5 2.0 2.5
4 Propylene glycol Anti-freezing Agent 02-10
5 Acrylic Copolymer Dispersing A gent 02-10
6 Non-ionic ethoxylate Wetting agent 01-05
7 Dimethyl Polysiloxane emulsion Defoamer 00.01-00.50
8 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3 -one Biocide 00.01-00.50

9 Xanthan Gum Thickener 00.01-00.50
10 Demineralised water Q.S.
Table 4 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in SC form. The active ingredients, pymetrozine, diafenthiuron and clothianidin are in technical grade. The entries for active ingredients, pymetrozine, diafenthiuron and clothianidin, in table 4 varies from that of table 3, as the entries in table 3 are for 100% pure compounds whereas the entries in Table 4 are for technical ones with certain percentage of impurities. The examples 8, 9, 10 of Table 3 corresponds to examples 11,12,13 of table 4.
Table 4: Quantities of active ingredients and raw material charged

Sr.
No. Components Weight (kg)

Example 11 Example 12 Example 13
1 Pymetrozine (Basis of 98.0%) 15.31 15.31 15.31
2 Diafenthiuron (Basis of 96.0%) 31.25 31.25 31.25
3 Clothianidin (Basis of 98.0%) 1.54 2.08 2.56
4 Propylene glycol 5.00 5.00 5.00
5 Acrylic Copolymer 5.00 5.00 5.00
6 Non-ionic ethoxylate 2.00 2.00 2.00
7 Dimethyl Polysiloxane emulsion 0.20 0.20 0.20

8 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3 -one 0.20 0.20 0.20
9 Xanthan gum 0.15 0.15 0.15
10 Demineralised water 39.35 38.81 38.33
Example 14: Process for the preparation of synergistic insecticidal composition in SC form
The acrylic copolymer (5 kg) and non-ionic ethoxylate (5 kg) were diluted in de-mineralised water and solubilized by high shear mixing. Then propylene glycol (5 kg), pymetrozine (15.31 kg), diafenthiuron (31.25 kg), clothianidin (1.54 kg), dimethyl polysiloxane emulsion (0.20 kg), 20% aqueous dipropylene glycol solution of l,2-benzisothiazolin-3-one (0.20 kg) were added and mixed to obtain a homogeneous mass. The homogeneous mass was grinded in bead mill. The grinding was carried out until a mean particle size of 3-5(D-90) microns was obtained. After grinding, 2% water solution of xanthan gum was added under low stirring to obtain the title composition.
Evaluation of bio-efficacy of the synergistic insecticidal composition against insect pests in cotton
Field trials were performed to evaluate the biological efficacy of the synergistic insecticidal composition of present invention against the common and hazardous pests. Table 5 provides treatment details of insecticidal compositions for evaluation of bio-efficacy against whitefly in cotton. The evaluation was performed by comparing the synergistic insecticidal composition in the present invention against the solo marketed reference products, such as Clothianidin 50%WG, Pymetrozine 50%WG and Diafenthiuron 50% WP.

Table 5

Particulars Treatment Dose/Hectare
Tl Pymetrozine (15%) + Diafenthiuron (30%) + Clothianidin(1.5%)WG 1000 g
T2 Pymetrozine (15%) + Diafenthiuron (30%) + Clothianidin (2.0%) WG 1000 g
T3 Pymetrozine (15%) + Diafenthiuron (30%) + Clothianidin (2.5%) WG 1000 g
T4 Clothianidin 50%WG 50g
T5 Pymetrozine 50%WG 300g
T6 Diafenthiuron 50%WP 600g
T7 Control Water spray
Method of observation
Five plants in each treatment were randomly tagged per plot and pre and post treatment observations were recorded. The number of insects were counted from three leaves one each from bottom, middle and top of plant before sprays as well as on three, seven and fifteen days after spraying (DAS). The population of insect is recorded on suitable no. of randomly selected plants per replication. Suitable no. of randomly selected leaves/panicles/twigs/inflorescence (or target plant part) per plant / tree are selected for observations. Suitable method is used to count the insect population. Pre-treatment population of insect is recorded one day before the spray of insecticide. The post-treatment population of insect, is recorded at suitable intervals after each spray.
Based on various doses, weighed quantity of test products were dissolved in 2.5 L of water/plot and sprayed uniformly.

