Claims:WE CLAIM:
1. An oil based antifungal formulation with enhanced uptake and activity comprising of combination of:
a. a strobilurin fungicide as first active ingredient,
b. a polymeric dithiocarbamate fungicide complex with zinc salt in the range of 31% to 60%,
c. rheology modifier, and
d. other agronomic additives.
2. The formulation as claimed in claim 1, wherein the formulation comprising of
a. methyl (2E)-2-{2-[6-(2-cyanophenoxy) primidin-4-yloxyl] phenyl}-3 methoxyacrylate as first active ingredient, and
b. manganese ethylenebis (dithiocarbamte) a polymeric complex with zinc salt as second active ingredient in the range of 31% to 60%.
c. rheology modifier, and
d. other agronomic additives.
3. The formulation as claimed in claim 1 and claim 2, wherein the said formulation is an oil- dispersion or suspension.
4. The formulation as claimed in claim 1 to claim 3, wherein the first active ingredient is preferably in the range of 5% to 15% of the total weight of the formulation.
5. The formulation as claimed in claim 1 to claim 4, wherein the formulation includes adjuvants in the range of 0.5 to 35% weight.
6. The formulation as claimed in claim 1 to claim 2, wherein the rheology modifier is based on natural polymers.
7. The formulation as claimed in 1 to claim 2, wherein the rheology modifier is, natural oils, mineral oils, preferably vegetable oil.
8. The formulation as claimed in 1 to claim 2, wherein the preferred range of rheology modifier is 0.1 to 15%.
9. The formulation as claimed in claim 1 to 8, wherein the oil is a mineral oil or vegetable oil which may be liquid triglycerides but more preferably is methylated vegetable oil.
10. The formulation as claimed in claim 9, wherein the vegetable oil is selected from a group of olive oil, kapok oil, castor oil, banana oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cotton seed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil or trans esterification products thereof or mixture thereof.
11. The formulation as claimed in claim 1 to claim 10, wherein the formulation include vegetable oil in the range of 5% to 70% by weight.
12. The formulation as claimed in claim 1 to claim 11, wherein the formulation further includes surfactants in ratio 1 to 20% by weight.
13. The formulation as claimed in claim 12, wherein surfactants include emulsifiers and dispersants.
14. The formulation as claimed in claim 12 to claim 13, wherein surfactants are anionic, cationic, non-ionic and ampholytic surfactants and mixtures thereof.
15. The formulation as claimed in claim 13 to claim 14, wherein surfactants are selected from non-ionic emulsifiers and dispersants such as polyalkoxylated, aliphatic alcohols.
16. The formulation as claimed in claim 14 wherein anionic surfactant is sulfosuccinates which are esterified once or twice with linear or branched aliphatic, cycloaliphatic and / or aromatic alcohols or sulfosuccinates which are esterified once or twice with poly alkalene oxide adducts of alcohols.
17. The formulation as claimed in claim 14 wherein anionic surfactant is salts of alkylarylsulfonic acid and sulfosuccinic acids and polyelectrolytes from polycondensation of napththalenesulfonate and formaldehyde.
18.The formulation as claimed in claim 14 wherein cationic and ampholytic surfactants may be quaternary ammonium salts, alkyl amino acids and betaine or imidazoline amphotensides.
19. The formulation as claimed in claim 1 to claim 18 characterized in its stability for a period up to two years at a storage temperature being ambient temperature.
20. A method of preparing an antifungal formulation as claimed in claim 1 to claim 19 comprising steps of:
a. pulverizing the mixed active ingredients to particle size of 20 – 50 micros by dry mill,
b. preparing a mixture of pulverized active ingredient with oil and other additives,
c. treating the mixture in a wet mill to reduce the particle size below 20 microns and preferably below 10 microns, and
d. adding rheology modifier to treated mixture at a temperature above 40° C.
21. The use of plant protection formulation as claimed in any of the preceding claim for controlling harmful fungi on crop plants.
22. The use as claimed in claim 21 for controlling the harmful fungi in fruit crops, vegetable crops, cereals crops, oil seed crops and grapevines.

