DESC:FORM 2

THE PATENTS ACT 1970
(SECTION 39 OF 1970)

&

THE PATENT RULES, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

SUSPO-EMULSION COMPOSITION OF DIAFENTHIURON AND PYRIPROXYFEN WITH BIOCIDE

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under Companies Act of 1956, having its principal place of business at Coromandel House, Sardar Patel Road, Secunderabad – 500 003, Telangana, India.

The following specification particularly describes the invention and the manner in which it is to be performed:
FIELD OF THE INVENTION
The present invention relates to suspo-emulsion composition of Diafenthiuron and Pyriproxyfen with a Biocide.

The present invention specifically relates to suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising biocide, dispersing agents, emulsifiers and optionally other agrochemically acceptable excipients.

The present invention specifically relates to suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising 1,2-benzisothiazolin-3-one, dispersing agents, emulsifiers and optionally other agrochemically acceptable excipients.

The present invention specifically relates to suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising 1,2-benzisothiazolin-3-one, polyoxyalkylene glycol butyl ether, ethoxylated TSP-phosphate ester and / or sodium naphthalene condensate formaldehyde as dispersing agents, calcium dodecyl benzene sulfonate as emulsifier and optionally other agrochemically acceptable excipients.

The present invention also relates to a process for the preparation of suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising the steps of preparing aqueous phase, preparing organic phase, adding organic phase to aqueous phase, wet milling, preparing gel suspension, adding gel suspension to the wet milled suspension and packaging.

BACKGROUND OF THE INVENTION
Diafenthiuron is a pro-insecticide and acaricide having low aqueous solubility but is readily soluble in many organic solvents. It is volatile and, based on its chemical properties, it is unlikely to leach to ground water. It is not persistent in most soil systems but may be very persistent in aquatic systems. It has a low mammalian toxicity but is moderate to highly toxic for most biodiversity including aquatic life, bees and worms.
Diafenthiuron is a chemical compound from the group of thioureas. It was introduced by Ciba-Geigy in 1990 as an insecticide and acaricide. The chemical name of Diafenthiuron is 1-tert-butyl-3-(2,6-di-isopropyl-4-phenoxyphenyl)thiourea. Diafenthiuron has a chemical formula of C23H32N2OS and molecular mass of 384.58 g/mol. It has structural formula of:

Diafenthiuron is mainly used to prevent and kill the pests and mites in cotton, fruit trees, vegetables, ornamental plants, soybeans and other crops. It also can be used to control the red spider on citrus tree and apple tree, the diamond back moth and other pests of cruciferous vegetables.

Pyriproxyfen is a pesticide which is found to be effective against a variety of insects. It was introduced in the US in 1996, to protect cotton crops against whitefly. It has also been found useful for protecting other crops. It is also used as prevention for flea control on household pets, for killing indoor and outdoor ants and roaches. Methods of application include aerosols, bait, carpet powders, foggers, shampoos and pet collars. Pyriproxyfen is a juvenile hormone analog and an insect growth regulator. It prevents larvae from developing into adulthood and thus rendering them unable to reproduce.

The chemical name of Pyriproxyfen is 2-[1-methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine. Pyriproxyfen has a chemical formula of C20H19NO3 and molecular mass of 321.37 g/mol. It has structural formula of:

Pyriproxyfen is a broad-spectrum insect growth regulator with insecticidal activity against public health insect pests: houseflies, mosquitoes and cockroaches. In agriculture and horticulture, Pyriproxyfen has registered uses for the control of scale, whitefly, bollworm, jassids, aphids and cutworms.

Suspo-emulsion (SE) formulations are used to combine two active ingredients with very different physical properties into one formulation. They are a combination of suspension concentrate (SC) and concentrated aqueous emulsion (EW) technologies.

Suspo-emulsion is a formulation containing both solid and liquid active ingredients dispersed in an aqueous phase. An aqueous suspo-emulsion is a mixture of water-insoluble active ingredients dispersed in an aqueous solution, where one (or more) of the active ingredients is in suspension form and one (or more) of the active ingredients is in emulsion form. The formulation is intended for dilution into water prior to spray application.

EP Publication No. 2 460 408 A1 discloses nematicidal compounds, their formulation as nematicidal composition and their use for controlling nematodes, preferably plant parasitic nematodes, wherein Diafenthiuron and Pyriproxyfen are nematicides. It discloses nematicidal suspo-emulstion composition to be used in agriculture or horticulture. However, neither specific suspo-emulsion compositions nor compositions of combination of Diafenthiuron and Pyriproxyfen are specifically enabled.

