DESC:FIELD OF THE INVENTION

The present invention relates to a synergistic pesticidal composition comprising of an insecticide and a fungicide. Particularly, the present invention relates to synergistic pesticidal composition of pymetrozine and cyproconazole with one or more agrochemical auxiliaries and a process thereof.

BACKGROUND OF THE INVENTION

Pesticides are substances or mixtures of substances that are mainly used in agriculture or in public health protection programs in order to protect plants from pests, weeds or diseases, and humans from vector-borne diseases, such as malaria, dengue fever, and schistosomiasis. Insecticides, fungicides, herbicides, rodenticides, and plant growth regulators are typical examples of pesticides.

In many economically important crops and cash crops such as rice, peppers, grapes and other agricultural crops, fungal infection and insect infestation may occur simultaneously. In order to control this farmer usually applies compositions comprising either single active or combinations of actives. Control of plant diseases and pests is an inevitable work in efficiently performing the agricultural production, and in order to achieve this purpose, synthetic pesticides have been used, resulting in making a remarkable achievement.

Pymetrozine is the only representative of the pyridine azomethines and is currently being developed worldwide for control of aphids and whiteflies in field crops, vegetables, ornamentals, cotton, hop, deciduous fruit, and citrus, and of the brown planthopper, Nilaparvata lugens. The compound appears to have great promise in integrated pest management (IPM) programs due to its high degree of selectivity, low mammalian toxicity, and safety to birds, fish, and nontarget arthropods.
Pymetrozine was discovered and is currently being registered and marketed by Ciba-Geigy with the tradenames “Fulfill”, “Relay” and “Sterling” in the USA and “Plenum” or “Chess” elsewhere.

The chemical name of pymetrozine is 6-methyl-4-[(E)-(pyridin-3-ylmethylene)amino]-4,5-dihydro-2H-[1,2,4]-triazin-3-one. The structure of pymetrozine is:

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

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

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

The mixing of insecticides with fungicides results in incompatibility of physical nature and may alter efficacy of the active ingredients. Hence, it requires due trial and experimentation to assess the compatibility of fungicides with insecticides and their influence on crops. Many pesticides with combination of one or more actives have been used by farmers. But still there is requirement for new combinations which can provide efficacy, low-cost benefit ratio, broad spectrum protection and decreased environmental load.

With increased use of chemical compounds as insecticides, herbicides, fungicides it has been observed that crops are becoming tolerant and resistant to use of composition comprising single active.

Hence, there is a need for combination of actives belonging to different classes and groups to allow for broader disease control spectrum that combines curative and preventive actives and has a lower dosage. Inventors of the present invention have surprisingly found the novel synergistic composition of an insecticide pymetrozine, and a fungicide cyproconazole with one or more agrochemical additives.

OBJECT OF THE INVENTION

The main object of the present invention is to provide a synergistic pesticidal composition of an insecticide and a fungicide.

Another object of the present invention is to provide a pesticidal combination of triazines, and triazole fungicide with one or more agrochemical auxiliaries.

Another object of the present invention is to provide a synergistic pesticidal composition of pymetrozine and cyproconazole with one or more agrochemical auxiliaries.

Yet another object of the present invention is to provide pesticidal oil dispersion (OD) composition comprising of pymetrozine and cyproconazole with one or more agrochemical auxiliaries.
Yet another objective of the present invention is to provide a process for the preparation of a pesticidal oil dispersion (OD) composition comprising the steps of taking pymetrozine and cyproconazole, stirring, milling, collecting, homogenizing, and packaging.

Yet another object of the present invention is to provide a synergistic pesticidal composition comprising an insecticidal and fungicidal combination that causes an enhanced insecticidal and fungicidal activity.

SUMMARY OF THE INVENTION

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

Another aspect of the present invention is to provide a pesticidal composition of triazines, and triazole fungicide with one or more agrochemical auxiliaries.

Another aspect of the present invention is to provide a pesticidal composition comprising combination of pymetrozine and cyproconazole with one or more agrochemical auxiliaries.

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

Yet another aspect of the present invention is to provide a pesticidal oil dispersion (OD) composition comprising:
a. pymetrozine in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. rheology modifiers in the range of 0.1% to 1.2% (w/w),
d. emulsifiers in the range of 5% to 10% (w/w), and
e. base oil in the range of 60% to 80% (w/w).

Yet another aspect of the present invention is to provide a pesticidal oil dispersion (OD) composition comprising:
a. pymetrozine in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. calcium alkyl benzene sulphonates in 2-ethylhexanol in the range of 2% to 5% (w/w),
d. castor oil ethoxylate with 36 mole EO in the range of 5% to 10% (w/w),
e. organic derivative of a hectorite clay in the range of 0.1% to 0.5% (w/w),
f. fumed silica in the range of 0.1% to 3% (w/w), and
g. methyl soyate oil in the range of 60% to 80% (w/w).