Dated this Twenty Seventh (27th) day of May, 2019

__________________________________
Dr. S. Padmaja
Agent for the Applicant
IN/PA/883 , Description:FORM 2

THE PATENTS ACT, 1970
(SECTION 39 OF 1970)
&
The Patents Rules, 2003

COMPLETE SPECIFICATION
(SECTION 10 and Rule 13)

OIL BASED FUNGICIDAL FORMULATION AND PROCESS FOR PREPARING AND USE THEREOF

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 describes and ascertains the nature of this invention and the manner in which it is to be performed:
This application is a patent of addition to pending Indian patent application No. IN 1777/CHE/2014 filed on April 02, 2014.

FIELD OF THE INVENTION
The present invention relates to stable oil based fungicidal composition comprising of a) strobilurin fungicide, b) polymeric dithiocarbamate fungicide complex with zinc salt, c) rheology modifier and other agronomic additives.

The present invention also relates to stable oil based fungicidal formulation with enhanced uptake and activity comprising of:
a) strobilurin fungicide as first active ingredient,
b) polymeric dithiocarbamate fungicide complex with zinc salt in the range of 31% to 60%,
c) rheology modifier, and
d) other agronomic additives.

The present invention specifically relates to (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy] phenyl}-3-methoxyacrylate (Azoxystrobin) as strobilurin fungicide, (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt(Mancozeb) in the range of 31% to 60%, (c) rheology modifier and other agronomic additives.

The present invention specifically relates to stable oil based fungicidal combination composition comprising (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate (Azoxystrobin), (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (Mancozeb) at a weight ratio of 0.1:20-20:1 molar ratio of first active ingredient to the second active ingredient, more preferably in the ratio of 1:10 and still more preferably in the ratio of 1: 5.93, (c) rheology modifier and other agronomic additives.
The present invention also relates to stable oil- based fungicidal combination suspension compositions comprising an agriculturally active solid having improved storage stability and enhanced performance in term of uptake, spreading, rainfastness and curativity.

The present invention also relates to a process for the preparation of stable oil based fungicidal combination composition comprising steps of: mixing, pulverizing and milling.

BACKGROUND OF THE INVENTION
Fungicides are biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality, and profit. Fungicides are used both in agriculture and to fight fungal infections in animals. It is clear that, although pesticides remain indispensable in agriculture, a great potential still exists to improve their efficiency and thus reduce their input into the environmental and food chain. Depending on the field of application, and the mode of application, and depending on physical, chemical and biological parameters, the active substances are employed as active substance formulation in the form of a mixture with customary carriers, adjuvants and additives.

Azoxystrobin (Azoxystrobin) is a strobilurin fungicide, and is chemically, methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate with protective and curative action, which are effective against a number of diseases caused by Oomycetes sp. Ascomycetes sp., Basidiomycetes sp. and Deuteromycetes sp.

Mancozeb is a dithiocarbamate salt fungicides, non-systemic agricultural fungicide with multi-site, protective action on contact which mainly inhibit binding of bacteria in vivo oxidation of pyruvate and pyruvate oxidation processes involved in lipoic dehydrogenase II mercapto group (SH). Widely used in the beet, cabbage, cabbage, celery, peppers, beans, tomatoes, eggplant, potatoes, melons, such as watermelons, cotton, peanuts, wheat, corn, rice, hops, tea, rubber, citrus, grapes, mango, banana, lychee, pear, persimmon, peach, rose, rose, tobacco.

Mancozeb is chemically, manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt which is listed under FRAC code M:03 The "M" refers to Chemicals with Multi-Site Activity. "M" FRAC groups are defined as generally considered as a low risk group without any signs of resistance developing to the fungicides.

The combinations with fungicidal active substances for widening the spectrum of action and/or for protecting the crop plants are also known. Though, the ability of these combination compounds to efficiently control diseases varies with a large number of the parameters including, but not limited, the type of the formulations of combination fungicide, the type of phytopathogenic fungi to be controlled, the type of the plant to be protected and ambient conditions, such as temperature, precipitations, humidity, length of the day, biological diversity of the micro environment, the like.
Therefore, formulations of fungicidal active substances in combinations should generally have good chemical and physical stability, good application properties, user friendliness, having good biological activity and enhanced efficacy combined with high selectivity. Proper formulation and efficient delivery systems of combinations fungicides are the key elements in the performance of different products. Recently, the use of vegetable oils (seed oils) and mineral oil has been increased since they are more biodegradable and originate from renewable resources. These oils are very useful in pesticide formulations as the both oil as well as active materials are expected to contribute to the biological activity (Wang and Liu, 2007).