Details of the experiment
Target pest: Whitefly
Crop: Cotton
Variety: NHH 44
Plot Size: 50 m2
Spacing: 75.0 x 45.0cm
Water volume/ha: 500 litres
Spray Equipment: Knapsack sprayers fitted with cone nozzle
Observation: Means of five plants, three leaves per plant
Application Stage: Two sprays at 15 days interval
Insect Pest Assessment: Pre-treatment population of white fly was recorded one day before the spray of insecticide from the tagged plants. The post-treatment population of insect was recorded at suitable intervals (3, 7 and 15 days) after each spray. The corrected percent reduction in target insect population over control was worked out using Henderson & Tilton Formula (1955) which is given below.
% reduction «J ^ shCclrf«ai^awi%BfaT3fta-a«aigtt « *m
of Insect = ftffiCsttfftfffl*ffil3ittkTkf«tWtBailtt
Population
Where, n = insect population; T = Treated; Co = Control

Table 6: Efficacy of different treatments on whitefly in cotton crop

Treatment Mean number of whitefly per three leaves Percent
Reduction Over
control

First spray Second spray

BS 3 DAS 7 DAS 15 DAS 3 DAS 7DAS 15 DAS

1 8.23 (2.95) 3.40 (1.97) 2.63 (1.77) 2.13 (1.62) 1.90 (1.55) 1.77 (1.51) 1.70 (1.48) 87.74
2 8.33 (2.97) 2.77 (1.81) 1.73 (1.49) 1.47 (1.40) 1.40 (1.38) 1.37 (1.37) 1.20 (1.30) 91.35
3 8.20 (2.95) 2.93 (1.85) 1.87 (1.54) 1.70 (1.48) 1.57 (1.44) 1.43 (1.39) 1.37 (1.37) 90.12
4 8.37 (2.98) 6.87 (2.71) 6.03 (2.56) 5.87 (2.52) 5.00 (2.35) 4.83 (2.31) 4.80 (2.30) 65.39
5 8.40 (2.98) 7.90 (2.90) 7.60 (2.85) 6.93 (2.73) 6.43 (2.63) 6.20 (2.59) 6.03 (2.56) 56.52
6 8.47 (2.99) 3.80 (2.07) 3.27 (1.94) 2.93 (1.85) 2.80 (1.82) 2.77 (1.81) 2.63 (1.77) 81.04
7 8.33 (2.97) 9.67 (3.19) 10.23 (3.28) 11.57 (3.47) 12.43 (3.60) 13.10 (3.69) 13.87 (3.79) 0.00
SEm± 0.008 0.211 0.249 0.284 0.302 0.321 0.345 —
CD @ (P = 0.05) 0.025 0.659 0.775 0.886 0.942 1.001 1.074 —
BS - Before spraying; DAS - Days after spraying;
Figures in parentheses are square root transformed values
The aforementioned trial results from Tables 6 indicate that Tl to T3 i.e. synergistic insecticidal composition of the present invention comprising pymetrozine, diafenthiuron and clothianidin formulated as WG are most effective

against whitefly as compared to the marketed reference products such as clothianidin 50% WG, pymerozine 50% WG and diafenthiuron 50% WP.
The yield of cotton from individual plots were recorded and expressed in kg per hectare and presented in Table 7.
Table 7: Yield of cotton based on different treatments

Treatments Yield (kg/hectare)
Tl 1072.22
T2 1162.59
T3 1107.41
T4 789.26
T5 724.37
T6 853.43
T7 616.67
SEm± 25.89
CD(p=0.05) 80.66
The highest yield of 1162.59 Kg ha"1 was observed in plots treated with T2. Overall, the yield was significantly higher when the plots were treated with the synergistic insecticidal composition of the present invention comprising pymetrozine, diafenthiuron and clothianidin formulated as WG as compared to the marketed reference products such as clothianidin 50% WG, pymetrozine 50% WG and diafenthiuron 50% WP.
The phytotoxic effect of different treatment schedules was observed in ten randomly selected plants from each plot at 15 days after treatment on 0-10 scale (Table 9) for yellowing, stunting, necrosis, epinasty and hyponasty. European Weed Research Council's Crop Phytotoxicity scoring is provided in Table 8.