Yet another aspect of the present invention is to provide a process for the preparation of pesticidal oil dispersion composition, wherein the process comprising steps of:
(a) adding base oil in a disperser,
(b) adding first rheology modifier under stirring at 40-45°C,
(c) cooling to 20-30°C,
(d) adding pymetrozine and cyproconazole under stirring to the obtained homogenized suspension,
(e) adding second rheology modifier under stirring at same temperature,
(f) milling the obtained mixture for 4 hours till the desired particle size distribution is achieved,
(g) transferring the milled material into a separate vessel and continue stirring at room temperature over a period of 2 hours, and
(h) packing the obtained oil dispersion into the drum.

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

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

DETAILED DESCRIPTION OF THE INVENTION

The terms "comprise", "comprises", and "comprising" are to be interpreted inclusively rather than exclusively. Likewise, the terms "include", "including", and "or" should all be construed to be inclusive, unless such a construction is clearly prohibited from the context. However, the embodiments provided by the present disclosure may lack any element that is not specifically disclosed herein. Thus, a disclosure of an embodiment defined using the term "comprising" is also a disclosure of embodiments "consisting essentially of” and "consisting of” the disclosed components. Where used herein, the term "example," particularly when followed by a listing of terms, is merely exemplary and illustrative, and should not be deemed to be exclusive or comprehensive. Any embodiment disclosed herein can be combined with any other embodiment disclosed herein unless explicitly indicated otherwise.
It is to be noted that, as used in the specification, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.

As used herein, the terms "crops" and "vegetation" can include, for instance, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.

As used herein, immature vegetation may be understood to include small vegetative plants prior to reproductive stage, and mature vegetation may be understood to include vegetative plants during and after the reproductive stage.

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

Another embodiment of the present invention is to provide a pesticidal combination of triazines, and triazole fungicide with one or more agrochemical auxiliaries.

Yet another embodiment of the present invention is to provide a pesticidal composition comprising combination of pymetrozine and cyproconazole with one or more agrochemical auxiliaries.

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

Yet another embodiment of the present invention is to provide a pesticidal oil dispersion (OD) composition comprising:
a. pymetrozine in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. rheology modifiers in the range of 0.1% to 1.2% (w/w),
d. emulsifiers in the range of 5% to 10% (w/w), and
e. base oil in the range of 60% to 80% (w/w).

Yet another embodiment of the present invention is to provide a pesticidal oil dispersion (OD) composition comprising:
a. pymetrozine in the range of 10% to 15% (w/w),
b. cyproconazole in the range of 10% to 20% (w/w),
c. calcium alkyl benzene sulphonates in 2-ethylhexanol in the range of 2% to 5% (w/w),
d. castor oil ethoxylate in the range of 5% to 10% (w/w),
e. organic derivative of a hectorite clay in the range of 0.1% to 0.5% (w/w),
f. fumed silica in the range of 0.1% to 3% (w/w), and
g. methyl soyate oil in the range of 60% to 80% (w/w).

In yet another embodiment the present invention provides pymetrozine and cyproconazole composition in a wettable powder (WP), or a water-dispersible granule (WDG), or a suspension concentrates (SC), or a suspoemulsion (SE) form.

According to the present invention, a wettable powder (WP), or a water dispersible granule (WDG) formulation comprises one or more agrochemical acceptable auxiliaries selected from wetting agent, dispersing agent, rheology modifier, and filler.

According to the present invention a suspension concentrate (SC), or a suspoemulsion (SE) formulations comprises one or more agrochemical acceptable auxiliaries selected from wetting agent, dispersing agent, antifreezing agent, biocide, defoamer, viscosity modifier, emulsifier, rheology modifier, disintegrating agent and base.
In one embodiment of the present invention there are two types of rheology modifiers employed to maintain stability of the composition.

According to the present invention the first rheology modifier as used herein includes but are not limited to organic derivative of a hectorite clay (like Benton 38, Benton 27, Benton 1000), xanthan gum, vegetable oil derivatives such as blend of vegetable oil base (SURFOM ESP 8105), guar gum, locust bean gum, carrageenan, alginates, methyl cellulose, carboxyethyl sodium carboxymethylcellulose, hydroxyethyl cellulose, modified starches; other polysaccharides and modified polysaccharides, polyethylene alcohol, glycerol alkyl resins, silicon dioxide and cellulose derivatives. The second rheology modifier is selected from natural oils, mineral oils such as kyros oil and fumed silicas such as Aerosil R974, Aerosil 200, Aerosil 972, Aerosil R816, Aerosil 300, and combination thereof.