Firstly, formulations using petroleum based solvent or water based solvent include emulsifable concentrates (EC), suspension concentrates (SC), soluble liquids (SL), etc. which are either unsafe to the environment or that do not give proper efficacy against target diseases due to lack of adhesion to the plant surface, particularly when the spray droplet hits the leaf for the first time as it tend to bounce back when they strike the plant surface resulting in lose of active ingredient. Further these types of the formulations tend to wash off or run off from the plant surface after application resulting into poor and short duration disease control.

Secondly, solid formulations like WP and WG/WDG, especially for Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt and it’s combinations are based on either bentonite silica, diatomaceous earth and talk powder which are either not environmental and user friendly or tends to deposit on plant surface in the form of powder which directly or indirectly inhibits photosynthetic activity in plant and effects on marketable quality of the fruits due to deposit of powdery stain on fruit.

Most of the plant disease especially late blight of Potato caused by Phytophthoraspp and downy mildew of grape caused by Parenospora spp. tends to occur and progress faster under higher humidity. Further, retention of water on leaf surface during frequent precipitation is also a pre-disposing factor for occurrence and severity of the diseases. In such condition, application of traditional formulation of fungicides like emulsifable concentrates (EC), suspension concentrates (SC), and soluble liquids (SL), WP and WDG tend to wash off or run off from the plant surface after application resulting into poor and short duration disease control.

Formulations comprising an agriculturally active solid suspended in plant oil and mineral oil, as the primary component of the continuous phase, have been found advantageous in the treatment of agricultural substrates. Examples of such formulations have been designated by Crop Life International as OD ("oil dispersion") and OF ("oil-miscible flowable concentrate") formulations. Such formulations provide certain advantages to the end user. They allow the formulation of active ingredients in solid suspended form, for those ingredients that cannot be formulated in water because of hydrolytic instability. Also, such formulations allow oil-based adjuvants to be incorporated into the formulation to enhance efficacy.

Further, in many cases active ingredients have a solubility limit on the amount that can be loaded into a formulation, such as an EC and SC formulations, and so suspension in an oil-based system can possibly load higher active ingredient strength formulations than would otherwise be possible. Formulation based on oil also enhances the performance of active ingredient in combinations in terms of uptake, spreading on plant surface, rainfastness and curativity. Unfortunately, a major limitation on an oil-based agricultural formulation, such as an OD or OS formulation, is the need to physically stabilize the formulation for potentially long periods of storage especially for two active ingredients in combinations which are having different chemical and physical properties, so that it can be in a consistently useable form for later end use. Further, difficulty has been experienced in stabilizing certain ingredients at their most desirable concentrations.

There is a need in the art to provide environmentally safer and stable fungicidal compositions having two active ingredients with different physical and chemical properties with the primary goals includes: (1) providing an environmentally safe, easy and effective combination formulation of two fungicidal active with enhanced efficacy and less impact on photosynthetic activities on plant upon dilution in a carrier such as water or oil, and spray application to an area to be treated (2) maintaining the stability of the product during storage.

The formulations in combination of manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (Mancozeb) with other fungicidal active substance, specially strobilurins, in the oil suspension (OS) or Oil dispersion (OD) are not known so far.

It was surprisingly and unexpectedly found by the present inventors that a selective combination of two fungicidal active ingredients comprising (a) Methyl (2E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate(azoxystrobin), (b) Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (mancozeb) in the ratio of 31% to 60% and (c) rheology modifierwas formulated in oil suspension or oil dispersion formulation is possesses enhanced efficacy, improved penetration and long duration control of phytopathogenic fungi as compared to its other traditional formulations with long storage stability across a wide temperature range and having no adverse impact on photosynthetic activity in plant and fruit quality because no stain on marketable fruits as compared with commercial WP and WDG formulations.

OBJECTIVE OF INVENTION
The main objective of the present invention is to provide stable oil based fungicidal composition comprising of a) strobilurin fungicide, b) polymeric dithiocarbamate fungicide complex with zinc salt, c) rheology modifier and other agronomic additives.