IN Patent Application No. 284/MUM/2014 discloses synergistic combination suspo-emulsion formulation comprising a) Pyriproxyfen as a free base or its agrochemically acceptable salts b) Diafenthiuron as a free base or its agrochemically acceptable salts c) Dispersant d) Antifreezing agent e) Anti-foaming agent f) Suspending agent g) Antimicrobial agent h) Thickener and i) Buffering agent.

US Publication No. 2010/0278890 A1 discloses suspo-emulsion comprising: water; lignosulfonate material; a first pesticide active; and second pesticide active. The pesticides may include, but are not limited to herbicides, insecticides, and fungicides. However, Diafenthiuron and Pyriproxyfen are not enabled in this application.

WO Publication No. 2020/154684 A1 discloses composition comprising an agricultural agent in particulate form; and microfibrillated cellulose; wherein the particulate form is selected from the group consisting of a liquid droplet, a gel, or a combination thereof; and wherein the agricultural agent in particulate form is part of a suspo-emulsion (SE). The composition disclosed in this application contain specifically microfibrillated cellulose along with Active Ingredients.

None of the prior art references discloses suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising 1,2-benzisothiazolin-3-one, polyoxyalkylene glycol butyl ether, ethoxylated TSP-phosphate ester and / or sodium naphthalene condensate formaldehyde as dispersing agents, calcium dodecyl benzene sulfonate as emulsifier and optionally other agrochemically acceptable excipients.

The polyoxyalkylene glycol butyl ether gives good solubility to Pyriproxyfen and by using this surfactant there is no need of using the solvent in the formulation. Sodium naphthalene condensate formaldehyde acts as a viscosity modifier which reduces the formulation density from thick to thin suspension. Calcium dodecyl benzene sulfonate gives complete emulsification in low dosage and acts as a dispersing agent to the suspension part. 1,2-benzisothiazolin-3-one which helps to prevent the bacterial/fungus growth in the formulation as suspo-emulsion containing major water part.

OBJECTIVE OF THE INVENTION
The main objective of the present invention is to provide a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen with a biocide.

Another objective of the present invention is to provide a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising biocide, dispersing agents, emulsifiers and optionally other agrochemically acceptable excipients.

Yet another objective of the present invention is to provide suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising 1,2-benzisothiazolin-3-one, polyoxyalkylene glycol butyl ether, ethoxylated TSP-phosphate ester and / or sodium naphthalene condensate formaldehyde as dispersing agents, calcium dodecyl benzene sulfonate as emulsifier and optionally other agrochemically acceptable excipients

Still another objective of the present invention is to provide a process for the preparation of suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising the steps of preparing aqueous phase, preparing organic phase, adding organic phase to aqueous phase, wet milling, preparing gel suspension, adding gel suspension and packaging.

SUMMARY OF THE INVENTION
Accordingly, the present invention provides a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen.

One embodiment of the present invention provides a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen with a biocide.

Another embodiment of the present invention provides a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen with a biocide, wherein the biocide is 2-benzisothiazolin-3-one.

Another embodiment of the present invention provides a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising biocide, dispersing agents, emulsifiers and optionally other agrochemically acceptable excipients.

Another embodiment of the present invention provides a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising 1,2-benzisothiazolin-3-one, polyoxyalkylene glycol butyl ether, ethoxylated TSP-phosphate ester and / or sodium naphthalene condensate formaldehyde as dispersing agents, calcium dodecyl benzene sulfonate as emulsifier and optionally other agrochemically acceptable excipients.

Another embodiment of the present invention provides a suspo-emulsion composition comprising:
(a) Diafenthiuron,
(b) Pyriproxyfen,
(c) biocide,
(d) dispersing agents,
(e) emulsifier,
(f) anti-freezing agent,
(g) defoamer,
(h) viscosity modifier,
(i) pH modifier, and
(j) solvent/filler.

Another embodiment of the present invention provides a suspo-emulsion composition comprising:
(a) Diafenthiuron in the range of 10% to 40% w/w,
(b) Pyriproxyfen in the range of 1% to 10% w/w,
(c) biocide in the range of 0.01% to 5% w/w,
(d) dispersing agents in the range of 1% to 20% w/w,
(e) emulsifier in the range of 1% to 10% w/w,
(f) anti-freezing agent in the range of 2% to 20% w/w,
(g) defoamer in the range of 1% to 5% w/w,
(h) viscosity modifier in the range of 2% to 10% w/w,
(i) pH modifier in the range of 5% to 20% w/w, and
(j) solvent/filler in the range of 20% to 60% w/w.