The concentration of rheology modifiers used in the present invention is from 0.1% to 1.2% (w/w). Preferably, concentration of the rheology modifier is 0.9 % (w/w) of the total weight of the composition.

The advantages in the present invention of using two rheology modifiers are:
i. Improved stability of the composition.
ii. Improved viscosity of the composition.
iii. Reduced phase separation thereby enhancing the homogeneity of the composition.
iv. Reduced sedimentation thereby enhancing the uniformity of the composition.
According to the present invention the rheology modifiers plays an important role in keeping the viscosity of the composition to minimize the oil separation and maintains the homogeneity.

According to the present invention, the dispersing agent as used herein includes but are not limited to ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers, Poly aryl alkylphenol polyethylene glycol phosphoric acid ester, Triethanol ammonium salt (DISPERSOGEN LFS), Calcium alkyl benzene sulphonate in 2-ethylhexanol (CALSOGEN 4814), n-C12 alkyl benzene sulfonate calcium salt Phosphate ester (SOPHROPHOR FLR), n-C12 alkyl benzene sulfonate calcium salt, n-C12 alkyl benzene sulfonate calcium salt (Phenylsulfonat CAL), calcium dodecyl benzene sulphonated (RHODOCAL 60 BER), polymeric esters (ATLOX 4916) and acrylic copolymer surfactant (ATLOX 4913). Preferred dispersing agents are calcium alkyl benzene sulphonate in 2-ethylhexanol (CALSOGEN 4814), Poly aryl alkylphenol polyethylene glycol phosphoric acid ester, Triethanol ammonium salt (DISPERSOGEN LFS), polymeric esters (ATLOX 4916), sodium lignosulphonate, alkyl naphthalene sulfonate condensate (Morwet D-425), ethoxylated alcohols (C12-16), (Tersperse 4894), Tersperse 2288, Borresperse NA (sodium naphthalene condensate formaldehyde and acrylic copolymer surfactant (ATLOX 4913).

The concentration of dispersing agent used in the present invention is from 5% to 7% (w/w). Preferably, the concentration of dispersing agent is 5% (w/w) of the total weight of the composition.

According to the present invention, the emulsifier as used herein includes but are not limited to nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers, aliphatic amine alkoxylates, polyoxy ethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty acid amide alkoxylates, fatty acid poly diethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isoforms tridecyl alcohol, fatty acid amides, alkyl poly glycosides, non-ionic surfactant blend (Atlox 309F), polyoxyethylene (40) sorbitol hexaoleate (Atlox G-1086), polyacrylate graft copolymer (DISPERSOGEN PSL 100), Calcium alkyl benzene sulphonate in 2-ethylhexanol (CALSOGEN 4814) with aromatic, alcoholic solvents and amine salts, Castor oil ethoxylate with 5 to 54 moles EO (EMULSOGEN EL 360), Tri-sec-butylphenol polyglycol ether with 4 EO (SAPOGENAT T 040), Ethoxylate of alkyl polyethylene glycol ether (Lutensol TO 5), EO/PO butyl ether (Ethylene 500 LQ), polyoxyethylene sorbitol ester (Tween 20) , Tristyryl phenol-polyethylene glycol ether (EMULSOGEN TS 160) or its combinations thereof.

The concentration of emulsifiers used in the present invention is from 5% to 10% (w/w). Preferably, concentration of emulsifiers is 8% (w/w).