Another objective of the present invention is to provide stable oil based fungicidal formulation with enhanced uptake and activity comprising of:
a) strobilurin fungicide as first active ingredient,
b) polymeric dithiocarbamate fungicide complex with zinc salt in the range of 31% to 60%,
c) rheology modifier, and
d) other agronomic additives.
Another objective of the present invention is to provide a stable oil based fungicidal composition comprising (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate(azoxystrobin) as strobilurin fungicide, (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (mancozeb) in the range of 31% to 60%, (c) rheology modifier and other agronomic additives.

Another objective of the present invention is to provide a stable oil based fungicidal composition comprising (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate as strobilurin fungicide, (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt at a weight ratio of 0.1:20-20:1 molar ratio of first active ingredient to the second active ingredient, more preferably in the ratio of 1: 5.93 (c) rheology modifier and other agronomic additives.

Another objective of the present invention is to provide storage stable formulation of oil suspension or oil dispersion of fungicidal combinations comprising (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate(azoxystrobin) as strobilurin fungicide, (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (mancozeb), (c) rheology modifier and other agronomic additives.

Another objective of the present invention is to provide enhanced efficacy, improved penetration in plant and long durations control of disease caused by phytopathogenic fungi on commercially cultivated crops, like cereals, grape, oil seeds, pulses, fruits plants, vegetables, ornamental plants, as compared to traditional formulations of same active ingredient combination, hence required less active ingredient.
Another objective of the present invention is to improve rain-fastness activity of the product and enhance the adhesion to the plant surface which have less power deposition on plant surface and marketable fruits and vegetables which does not inhibit the photosynthetic activities of the commercial crop plants as compared to traditional formulations of manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt and its combinations with other fungicidal active ingredients.

SUMMARY OF INVENTION
Accordingly, the present invention provides stable oil based fungicidal composition comprising:
a) strobilurin fungicide,
b) polymeric dithiocarbamate fungicide complex with zinc salt in the range of 31% to 60%,
c) rheology modifier, and
d) other agronomic additives.

In one embodiment, the present invention provides stable oil based fungicidal formulation with enhanced uptake and activity comprising of:
e) strobilurin fungicide as first active ingredient,
f) polymeric dithiocarbamate fungicide complex with zinc salt in the range of 31% to 60%,
g) rheology modifier, and
h) other agronomic additives.

In another embodiment, the present invention provides a stable oil based fungicidal combination composition of (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate (azoxystrobin) as strobilurin fungicide, (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (mancozeb) in the range of 31% to 60%, (c) rheology modifier and other agronomic additives.

In another embodiment, the present invention provides fungicidal combination composition comprising:
5 % to 15% (w/w) of strobilurin fungicide as first active ingredient,
31% to 60% (w/w) of polymeric dithiocarbamate fungicide complex with zinc salt as second active ingredient,
0.01% to 15% (w/w) of rheology modifier,
5% to70 %(w/w) of oil,
1 to 20% (w/w) of surfactants,
0.5 to 30% (w/w)of other agronomic additives.

In another embodiment, the present invention provides method of preparing a fungicidal formulation comprising the steps of:
a. pulverizing the mixed active ingredients to particle size of 20 – 50 microns by dry mill,
b. preparing a mixture of pulverized active ingredient with oil and other additives,
c. treating the mixture in a wet mill to reduce the particle size below 20 microns and preferably below 10 microns, and
d. adding rheology modifier to treated mixture at a temperature above 40°C.

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 stable oil based fungicidal composition comprising:
a) strobilurin fungicide,
b) polymeric dithiocarbamate fungicide complex with zinc salt in the range of 31% to 60%,
c) rheology modifier,and
d) other agronomic additives.

The present invention provides stable oil based fungicidal formulation with enhanced uptake and activity comprising of:
a) strobilurin fungicide as first active ingredient,
b) polymeric dithiocarbamate fungicide complex with zinc salt is in the range of 31% to 60%,
c) rheology modifier, and
d) other agronomic additives.

The present invention provides a stable oil based fungicidal composition of (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate (azoxystrobin) as strobilurin fungicide, (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (mancozeb) in the range of 31% to 60%, (c) rheology modifier and other agronomic additives.