Another embodiment of the present invention provides a suspo-emulsion composition comprising:
(a) Diafenthiuron,
(b) Pyriproxyfen,
(c) 1,2-benzisothiazolin-3-one,
(d) polyoxyalkylene glycol butyl ether,
(e) ethoxylated TSP-phosphate ester,
(f) sodium naphthalene condensate formaldehyde,
(g) calcium dodecyl benzene sulfonate,
(h) propylene glycol,
(i) polydimethylsiloxane,
(j) xanthomonas campestris,
(k) solution of potassium hydrogen phosphate salt and sodium hydroxide, and
(l) distilled water.

Another embodiment of the present invention provides a suspo-emulsion composition comprising:
(a) Diafenthiuron in the range of 10% to 40% w/w,
(b) Pyriproxyfen in the range of 1% to 10% w/w,
(c) 1,2-benzisothiazolin-3-one in the range of 0.01% to 5% w/w,
(d) polyoxyalkylene glycol butyl ether in the range of 3% to 10 % w/w,
(e) ethoxylated TSP-phosphate ester in the range of 0.1% to 5% w/w,
(f) sodium naphthalene condensate formaldehyde in the range of 0.1% to 5% w/w,
(g) calcium dodecyl benzene sulfonate in the range of 1% to 10% w/w,
(h) propylene glycol in the range of 2% to 20% w/w,
(i) polydimethylsiloxane in the range of 1% to 5% w/w,
(j) xanthomonas campestris in the range of 2% to 10% w/w,
(k) solution of potassium hydrogen phosphate salt and sodium hydroxide in the range of 5% to 20% w/w, and
(l) distilled water in the range of 20% to 60% w/w.

Yet another embodiment of the present invention provides a process for the preparation of suspo-emulsion composition comprising steps of:
(a) preparing the aqueous phase,
(b) preparing the organic phase,
(c) adding organic phase to aqueous phase,
(d) wet milling and preparing gel suspension, and
(e) packing.

Yet another embodiment of the present invention provides a process for the preparation of suspo-emulsion composition comprising steps of:
(a) preparing the aqueous phase comprising:
i. adding polyalkoxylated butyl ether to propylene glycol under stirring,
ii. adding ethoxylated TSP-phosphate ester, water and 1,2 benzisothiazolin-3-one under stirring,
iii. adding polydimethylsiloxane and buffer solution,
iv. adding diafenthiuron, sodium naphthalene condensate formaldehyde and homogenizing the mixture,
(b) preparing the organic phase comprising:
i. heating polyalkoxylated butyl ether,
ii. adding Pyriproxyfen under stirring,
iii. adding calcium dodecyl benzene sulfonate and stirring,
(c) adding organic phase to aqueous phase under stirring,
(d) milling the slurry obtained in step (c) to obtain desired particle size,
(e) preparing gel suspension by adding xanthomonas campestris to propylene glycol then benzisothiazolin-3-one and adding to the distilled water under stirring, and
(f) adding gel suspension obtained in step (e) to slurry obtained in step (d).

DETAILED DESCRIPTION OF THE INVENTION
The term "comprising", which is synonymous with "including", "containing", or "characterized by" here is defined as being inclusive or open-ended, and does not exclude additional, unrecited elements or method steps, unless the context clearly requires otherwise.

The present invention provides a suspo-emulsion composition of Diafenthiuron and Pyriproxyfen comprising 1,2-benzisothiazolin-3-one, dispersing agents, emulsifiers and optionally other agrochemically acceptable excipients.

The present invention provides a suspo-emulsion composition comprising Diafenthiuron, Pyriproxyfen, biocide, dispersing agents, emulsifier, anti-freezing agent, defoamer, viscosity modifier, pH modifier and solvent/filler.

The concentration of ¬¬¬ Diafenthiuron used in the suspo-emulsion composition is from 10% to 40% w/w of the total weight of the composition. Preferably used concentration of Diafenthiuron is from 15% to 30% w/w of the total weight of the composition.

The concentration of ¬¬¬ Pyriproxyfen used in the suspo-emulsion composition is from 1% to 10% w/w of the total weight of the composition. Preferably used concentration of ¬¬¬ Pyriproxyfen is from 4% to 8% (w/w) of the total weight of the composition.