According to the present invention, the emulsifier used for the present invention can also perform as surfactant, dispersant, foaming agent, or detergent.
As used herein, the term “wetting agent” may be understood as a chemical substance which is typically a surfactant used to reduce the surface tension of the water by penetrating in between the water molecules and thus reducing the cohesion between them. The waxy surface of many insects, fungi, and plants makes it difficult for most water-based pesticides solution to penetrate to their target. Hence these wetting agents help the solution to spread on the leaf surface thus increasing their efficiency. These agents aid in the milling process.
According to the present invention, the wetting agent is selected from non-ionic surfactants such as alkoxylates, fatty alcohol alkoxylates, siloxanes/silicones, alkylphenol alkoxylates, fatty acid alkoxylates, alkoxylated amines, alkoxylated fatty acid amides, terminally blocked alkoxylates, fatty acid esters of polyhydroxy compounds, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkylpolyglucosides, amine oxide, and combinations thereof.
Alkoxy groups may suitably be ethoxy, propoxy, or a combination of ethoxy and propoxy groups in random or block configuration. The non-limiting examples of the non-ionic surfactants include: alcohol alkoxylates (such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides (such as ethoxylated soybean, castor and rapeseed oils); alkylphenol alkoxylates (e.g., octyl- (such as the Triton X series), nonyl- (such as the Tergitol HP series), dinonyl-, or dodecyl-)); ethoxylated fatty acids; ethoxylated fatty esters and oils (such as Break Thru SP 133); ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers (such as block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids), alkyd PEG (polyethylene glycol) resins, alkyd type copolyesters, graft or comb polymers, and star polymers; polyethylene glycols (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides; and combinations thereof. The non-limiting examples of sorbitan fatty acid esters include sorbitan monolaurates (e.g., Span 20), sorbitan monopalmitates (e.g., Span 40), sorbitan monostearates (e.g., Span 60), sorbitan tristearates (e.g., Span 65), sorbitan monooleates (e.g., Span 80), sorbitan trioleates (e.g., Span 85), and combinations thereof. Non-limiting examples of polyethoxylated sorbitan fatty acid esters include Tween 20, Tween 21, Tween 40, Tween 60, Tween 80, and Surfonic L24-4. Non-limiting examples of sorbitol ethoxylate esters that may be suitable for the biopesticides described herein include polyoxyethylene sorbitol oleates (e.g., Arlatone TV), polyoxyethylene sorbitol hexaoleates (e.g., Cirrasol G-1086), polyoxyethylene sorbitol hexaoleates (e.g., Cirrasol G-1096), polyoxyethylene oleate-laurates (e.g., Atlox 1045AR), and combinations thereof.
According to the present invention, the wetting agents are selected from anionic surfactants comprising alkylaryl sulfonic acids and their salts; carboxylated alcohols; diphenyl sulfonate derivatives; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; salts of sulfates of alkoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts; and combinations thereof. Non-limiting examples of cationic counterions of the anionic surfactants in salt form may include, but are not limited to, alkali metal, alkaline-earth metal, ammonium, or (C1-6) alkyl ammonium cation.
According to the present invention, the non-limiting examples of the anionic surfactants that are used as wetting agents includes ammonium lauryl sulfate; magnesium lauryl sulfate; sodium 2-ethyl-hexyl sulfate; sodium octyl sulfate; sodium oleyl sulfate; sodium tridecyl sulfate; triethanolamine lauryl sulfate; ammonium nonylphenol ether sulfate; ammonium monoxynol-4-sulfate; sulfo succinamates; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid (Aerosol OT 75 PG); calcium naphthalene sulfonates (DAXAD 19LCAD); sodium methyl oleyl taurate (Geropon T-77); sodium dodecylbenzene sulfonate; N-oleyl N-methyl taurate; 1,4-dioctoxy-1,4-dioxo-butane-2-sulfonic acid; sodium lauryl sulphate; sodium lauryl ether sulfate (Steol CS-370); calcium dodecylbenzenesulfonate (Rhodacal 60 BE and 70 B); isopropyl amine dodecylbenzenesulfonate (Bio-Soft N-411); and sodium diisopropyl naphthalenesulfonate (Morwet IP). In yet another embodiment of the present invention, the wetting agent is 2,4,7,9-tetramethyldec-5-yne-4,7-diol (Surfynol 104).
According to the present invention, the wetting agent is 2, 5, 8,11 tetramethyl 6 dodecyn-5,8 diol ethoxylate (Dynol 607). In yet another embodiment of the present invention, the wetting agent is alkoxylated phosphate ester (e.g., Agrilan 1015). In yet another embodiment of the present invention, the wetting agent is amine salts of polyether (e.g., Soprophor FL, Unitop FL). In yet another embodiment of the present invention, the wetting agent is polyoxyethylene alkyl ether (e.g., Atlox 4894). In yet another embodiment of the present invention, the wetting agent is C2-16 ethoxylated alcohols (e.g., Tersperse 4894) and (Tersperse 2288).