The term "agrochemically effective amount" is that quantity of active agent, applied in any amount which will provide the required control of diseases caused by phytopathogenic fungi on commercial crops. The particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

The active compound combinations according to the invention have very good fungicidal properties and can be employed for controlling phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,Deuteromycetes, etc, which causes the disease in field and green house crops like cereals, pulses, oilseeds, vegetables, fruits, spices and ornamental crops. The composition of the present invention could be applied to plants, seeds, fruits, soil as preventive and curative state.

Therefore, in one aspect, the present invention provides a stable oil suspension or oil dispersion formulation of fungicidal comprising an agrochemically effective amount of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate; and an agrochemically effective amount of Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt.

In an embodiment, Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate (azoxystrobin) is preferably in the range of 5 % to 15 % of the total weight of the formulation of the compositions according to the present invention, still more preferably 7% of the total weight of the compositions according to the present invention.

In an embodiment, Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt is preferably the range of 31% to 50% by total weight of the compositions according to the present invention. Most preferably, Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt comprises 40% by total weight of the composition according to the present invention.

However, the molar ratios of the active compounds in the active compound combinations of present invention can be varied within a certain range. Preferred molar ratios are of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt are present in a ratio of from 0.1:20 to 20:1. Particularly preferred mixing ratios are of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt are present in weight ratio of from 1:10. In a very particularly preferred mixing molar ratio of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt are present in a ratio 1:5.93.

In preferred embodiment the said oil dispersion or oil suspension comprises from 5 % to 15% (w/w) of strobilurin fungicide as first active ingredient,
31% to 60% (w/w) of polymeric dithiocarbamate fungicide complex with zinc salt as second active ingredient,
0.01% to 15% (w/w) of rheology modifier,
5% to 70% (w/w) of oil,
1 to 20% (w/w) of surfactants,
0.5 to 30% (w/w) of other agronomic additives.

In one preferred embodiment of the present invention, the fungicides active ingredients comprises methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc, preferably in a concentration of greater than 400g/L and less than 700 g/L. In another preferred form, the formulation comprises Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy] phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc in a concentration of 620g/L and rheology modifier in the concentration of 0.1 to 15 wt %.

The present inventors have advantageously been able to produce a formulation comprising Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc in a concentration of 620g/L, which formulation has been found to be stable long- term with no adverse effects on viscosity. In this formulation, no hard-packed layer is observed and the formulation remains fluid/pourable after heat stability studies at 54°C for two weeks time period. The advantage provided by the present invention is that it achieves a superior stable high loading suspension formulation of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc. The formulation also affords excellent ease of dispensability into water and results in a stable emulsion and suspension.

Rheology modifiers are sometimes referred to as thickeners or viscosity modifiers. A good rheology modifier structures the formulation but when a force is applied it becomes flowable and easily poured. Without proper stabilisation, products can suffer formulation breakdown mechanisms such as flocculation and coalescence. The significant role of polymeric surfactant or dispersants and emulsifiers in producing highly stable formulations is that it will keep particles apart from each other preventing these formulation breakdown processes.

However, another variant that needs to be considered for formulation stabilization is the viscosity or thickness of the formulation. Increasing the viscosity of a formulation improves stability, by acting as a barrier to sedimentation and creaming which can be altered by adding a rheology modifier. To obtain the desired level of stability to particle sedimentation in composition, choosing the rheology modifier and the polymer or oligomer capable of hydrogen bonding that provides the desired thickening effect is necessary.

There are a variety of materials, both natural and man-made, that have been used as rheology modifiers to stabilize oil dispersion formulations against sedimentation such as, for example, clays and organoclays, hydrophilic and hydrophobic silicas, hydrogenated castor oils and their derivatives, polyamides, oxidized waxes, associative thickeners, which form structures by themselves due to their limited solubility in solvents, and steric dispersants (e.g., comb polymers such as polyvinylpyrrolidinones or polyacrylates).

The agrochemical oil dispersion or oil suspension of the present invention can comprise from 0.1 to 15 % wt of rheology modifiers to improve the stability of the composition. Preferred rheology modifiers include, natural polymers selected from the group guar gum, locust bean gum, xanthan gum, carrageenan, alginates, methyl cellulose, carboxymethyl sodium carboxymethylcellulose, hydroxyethylcellulose, modified starches; other polysaccharides and modified polysaccharides, polyethylene alcohol, glycerol alkyl resinsand cellulose derivatives, natural oils, mineral oils such as kyros oil, vegetable oil derivatives such as SURFOM® ESP 8105, the organoclays such as Bentone, Bentone SD and Benathix Plus and the fumed silicas such as Aerosil R974, Aerosil 200 and Aerosil 972, Aerosil R816 (silanehexadecyltrimethoxy hydrolysis product with silica), and equivalent products thereof, preferably used is aerosilR816 (silanehexadecyltrimethoxy hydrolysis product with silica).