Biocide used in the composition of the present invention includes but not limited to 1,2-benzisothiazolin-3-one (Proxel GXL).

The concentration of biocide used in the used in the present composition is from 0.01% to 5% w/w of the total weight of the composition. Preferably used concentration of biocide is 0.05% to 1% w/w of the total weight of the composition.

Dispersing agents used in the composition of the present invention includes but not limited to sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX), polyalkoxylated butyl ether (ETHYLAN NS500LQ), ethoxylated TSP-phosphate ester (ARGILAN 1015), polyalkylene oxide block copolymer (TOXIMUL 8323), iso-tridecyl alcohol polyglycol ether (8EO) (GENAPOL X 080), polyoxyethylene alkyl ether (ATLOX 4894), polymethyl methacrylate-polyethylene glycol graft copolymer (ATLOX 4913), tristyrylphenol polyethoxyether phosphate (SOPROPHOR 3D33) and combinations thereof.

The concentration of dispersing agents used in the present composition is from 1% to 20% w/w of the total weight of the compositions. Preferably used concentration of dispersing agents is 5% to 15% w/w of the total weight of the composition.

The emulsifier used in the composition are anionic & nonionic surfactants. The anionic surfactants may be polyarylphenol polyalkoxyether sulfates and/or phosphates; C8-18 alcohol polyalkoxyether phosphates, carboxylates, and/or citrates; alkyl benzenesulfonic acids; C8-20 alkyl carboxylates including fatty acids; C8-20 alcohol sulfates; C8-20 alcohol phosphate mono- and diesters; C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene ether carboxylates, sulfates and sulfonates; C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene phosphate mono- and diesters; C8-20 alkylbenzene sulfonates (GERONOL FF4 AND GERONOL FF6 etc), naphthalene sulfonates and formaldehyde condensates thereof; lignosulfonates; C8-20 alkyl sulfosuccinates and sulfosuccinamates; C8-20 acyl glutamates, sarcosinates, isethionates and taurates; water-soluble soaps and mixtures thereof.

Non-ionic surfactant is a water-soluble, 20 to 250 ethylene glycol ether groups containing poly adducts of ethylene oxide and propylene oxide (TOXIMUL 8320), ethylene diamino polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl moiety, the substances normally contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of non-ionic surfactants are nonylphenol polyethoxy ethanols, vegetable oil poly glycol ethers, poly adducts of ethylene oxide and propylene oxide, tributyl phenoxy polyethoxy ethanol (ETHYLAN NS 500), octyl phenoxy polyethoxy ethanol.

Emulsifier used in the composition of the present invention includes calcium dodecyl benzene sulfonate (RHODOCAL 60BER), polyoxyethylene sorbitan monolaurate (TWEEN 20) or combinations thereof.

The concentration of emulsifier used in the present composition is from 1% to 10% w/w of the total weight of the composition. Preferably used concentration of emulsifier is 2% to 6% (w/w) of the total weight of the composition.

Anti-freezing agent used in the composition of the present invention includes but not limited to ethylene glycol, propylene glycol, glycerine or urea. Preferably used anti-freezing agent is propylene glycol.

The concentration of anti-freezing agent used in the present composition is from 2% to 20% w/w of the total weight of the composition. Preferably used concentration of anti-freezing agent is 4% to 10% (w/w) of the total weight of the composition.

Defoamer used in the composition of the present invention includes but not limited to silicon based defoamers like polydimethylsiloxane (UNISIL DEFOAMER).

The concentration of defoamer used in the present composition is from 1% to 5% w/w of the total weight of the composition. Preferably used concentration of defoamer is 1% to 2% w/w of the total weight of the composition.

Viscosity modifier used in the composition of the present invention includes xanthomonas campestris (RHODOPOL Gel).

The concentration of viscosity modifier used in the present composition is from 2% to 10% w/w of the total weight of the composition. Preferably used concentration of viscosity modifier is 4% to 6% w/w of the total weight of the composition.

pH modifier used in the composition of the present invention includes but not limited to buffer of potassium hydrogen phosphate and sodium hydroxide .

The concentration of pH modifier used in the present composition is from 5% to 20% w/w of the total weight of the composition. Preferably used concentration of pH modifier is 5% to 15% w/w of the total weight of the composition.