According to the present invention, the wetting agent is present in an amount in the range of about 1% to 5% (w/w). Preferably, 2% of the total weight of the composition.
As used herein, the term “anti-freezing agent” may be understood as a chemical substance which prevents the said formulation from freezing.
According to the present invention, the anti-freezing agents are selected from the propylene glycol, glycerol, urea, and combinations thereof. In another embodiment of the present invention, the anti-freezing agent is propylene glycol. In yet another embodiment of the present invention the anti-freezing agent is glycerol. In yet another embodiment of the present invention, the anti-freezing agent is a mixture of propylene glycol and glycerol.
According to the present invention, the anti-freezing agent is present in an amount in the range of about 5% to 15% (w/w). Preferably, 10% of the total weight of the composition.
As used herein, the term “biocide” may be understood as a chemical substance used to destroy, deter, render harmless, or exert a controlling effect on any harmful organism. The addition of these biocides to the agricultural formulations helps to prevent the possible growth of micro-organisms for longer duration.
According to the present invention, the biocides are selected from but are not limited to bactericides such as Legend MK (mixture of 5-chloro-2-methyl-3(2H)-isothiazolone with 2-methyl-3(2H)-isothiazolone), EDTA (ethylenediaminetetraacetic acid), formaldehyde, benzoic acid, or 1,2-benzisothiazol-3(2H)-one or its salts, e.g., Proxel BD or Proxel GXL (Arch), Acticide LA 1209, Acticide SPX, Proxel GXL, KathonCG/ICP and KathonCG/ICPII. In another embodiment of present invention, the biocide is selected from 2-Bromo-2-nitropropane-1, 3-diol, 5-Chloro-2-methyl-2H-isothiazol-3-one, 2-Methyl-2H-isothiazol-3-one, and combinations thereof. In yet another embodiment of present invention, the biocide is Nipacide BIT-20.
According to the present invention, the biocide is present in an amount in the range of about 0.08% to 1% (w/w), preferably 0.1% of the total weight of the composition.
As used herein, the term “viscosity modifier” may be understood as a chemical substance used to alter the viscosity or the thickness of a liquid. These are the substances that alter the fluid resistance to flow.
According to the present invention, the viscosity modifiers are selected from but are not limited to such as block polymers of ethylene oxide and propylene oxide, e.g., antarox F-88 (Rhodia, Inc.), sodium chloride, sodium sulfate, polyvinyl alcohol, and ethyl alcohol. In another embodiment of the present invention, the viscosity modifier selected is hydrated magnesium aluminosilicate, xantham gum (e.g., AG-RHO POL 23), and combinations thereof. In yet another embodiment of the present invention, the viscosity modifier is preferably xantham gum (e.g., AG-RHO POL 23).
According to the present invention, the viscosity modifier is present in an amount in the range of about 0.1% to 15% (w/w). Preferably, 10% of the total weight of the composition.
As used herein, the term “defoamer” may be understood as a chemical additive which is used to reduce and hinder the formation of foam in the liquid formulations.
According to the present invention, the defoamers are selected from but are not limited to insoluble oils, polydimethylsiloxanes(e.g. SAG-1572) and other silicones, certain alcohols, stearates , glycols among others.
According to the present invention, the defoamer is present in an amount in the range of about 0.2% to 1% (w/w). Preferably, 0.5% of the total weight of the composition.
As used herein, the term “buffer” may be understood as substances that adjust the pH of a solution. They can be either weak acids or weak bases or mixtures thereof that make a buffer solution.
According to the present invention, buffers are selected from but are not limited to phosphate buffer (e.g., disodium hydrogen phosphate), acetate buffer, citrate buffer among others.
According to the present invention, the buffer is present in an amount in the range of about 0.1% to 1% (w/w). Preferably, 0.5% of the total weight of the composition.
According to the present invention, the filler used in the present invention is maize starch and is present in an amount in the range of about 40% to 70% (w/w). Preferably, 65% of the total weight of the composition.
In another embodiment the suitable disintegrating agent of the present invention is selected from ammonium sulphate, sodium tripolyphosphate, sodium salt of naphthalene sulfonate and sodium polycarboxylate.
According to the present invention, the disintegrating agent is present in the composition in a range of 0.5% to 0.1% (w/w) of the total weight of the composition.