Table 8: Phytotoxicity visual scoring 0-10 (EWRC system)

Description of crop Rating Remarks Description of crop Rating Remarks
No injury, normal 0 Immune Severe injury, no recovery possible 6 Moderately tolerant
Slight injury / discoloration 1 Resistant Sever injury, stand loss 7 Susceptible
Some stand crop, stunning / discoloration 2 Moderately Almost
destroyed, a few plants surviving 8 Susceptible
Injury more pronounced but not persistent 3 Tolerant Very few plants alive 9 Highly susceptible
Moderate injury, recovery possible 4 Tolerant Complete destruction 10 Highly susceptible
Injury more persistent, recovery more doubtful 5 Moderately tolerant

Table 9. Phytotoxic effect of synergistic composition of the present invention on Cotton plant

Phytotoxiciry rating
ein Clearing
Leaf
Treatments ~~*" yeui
tip Wilting ^]QO^„„ Necrosis Epinasty Hyponasty
injury

Tl

0

0

0

0

0

0

T2
T3
T7
The synergistic insecticidal composition of the present invention gave good control of major insects of cotton along with significant increase in yield and better economics to farmers as compared to the marketed reference products. Additionally, the use of the composition resulted in better crop condition, i.e. fresh green leaves and better yield and did not produce any phytotoxic symptoms on the plants.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.

We claim:

1.A synergistic insecticidal composition comprising:
a) pymetrozine;
b) diafenthiuron;
c) at least one insecticide selected from the group comprising
thiamethoxam, imidacloprid, acephate, lambda cyhalothrin, chlorpyrifos,
acetamiprid and clothianidin; and
d) excipients.
2. The synergistic insecticidal composition as claimed in claim 1, wherein the insecticide is clothianidin.
3. The synergistic insecticidal composition as claimed in claim 1, wherein pymetrozine, diafenthiuron and clothianidin are present in a weight ratio in the range from about 1:5:0.1 to 30:50:10.
4. The synergistic insecticidal composition, as claimed in claim 1, wherein pymetrozine is present in an amount in the range from about 1 to 30% w/w, diafenthiuron is present in an amount in the range from about 5 to 50% w/w, and clothianidin is present in an amount in the range from about 0.1 to 10% w/w.
5. The synergistic insecticidal composition, as claimed in claim 1, wherein the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, disintegration agent, thickener, filler.
6. The synergistic insecticidal composition as claimed in claim 1, wherein the composition is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion

water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) 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).
7. The synergistic insecticidal composition as claimed in claim 1 to 6, wherein the composition is formulated as suspension concentrate and water-dispersible granule.
8. The synergistic insecticidal composition, as claimed in claim 5 and 7, wherein the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, defoamer, biocide, thickener, and wherein the formulation is a suspension concentrate.
9. The synergistic insecticidal composition, as claimed in claim 5 and 7, wherein the excipient is selected from the group comprising dispersing agent, wetting agent, anti-freezing agent, disintegration agent, defoamer, filler, and wherein the formulation is water dispersible granule.
10. The synergistic insecticidal composition as claimed in claim 5, wherein the dispersing agent is selected from the group comprising amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, naphthalene sulphonate of formaldehyde condensate, lignin based sulphonate and

combinations thereof, and present in an amount in the range from 2 to 10%
w/w.
11. The synergistic insecticidal composition as claimed in claim 5, wherein the wetting agent is selected from the group consisting of ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate and combinations thereof, and present in an amount in the range from 1 to 5% w/w.
12. The synergistic insecticidal composition as claimed in claim 5, wherein the anti-freezing agent is selected from the group consisting of propylene glycol, diethylene glycol, monoethylene glycol and combinations thereof, and present in an amount in the range from 2 to 10% w/w.
13. The synergistic insecticidal composition as claimed in claim 5, wherein the defoamer is dimethyl polysiloxane emulsion and present in an amount in the range from 0.01 to 1% w/w.
14. The synergistic insecticidal composition as claimed in claim 5, wherein the disintegration agent is selected from citric acid and sodium bicarbonate and present in an amount in the range from 1 to 2% w/w.
15. The synergistic insecticidal composition as claimed in claim 5, wherein the biocide is selected from the group consisting of 20% aqueous dipropylene glycol solution of l,2-benzisothiazolin-3-one, formaldehyde and combinations thereof and present in an amount in the range from 0.01 to 0.50% w/w.
16. The synergistic insecticidal composition as claimed in claim 5, wherein the thickener is xanthan gum and present in an amount in the range from 0.01 to 0.50% w/w.

17. The synergistic insecticidal composition as claimed in claim 5, wherein the filler is selected from bentonite clay, china clay, silica, kaolin and diatomaceous earth.