Filler/solvent used in the composition of the present invention includes but not limited to purified water, aromatic hydrocarbons, aliphatic hydrocarbons, dialkylene glycol dialkyl ethers (diethylene glycol dimethyl ether), propylene glycol, ketones, alkyl esters of acetic acid or mixtures thereo. Aromatic and aliphatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosene or substituted naphthalenes, Naphthalene- depleted C11 aromatic fluid (Solvesso 200ND), polar aprotic solvents such as DMSO, DMF, NMP etc, blend of N,N-dimethyl octan/ decanamide (ARMID DM810), mixtures of mono- and polyalkylated aromatics are commercially available under the registered trademarks, SOLVENT C-IX, SOLVESSO® and SHELLSOL® and Petrol Spezial®. Preferably used filler/solvent is purified water.

The concentration of filler/solvent used in the present composition is from 20% to 60% w/w of the total weight of the composition. Preferably used concentration of filler is 30% to 50% (w/w) of the total weight of the composition.

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

Diafenthiuron 25 % + Pyriproxyfen 5% SE composition:
Example-1:
Sr.No. Composition %W/W Quantity in gm
1. Diafenthiuron tech @ 96% (b) 25 % 26.04 260.4
2. Pyriproxyfen tech @ 97.41 (b) 5% 5.13 51.3
3. Propylene glycol 5.0 50
4. Polyalkoxylated butyl ether (ETHYLAN NS500LQ) 7.0 70
5. Ethoxylated TSP-phosphate ester (ARGILAN 1015) 1.0 10
6. 1,2-benzisothiazolin-3-one (PROXEL GXL) 0.1 1.0
7. Polydimethylsiloxane (UNISIL DEFOAMER) 1.0 10
8. Sodium naphthalene condensate formaldehyde (DISPERSOGEN Max) 1.0 10
9. Calcium dodecyl benzene sulfonate (RHODOCAL 60BER) 2.0 20
10. RHODOPOL Gel 5.0 50
11. Distilled water 36.73 367.3
12. Buffer 10 100
Total 100 1000

Manufacturing process
Step 1: preparation of aqueous phase
• Propylene glycol taken in vessel and polyalkoxylated butyl ether (ETHYLAN NS500LQ) was added under stirring.
• Ethoxylated TSP-phosphate ester (ARGILAN 1015), water and 1,2-benzisothiazolin-3-one (PROXEL GXL) were added under stirring followed by adding polydimethylsiloxane (UNISIL DEFOAMER) and buffer solution.
• Mixture was stirred for 15 minutes and Diafenthiuron technical was added.
• Mixture was homogenized and sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX), mixture was further homogenized.

Step 2: preparation of organic phase
• Polyalkoxylated butyl ether (ETHYLAN NS500LQ) heated in a vessel to 40°C.
• Pyriproxyfen technical was added slowly under stirring till clear solution forms.
• Calcium dodecyl benzene sulfonate (RHODOCAL 60BER) was added and stirred for 30 mins.

Step 3: addition of organic phase to aqueous phase
• Organic phase is slowly added to aqueous phase under stirring and continued the stirring for 1hr.

Step 4: wet milling of slurry
• Wet slurry passed through dyno-mill at temperature less than 35° C and collected in separate vessel.
• Continuous stirring maintained in vessels to avoid the sedimentation.
• Sample was analysis to check the particle size distribution (PSD).
• Milling process repeated till desired particle size obtained (i.e d90 < 15 µ)

Step 5: preparation of 2.0% RHODOPOL 23 W gel (gel suspension)
• Rhodapol 23W added in propylene glycol then benzisothiazolin-3-one (PROXEL GXL) 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.

Step 6: gelling of wet milled slurry
• Require quantity of gel added to the wet slurry prepared in step 4 and stirred the mixture for ~3 h for homogenization.
• Material was packed in suitable bottle.

Example-2:
Sr.No. Composition %W/W Quantity in gm
1. Diafenthiuron tech @ 96% (b) 25 % 26.04 260.4
2. Pyriproxyfen tech @ 97.41 (b) 5% 5.13 51.3
3. Propylene glycol 5.0 50
4. Polyalkylene oxide block copolymer (TOXIMUL 8323) 7.0 70
5. Iso-tridecyl alcohol polyglycol ether (8EO) (GENAPOL X 080) 1.0 10
6. 1,2-benzisothiazolin-3-one (PROXEL GXL) 0.1 1.0
7. Polydimethylsiloxane (UNISIL DEFOAMER) 1.0 10
8. Sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX) 1.0 10
9. Calcium dodecyl benzene sulfonate (RHODOCAL 60BER) 2.0 20
10. RHODOPOL Gel 5.0 50
11. Distilled water 36.73 367.3
12. Buffer 10 100
Total 100 1000