According to the present invention one or more surface active agents commonly known as surfactants are advantageously employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes.

Base oil as used herein includes but are not limited to methyl soyate oil, rapeseed oil, olive oil, castor oil, rape oil, corn oil, cottonseed oil, helianthus sunflower oil, vegetable oil, mineral oil, paraffin oil, palm methyl ester oil. Preferred, base oil is methyl soyate oil, palm methyl ester oil, helianthus sunflower oil, paraffin oil, vegetable oil and its derivatives.

The concentration of base oil used in the present invention is from 60% to 80% (w/w). Preferably, concentration of base oil is 70% (w/w) of the total weight of the composition.

The present invention provides a pesticidal oil dispersion (OD) composition with good sticking property, penetration and rain fasting properties, saves operational cost by milling the material, requires low dose compared to water dispersible granules, industrially and economically feasible process.

Yet another embodiment of the present invention is to provide a process for the preparation of pesticidal oil dispersion composition, wherein the process comprising steps of:
(a) adding base oil in a disperser,
(b) adding first rheology modifier under stirring at 40-45°C,
(c) cooling to 20-30°C,
(d) adding pymetrozine and cyproconazole under stirring to the obtained homogenized suspension,
(e) adding second rheology modifier under stirring at same temperature,
(f) milling the obtained mixture for 4 hours till the desired particle size distribution is achieved,
(g) transferring the milled material into a separate vessel and continue stirring at room temperature over a period of 2 hours, and
(h) packing the obtained oil dispersion into the drum.

According to the present invention the desired particle size of the composition is less than 20 microns, preferably less than 15 microns to keep the suspension transparent.

The further embodiment of the present invention is illustrated by the following examples, which are provided merely to be exemplary of the inventions and are 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:

Example-1: cyproconazole 10% + pymetrozine 12% Oil dispersion (OD)

S. No. Ingredients Function Quantity (in %w/w)
1. Cyproconazole @98 % (b) 10% Active ingredient 10.41
2. Pymetrozine @ 99% (b) 12 % Active ingredient 12.12
3. CALSOGEN 4814
(Calcium alkyl benzene
sulphonate in 2-ethylhexanol) Dispersing agent 3.0
4. Emulsogen EL 360 (Castor oil
ethoxylate with 36 mole EO) Emulsifier 5.0
5. Bentone 38 (a hectorite clay) Rheology modifier 0.4
6. Aerosil R 816 (fumed silica) Rheology modifier 0.5
7. MSO (methyl soyate oil) Vegetable oil Base oil 68.57
Total 100

Manufacturing process:

Cyproconazole and pymetrozine were dissolved in methyl soyate oil and to this mixture was added organic derivative of a hectorite clay. To this was added benzenesulfonic acid C10-13-alkyl derivatives calcium salt 2-ethylhexanol (Calsogen 4814) followed by castor oil ethoxylate with 36 mole EO, fumed silica (Aerosil R 816). The sample was milled at 25°C and particle size is maintained at <5µ. The sample is checked for quality analysis and packed in HDPE drum.

Example-2: cyproconazole 10% + pymetrozine 12% Wettable Powder (WP)

S. No. Ingredients Function Quantity (in %w/w)
1. Cyproconazole @98 % (b) 10% Active ingredient 10.41
2. Pymetrozine @ 99% (b) 12 % Active ingredient 12.12
3. Morwet IP (sodium isopropyl
naphthalene sulfonate) Wetting agent 2.5
4. Morwet D-425 (Alkylnaphthalene
sulfonate condensate) Dispersing agent 5.0
5. Sodium lignosulphonate Dispersing agent 4.0
6. Silicon dioxide Rheology modifier 1.0
7. Maize starch Filler 64.97
Total 100

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

Example-3: cyproconazole 10% + pymetrozine 12% Water dispersible granules (WDG)

S. No. Ingredients Function Quantity (in %w/w)
1. Cyproconazole @98 % (b) 10% Active ingredient 10.41
2. Pymetrozine @ 99% (b) 12 % Active ingredient 12.12
3. Morwet IP (sodium isopropyl
naphthalene sulfonate) Wetting agent 2.5
4. Morwet D-425 (Alkylnaphthalene
sulfonate condensate) Dispersing agent 5.0
5. Sodium lignosulphonate Dispersing agent 4.0
6. Ammonium sulphate Disintegrating agent 1.0
7. Maize starch Filler 64.97
Total 100

Manufacturing process:

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

Example-4: cyproconazole 10 % + pymetrozine 12 % Suspension concentrate (SC)

S. No. Ingredients Function Quantity (in %w/w)
1. Cyproconazole @98 % (b) 10% Active ingredient 10.41
2. Pymetrozine @ 99% (b) 12 % Active ingredient 12.12
3. Atlox 4894 (Fatty Alcohol Ethoxylate) Wetting agent 1.5
4. Atlox 4913 (polymethyl methacrylate-polyethylene glycol graft copolymer) Dispersing agent 2.0
5. Nipacide Bit 20 (1,2-Benzisothiazol-3(2H)-one) Biocide 0.1
6. Sag 1572 (Polydimethylsiloxane antifoam emulsion) Defoamer 0.5
7. Xanthan gum Viscosity modifier 10
8. Water Base 63.37
Total 100

Manufacturing process:

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

Example-5: cyproconazole 10 % + pymetrozine 12 % Suspoemulsion (SE)