The oil is a water-insoluble liquid organic medium and may be any of those agricultural oils commonly used in the trade for making oil dispersions for agricultural use. Suitable agricultural oils in the dispersions of the invention are, for example: linear or branched C8 to C30paraffinshaving boiling points above 140°C (paraffin oils), for example octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, their mixtures, or mixtures thereof with higher boiling homologs, such as hepta-, octa-, nona-decane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and the branched chain isomers thereof; aromatic or cycloaliphatic, which may be unsubstituted or substituted, C7- to C18-hydrocarbon compounds such as mono- or polyalkyl-substituted benzenes, or mono- or polyalkyl-substituted naphthalenes; vegetable oils such as liquid triglycerides for example olive oil, kapok oil, castor oil, banana oil, kyros oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cotton seed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, or also transesterification products thereof, e.g. alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester; animal oil, such as whale oil, cod-liver oil, or mink oil; liquid esters of C1 to C12monoalcohols or polyols, for example butanol, n-octanol, i-octanol, dodecanol, cyclopentanol, cyclohexanol, cyclooctanol, ethylene glycol, propylene glycol or benzyl alcohol, with C2 to C12 carboxylic or polycarboxylic acids, such as caproic acid, capric acid, caprylic acid, peiargonic acid, succinic acid and glutaric acid; or with aromatic carboxylic acids such as benzoic acid, toluic acid, salicylic acid and phthalic acid. Esters which can be used in the oil dispersions of the invention are thus, for example, benzyl acetate, caproic acid ethyl ester, peiargonic acid ethyl ester, benzoic acid methyl or ethyl ester, salicylic acid methyl, propyl, or butyl ester, diesters of phthalic acid with saturated aliphatic or alicyclic C1 to C12 alcohols, such as phthalic acid dimethyl ester, dibutyl ester, diisooctyt ester; liquid amides of C1-C3 amines, aikylamines or alkanolamines with C6 - C18 carboxylic acids; or mixtures thereof.

Preferably the oil is obtained from renewable resources and is vegetable oil is corn oil, soybean oil, sunflower oil or rapeseed oil or transesterification products thereof such as rapeseed oil methyl esters, ethyl esters, propyl esters, butyl esters etc. According to a particular embodiment, the oil is a vegetable oil.

According to a particular embodiment, the oil is preferably banana oil is from about 5 % to 70% of the total weight of the formulation but more preferably in the range of 20% to 50% by total weight of the compositions according to the present invention.

In a preferred embodiment, the agrochemical oil dispersion of the invention further comprises from 1 to 20 wt%, preferably from 1 to 8 wt%, of surfactants, such as emulsifiers and dispersants. Surfactants are used not only to improve dispersion and to emulsify oil upon dilution in water, but also to increase suspension stability, wetting ability, penetration and translocation, and to provide the mixing ability and suspension/emulsion stability of a product after dilution. As surfactants, anionic, cationic, non-ionic and ampholytic surfactants and mixtures thereof can be used. Suitable surfactants are, for example, nonionic emulsifiers and dispersants, such as: polyalkoxylated, preferably polyethoxylated, saturated and unsaturated aliphatic alcohols, having 8 to 24 carbon atoms in the alkyl radical, which is derived from the corresponding fatty acids or from petrochemical products, and having 1 to 100, preferably 4 to 40, ethylene oxide units (EO); polyalkoxylated, preferably polyethoxylated; polyalkoxylated, preferably polyethoxylated, alkylphenols having one or more alkyl radicals, such as, for example, nonylphenol or tri-sec- butylphenol, and a degree of ethoxylation of between 2 and 40, preferably from 4 to 20; polyalkoxylated, preferably polyethoxylated, hydroxyl-fatty acids or glycerides which contain hydroxyl-fatty acids, such as, for example, castor oil, having a degree of ethoxyiation of between 10 and 80; sorbitan or sorbitol esters with fatty acids or polyalkoxylated, preferably polyethoxylated, sorbitan or sorbitol esters; polyalkoxylated, preferably polyethoxylated, amines; di- and tri-block copolymers, for example from alkylene oxides, for example from ethylene oxide and propylene oxide, having average molar masses between 200 and 8000 g/mol, preferably from 1000 to 4000; alkylpolyglycosides or polyalkoxylated, preferably polyethoxylated, alkylpolyglycosides.Preferrednonionic surfactants are polyethoxylated alcohols, preferably from renewable resources, such as ethoxylated (4-8 EO) C12-C14 natural alcohol; polyethoxylated triglycerides which contain hydroxyfattyacids.Preferablynon-ionic surfactant is Lutensol (Ethoxylate of alkyl polyethylene glycol ether).Lutensol® is a non-ionic surfactant. It is alkyl polyethylene glycol ether made from a C10-Guerbet alcohol and ethylene oxide which contains also higher alkylene oxide in small amounts.