Manufacturing process
Step 1: preparation of aqueous phase
• Propylene glycol taken in vessel and polyalkylene oxide block copolymer (TOXIMUL 8323) was added under stirring.
• Iso-tridecyl alcohol polyglycol ether (8EO) (GENAPOL X 080), water and 1,2-benzisothiazolin-3-one (PROXEL GXL) were added under stirring followed by adding polydimethylsiloxane (UNISIL DEFOAMER) and buffer solution.
• Mixture was stirred for 15 minutes and Diafenthiuron technical was added.
• Mixture was homogenized and sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX), mixture was further homogenized.

Step 2: preparation of organic phase
• Polyalkylene oxide block copolymer (TOXIMUL 8323) heated in a vessel to 40°C.
• Pyriproxyfen technical was added slowly under stirring till clear solution forms.
• Calcium dodecyl benzene sulfonate (RHODOCAL 60BER) was added and stirred for 30 mins.

Step 3: addition of organic phase to aqueous phase
• Organic phase is slowly added to aqueous phase under stirring and continued the stirring for 1hr.

Step 4: wet milling of slurry
• Wet slurry passed through dyno-mill at temperature less than 35° C and collected in separate vessel.
• Continuous stirring maintained in vessels to avoid the sedimentation.
• Sample was analysis to check the particle size distribution (PSD).
• Milling process repeated till desired particle size obtained (i.e d90 < 15 µ)

Step 5: preparation of 2.0% RHODOPOL 23 W gel (gel suspension)
• Rhodapol 23W added in propylene glycol then benzisothiazolin-3-one (PROXEL GXL) 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.

Step 6: gelling of wet milled slurry
• Require quantity of gel added to the wet slurry prepared in step 4 and stirred the mixture for ~3 h for homogenization.
• Material was packed in suitable bottle.

Example-3:
Sr.No. Composition %W/W Quantity in gm
1. Diafenthiuron tech @ 96% (b) 25 % 26.04 260.4
2. Pyriproxyfen tech @ 97.41 (b) 5% 5.13 51.3
3. Propylene Glycol 5.0 50
4. Polyoxyethylene alkyl ether (ATLOX 4894) 7.0 70
5. Polymethyl methacrylate-polyethylene glycol graft copolymer (ATLOX 4913) 1.0 10
6. 1,2-benzisothiazolin-3-one (PROXEL GXL) 0.1 1.0
7. Polydimethylsiloxane (UNISIL DEFOAMER) 1.0 10
8. Sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX) 1.0 10
9. Calcium dodecyl benzene sulfonate (RHODOCAL 60BER) 2.0 20
10. RHODOPOL Gel 5.0 50
11. Distilled water 36.73 367.3
12. Buffer 10 100
Total 100 1000

Manufacturing process
Step 1: preparation of aqueous phase
• Propylene glycol taken in vessel and Polyoxyethylene alkyl ether (Atlox 4894) was added under stirring.
• Polymethyl methacrylate-polyethylene glycol graft copolymer (ATLOX 4913), water and 1,2-benzisothiazolin-3-one (PROXEL GXL) were added under stirring followed by adding polydimethylsiloxane (UNISIL DEFOAMER) and buffer solution.
• Mixture was stirred for 15 minutes and Diafenthiuron technical was added.
• Mixture was homogenized and sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX), mixture was further homogenized.

Step 2: preparation of organic phase
• Polyoxyethylene alkyl ether (ATLOX 4894) heated in a vessel to 40°C.
• Pyriproxyfen technical was added slowly under stirring till clear solution forms.
• Calcium dodecyl benzene sulfonate (RHODOCAL 60BER) was added and stirred for 30 mins.

Step 3: addition of organic phase to aqueous phase
• Organic phase is slowly added to aqueous phase under stirring and continued the stirring for 1hr.

Step 4: wet milling of slurry
• Wet slurry passed through dyno-mill at temperature less than 35° C and collected in separate vessel.
• Continuous stirring maintained in vessels to avoid the sedimentation.
• Sample was analysis to check the particle size distribution (PSD).
• Milling process repeated till desired particle size obtained (i.e d90 < 15 µ)

Step 5: preparation of 2.0% RHODOPOL 23 W gel (gel suspension)
• Rhodapol 23W added in propylene glycol then benzisothiazolin-3-one (PROXEL GXL) 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.