S. No. Ingredients Function Quantity (in %w/w)
1. Cyproconazole @98 % (b) 10% Active ingredient 10.41
2. Pymetrozine @ 99% (b) 12 % Active ingredient 12.12
3. Propylene Glycol Anti-freezing agent 6.0
4. Tersperse 4894 (Alcohols, C12-16, ethoxylated) Dispersing agent 2.0
5. Tersperse 2288 Wetting agent 2.0
6. Proxel GXL (Benzisothiazolin3-one) Biocide 0.7
7. SAG 1572 (Polydimethylsiloxane) Defoamer 0.5
8. Borresperse NA (Sodium naphthalene condensate formaldehyde) Dispersing agent 2.0
9. Emulsogen TS 160 (Tristyryl phenol-polyethylene glycol ether) Emulsifier 2.0
10. Agrhopol 23W Rheology modifier 4.0
11. Water Base 58.27
Total 100

Manufacturing process:

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

Example 6: Efficacy study for combination of Cyproconazole 10% and Pymetrozine 12% Oil dispersion (OD)

Field And Synergy Studies
The sheath blight is caused by the fungal pathogen Rhizoctonia solani. This potentially devasting disease can infect rice foliage at any stage of crop development. It is a major threat to many crops and can also affect the crop stand and yield. Rhizoctonia solani fungus is cosmopolitan, polyphagous, widely distributed in tropical, subtropical, and temperate regions and for its development requires hot and humid environment. The fungus spreads in the field by growing its runner hyphae from tiller to tiller, from leaf to leaf, and from plant to plant, resulting in a circular pattern of damage. The infection spreads most quickly when susceptible varieties are grown under favorable conditions such as warm temperature (28 to 32°C), high humidity (95% or above), and dense stands with a heavily developed canopy.

Two species of planthopper infest rice. These are the brown planthopper (BPH), Nilaparvata lugens (Stal); and the white backed planthopper (WBPH), Sogatella furcifera (Horvath). High population of planthoppers cause leaves to initially turn orange yellow before becoming brown and dry and this is a condition called hopper burn that kills the plant. BPH can also transmit Rice Ragged Stunt and Rice Grassy Stunt diseases. Neither disease can be cured. Planthoppers can be a problem in rainfed and in irrigated wetland environments. It also occurs in areas with continuous submerged conditions in the field, high shade, and humidity. Closed canopy of the rice plants, densely seeded crops, excessive use of nitrogen, and early season insecticide spraying also favors insect development.

Hopper burn is like the feeding damage or "bug burn" caused by the rice black bug. To confirm hopper burn caused by planthoppers, check for the presence of sooty molds at the base of the plant. The feeding damage caused by planthoppers results in the yellowing of the plants. At high population density, hopper burn, or complete drying of the plants is observed. At this level, crop loss may be 100%.

Appropriate analysis of plant response to herbicide combination is critical in determining the type of activity observed. The most widely used model is the one Gowing* derived and Colby** modified. Gowing described a mathematical formula for calculating the predicting response values for pesticide mixtures. He suggested the expected (E) percent inhibition of growth induced by pesticide A plus pesticide B and plus pesticide C is as follows, *(Jerry Flint et al, 1988) ***

B1 (100 – A1)
E = A1 +
100

Where,
A1 = observed efficacy of cyproconazole at the same concentration as used in the mixture.
B1 = observed efficacy of pymetrozine at the same concentration as used in the mixture.

When the percentage of pesticidal control observed for the combination is greater than the expected percentage, there is a synergistic effect. (Ratio of O/E > 1, means synergism observed.)

Reference:
*Gowing, D. P. 1960. Comments on tests of herbicide mixtures. Weeds 8:379–391.
**Colby, S. R. 1967. Calculating synergistic and antagonistic responses of herbicide combinations. Weeds 15:20–22
*** Jerry Flint et al, 1988. Analyzing Herbicide Interactions: A Statistical Treatment of Colby's Method. Weed Technology 2: 304-309

The oil dispersion combination of Cyproconazole 10% and Pymetrozine 12%, application rates, plant species tested, and results are given in the following tables:
The field trial was conducted to evaluate the efficacy of innovative mixtures of Cyproconazole and Pymetrozine against sheath blight and BPH in rice crop. The trial was conducted with randomized block design with net plot size of 5m x 6m. Rice crops were raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting.

The visual observations were recorded for % disease and insect control from ten hills per plot. The observations were recorded before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 1: % Sheath blight disease control in rice:

Compositions Dose
(g AI/ha) Percent disease control – rice sheath blight
07 DAA 14 DAA
Cyproconazole 10% + Pymetrozine 12% OD 220 94 88
Cyproconazole 100 90 80
Pymetrozine 120 70 55
OD – Oil Dispersion, and DAA - Days after application.
The trial results in Table 1 shows that excellent efficacy of premix sample of Cyproconazole 10% and Pymetrozine 12% observed against sheath blight disease of rice as compared to solo treatments.

Table 2: % BPH control in rice:
Compositions Dose
(g AI/ha) % Control – rice BPH
07 DAA 14 DAA
Cyproconazole 10% + Pymetrozine 12% OD 220 95 88
Cyproconazole 100 68 50
Pymetrozine 120 84 70
OD – Oil Dispersion, and DAA - Days after application.
The trial results in Table 2 shows that excellent efficacy of premix sample of Cyproconazole 10% + Pymetrozine 12% OD is observed against BPH in rice as compared to solo treatments.

Table 3: % Sheath blight disease control at 14 DAA
Compositions Dose
(g AI /ha) % Sheath blight disease control
Actual
Cyproconazole 100 80
Pymetrozine 120 55
Cyproconazole 10% + Pymetrozine 12% OD 220 88
Ratio of O/E 1.1
OD – Oil Dispersion, and DAA - Days after application.
Table 4: % BPH control at 14 DAA
Compositions Dose
(g AI/ha) % Control – rice BPH
Actual
Cyproconazole 100 50
Pymetrozine 120 70
Cyproconazole 10% + Pymetrozine 12% OD 220 88
Ratio of O/E 1.26
OD – Oil Dispersion, and DAA - Days after application.
The results in tables 3 & 4 clearly demonstrate that premix sample of Cyproconazole 10% + Pymetrozine 12% OD helps in controlling both rice sheath blight disease and BPH in rice. The large O/E difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.
The above description is for the purpose of illustrating and not limiting the present invention and teaching the person of ordinary skill in the art how to practice the invention. It is not intended to detail all those obvious modifications and variations of it which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention as defined in the appended claims. The claims are meant to cover the claimed components and steps in any sequence which is effective to meet the objectives there intended unless the context specifically indicates the contrary. ,CLAIMS:We claim:

1. A pesticidal synergistic composition comprising triazine insecticide, and triazole fungicide with one or more agrochemical auxiliaries.
2. The pesticidal composition as claimed in claim 1, the triazine insecticide is pymetrozine and triazole fungicide is cyproconazole.
3. The pesticidal composition as claimed in claim 1 and 2 comprising pymetrozine present in a range from 10% to 15% (w/w), cyproconazole present in a range from 10% to 20% (w/w) and agrochemical auxiliaries in the range of 10 to 70% (w/w).
4. The pesticidal composition as claimed in claim 3, wherein the agrochemical auxiliaries are selected from the group comprising a rheology modifier, a dispersing agent, an emulsifier, a base oil, a wetting agent, an antifreezing agent, a biocide, a defoamer, a viscosity modifier, a filler, and a base.
5. The pesticidal composition as claimed in claim 3, wherein the composition formulation is selected from an oil dispersion (OD), a wettable powder (WP), a water-dispersible granule (WDG), a suspension concentrate (SC), and a suspoemulsion (SE).
6. The pesticidal composition as claimed in claim 3, wherein the composition is an oil dispersion (OD) formulation comprising:
a) pymetrozine in the range of 10% to 15% (w/w),
b) cyproconazole in the range of 10% to 20% (w/w),
c) rheology modifiers in the range of 0.1% to 1.2% (w/w),
d) emulsifiers in the range of 5% to 10% (w/w), and
e) base oil in the range of 60% to 80% (w/w).
7. The pesticidal composition as claimed in claims 4 and 6, wherein the rheology modifier is selected from the group comprising organic derivative of a hectorite clay, fumed silica, polyethylene alcohol, glycerol alkyl resins, silicon dioxide and a combination thereof.
8. The pesticidal composition as claimed in claims 4 and 6, wherein the emulsifier is selected from the group comprising of castor oil ethoxylate with 36 moles EO, tri-sec-butylphenol polyglycol ether with 4 EO, polyoxyethylene sorbitol ester, and tristyryl phenol-polyethylene glycol ether.
9. The pesticidal composition as claimed in claims 4 and 6, wherein the base oil is selected from selected from methyl soyate oil, vegetable oil, and helianthus sunflower oil.
10. A process for the preparation of the pesticidal composition in an oil dispersion (OD) formulation is comprising the steps of:
(a) adding a base oil in a disperser;
(b) adding a first rheology modifier under stirring at 40-45°C;
(c) cooling to 20-30°C;
(d) adding pymetrozine and cyproconazole under stirring to the obtained homogenized suspension;
(e) adding second rheology modifier under stirring at same temperature;
(f) milling the obtained mixture for 4 hours till the desired particle size distribution is achieved;
(g) transferring the milled material into a separate vessel and continue stirring at room temperature over a period of 2 hours; and
(h) packing the obtained oil dispersion into the drum.