Step 6: gelling of wet milled slurry
• Require quantity of gel added to the wet slurry prepared in step 4 and stirred the mixture for ~3 h for homogenization.
• Material was packed in suitable bottle.

Example-4:
Sr.No. Compositions %W/W Quantity in gm
1. Diafenthiuron tech @ 96% (b) 25 % 26.04 260.4
2. Pyriproxyfen tech @ 97.41 (b) 5% 5.13 51.3
3. Propylene glycol 5.0 50
4. Tristyrylphenol polyethoxyether phosphate (SOPROPHOR 3D33) 7.0 70
5. Polymethyl methacrylate-polyethylene glycol graft copolymer (ATLOX 4913) 1.0 10
6. 1,2-benzisothiazolin-3-one (PROXEL GXL) 0.1 1.0
7. Polydimethylsiloxane (UNISIL DEFOAMER) 1.0 10
8. Sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX) 1.0 10
9. Polyoxyethylene sorbitan monolaurate (TWEEN 20) 2.0 20
10. RHODOPOL Gel 5.0 50
11. Distilled water 36.73 367.3
12. Buffer 10 100
Total 100 1000

Manufacturing process
Step 1: preparation of aqueous phase
• Propylene glycol taken in vessel and Tristyrylphenol polyethoxyether phosphate (SOPROPHOR 3D33) was added under stirring.
• Polymethyl methacrylate-polyethylene glycol graft copolymer (ATLOX 4913), water and 1,2-benzisothiazolin-3-one (PROXEL GXL) were added under stirring followed by adding polydimethylsiloxane (UNISIL DEFOAMER) and buffer solution.
• Mixture was stirred for 15 minutes and Diafenthiuron technical was added.
• Mixture was homogenized and sodium naphthalene condensate formaldehyde (DISPERSOGEN MAX), mixture was further homogenized.

Step 2: preparation of organic phase
• Polyalkoxylated butyl ether (ETHYLAN NS500LQ) heated in a vessel to 40°C.
• Pyriproxyfen technical was added slowly under stirring till clear solution forms.
• Polyoxyethylene sorbitan monolaurate (TWEEN 20) was added and stirred for 30 mins.

Step 3: addition of organic phase to aqueous phase
• Organic phase is slowly added to aqueous phase under stirring and continued the stirring for 1hr.

Step 4: wet milling of slurry
• Wet slurry passed through dyno-mill at temperature less than 35° C and collected in separate vessel.
• Continuous stirring maintained in vessels to avoid the sedimentation.
• Sample was analysis to check the particle size distribution (PSD).
• Milling process repeated till desired particle size obtained (i.e d90 < 15 µ)

Step 5: preparation of 2.0% RHODOPOL 23 W gel (gel suspension)
• Rhodapol 23W added in propylene glycol then benzisothiazolin-3-one (PROXEL GXL) 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.

Step 6: gelling of wet milled slurry
• Require quantity of gel added to the wet slurry prepared in step 4 and stirred the mixture for ~3 h for homogenization.
• Material was packed in suitable bottle.

Field efficacy trials

Trial 1- Sucking pest complex of Cotton Crop
The field efficacy trials were conducted to evaluate the efficacy of innovative mixtures of Pyriproxyfen and Diafenthiuron against sucking insects in cotton. The trials were laid out with randomized block design with net plot size of 5m x 6m. Cotton crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack sprayer with 500 liter of water spray volume per hectare at 40-50 days after sowing. The observations were recorded by counting the no. of sucking insects (Whitefly adult and Nymph, Jassids, Thrips and Mites) per leaf from six leaves per plant. The observations were taken from randomly selected five plants per plot. The observations were recorded at before spraying and 10 DAA (Days after application).

Table 1: Effect of treatment on efficacy against sucking Pests control in Cotton

Compositions
Dose Gram Active/hectare % Insect Control at 10 DAA

Whiteflies adults
Whiteflies Nymphs
Thrips
Jassids
Mites
Pyriproxyfen 5% + Diafenthiuron 25 % SE 62.5 + 312.5 98.5 98.0 84.5 60.0 82.5
Pyriproxyfen 10% EC 62.5 88.0 82.0 28.0 18.0 25.0
Diafenthiuron 50% WP 312.5 69.0 74.0 53.5 39.6 57.8
SE- Suspoemulsion, WP Wettable Powder, EC Emulsifiable Concentrate, DAA Days after Application

Results presented in Tables 1 shows that excellent efficacy observed in the combination of Pyriproxyfen 5% + Diafenthiuron 25 % SE as compared to solo products against sucking pest complex whiteflies, Thrips, Jassids & Mites. Solo products were not able to provide satisfactory and broad-spectrum control of Whiteflies, Thrips, Jassids & Mites. However, in combination the efficacy improved significantly which shows a synergistic effect of two actives in controlling sucking pest complex in cotton.

,CLAIMS:WE CLAIM:
1. The suspo-emulsion composition comprising:
(a) Diafenthiuron in the range of 10% to 40% w/w,
(b) Pyriproxyfen in the range of 1% to 10% w/w,
(c) biocide in the range of 0.01% to 5% w/w,
(d) dispersing agents in the range of 1% to 20% w/w,
(e) emulsifier in the range of 1% to 10% w/w,
(f) anti-freezing agent in the range of 2% to 20% w/w,
(g) defoamer in the range of 1% to 5% w/w,
(h) viscosity modifier in the range of 2% to 10% w/w,
(i) pH modifier in the range of 5% to 20% w/w, and
(j) solvent/filler in the range of 20% to 60% w/w.

2. The composition as claimed in claim 1, wherein biocide is 2-benzisothiazolin-3-one.

3. The composition as claimed in claim 1, wherein dispersing agents are selected from sodium naphthalene condensate formaldehyde, polyalkoxylated butyl ether, ethoxylated TSP-phosphate ester, polyalkylene oxide block copolymer, iso-tridecyl alcohol polyglycol ether (8EO), polyoxyethylene alkyl ether, polymethyl methacrylate-polyethylene glycol graft copolymer, tristyrylphenol polyethoxyether phosphate or combinations thereof.

4. The composition as claimed in claim 1, wherein emulsifier is calcium dodecyl benzene sulfonate, polyoxyethylene sorbitan monolaurate or combinations thereof.

5. The composition as claimed in claim 1, wherein anti-freezing agent is ethylene glycol, propylene glycol, glycerine and urea.

6. The composition as claimed in claim 1, wherein defoamer is polydimethylsiloxane.

7. The composition as claimed in claim 1, wherein viscosity modifier is xanthomonas campestris.

8. The composition as claimed in claim 1, wherein pH modifier is potassium hydrogen phosphate and sodium hydroxide.

9. The composition as claimed in claims 1 - 8, wherein suspo-emulsion composition comprising:
(a) Diafenthiuron in the range of 10% to 40% w/w,
(b) Pyriproxyfen in the range of 1% to 10% w/w,
(c) 1,2-benzisothiazolin-3-one in the range of 0.01% to 5% w/w,
(d) polyoxyalkylene glycol butyl ether in the range of 3% to 10 % w/w,
(e) ethoxylated TSP-phosphate ester in the range of 0.1% to 5% w/w,
(f) sodium naphthalene condensate formaldehyde in the range of 0.1% to 5% w/w,
(g) calcium dodecyl benzene sulfonate in the range of 1% to 10% w/w,
(h) propylene glycol in the range of 2% to 20% w/w,
(i) polydimethylsiloxane in the range of 1% to 5% w/w,
(j) xanthomonas campestris in the range of 2% to 10% w/w,
(k) solution of potassium hydrogen phosphate salt and sodium hydroxide in the range of 5% to 20% w/w, and
(l) distilled water in the range of 20% to 60% w/w.

10. The process for the preparation of suspo-emulsion composition as claimed in claim 9, wherein the process comprising steps of:
(a) preparing the aqueous phase comprising:
i. adding polyalkoxylated butyl ether to propylene glycol under stirring,
ii. adding ethoxylated TSP-phosphate ester, water and 1,2 benzisothiazolin-3-one under stirring,
iii. adding polydimethylsiloxane and buffer solution,
iv. adding diafenthiuron, sodium naphthalene condensate formaldehyde and homogenizing the mixture,
(b) preparing the organic phase comprising:
i. heating polyalkoxylated butyl ether,
ii. adding Pyriproxyfen under stirring,
iii. adding calcium dodecyl benzene sulfonate and stirring,
(c) adding organic phase to aqueous phase under stirring,
(d) milling the slurry obtained in step (c) to obtain desired particle size,
(e) preparing gel suspension by adding xanthomonas campestris to propylene glycol then benzisothiazolin-3-one and adding to the distilled water under stirring, and
(f) adding gel suspension obtained in step (e) to slurry obtained in step (d).

Dated this First (1st) day of April, 2022

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