Anionic surfactants are for example: polyalkoxylated, preferably polyethoxylated, surfactants which are ionically modified, for example by conversion of the terminal free hydroxyl function of the alkylene oxide block into a sulfate or phosphate ester; polyelectrolytes, such as lignosulfonates, condensates of naphthalenesulfonate and formaldehyde, polystyrenesulfonate or sulfonated unsaturated or aromatic polymers; anionic esters of alkylpolyglycosides, such as alkylpolygiucosidesulfosuccinate or citrate; sulfosuccinates which are esterified once or twice with linear, or branched aliphatic, cycloaliphatic and/or aromatic alcohols, or sulfosuccinateswhichareesterifted once or twice with (poly)alkylene oxide adducts of alcohols. Preferred anionic surfactants are, for example, salts of aikylarylsulfonic and sulfosuccinic acids, and polyelectrolytes Examples of cationic and ampholytic surfactants are quanternary ammonium salts, alkyl amino acids, and betaine or imidazolineamphotensides.

In a preferred embodiment, the present invention relates to agrochemical oil dispersion of the invention further comprises dispersant from 0.5 to 1wt%, are selected from the group consisting of polycondensation product of naphthalene sulfonic acid, Polysorbate 20, 60 and 80; glycerylmonooleate/propylene glycol mixture; glycerylmonooleate; sorbitanmonooleate; oleyl alcohol; and linoleic acid. Preferred dispersant is used in the agrochemical oil dispersion composition is Tamol® polycondensation product of naphthalene sulfonic acid.

The oil dispersion or oil suspension according to the invention can comprise from 0.5 to 35 wt% of adjuvants commonly used in this field and well known to those expert in the art, such as wetting agents, antidrift agents, adhesives, penetrants, stickers and spreaders.

In addition to each of the aforementioned components said oil dispersion may also comprise from 0.1 to 10 wt% of other agronomic additives and "crop management" substances such as oil-soluble agrochemical active ingredient, water mixing and/or water soluble carrier and/or de-flocculation agents (e. g. kaolin, Mn compounds), antifoam agents (e. g. silicon-based), antifreeze agents, dyes (e. g. azo dyes), preservatives (e, g. biocide and/or antioxidant), fillers, perfumes, evaporation inhibitors, pH modulators, etc.

The oil suspension concentrates or oil dispersion according to the invention can be prepared in a manner known per se. In the method of the invention, the solid active ingredients are expediently employed in the finely ground state, that is as a micronized powder of less than 20 microns in size on average, preferably of less than 10 microns, or they may be reduced to this particle average size during step i).

In one embodiment it is possible to prepare the mixture of step i) by first coarse wet-milling and then fine wet-milling the active ingredient, so that the final average particle size is below 20 microns, preferably below 10 microns, in the presence of the oil, Milling can be carried out in a colloid mill, ball mill, sand mill, and preferably in grinding ball mills.

In a further embodiment it is possible to prepare the mixture of step i) by mixing the oil, the possible other liquid additives and the solid ingredients that have been preliminarily pulverized to a particle size of from about 20 to 50 microns by a dry mill, and then subjecting the mixture to fine treatment by a wet-mill, such as a ball mill, a sand mill etc., so that the final average particle size is below 20 microns, preferably below 10 microns.

The agrochemical oil dispersions of the invention have Brookfieid® viscosity of at least 300 mPa*s, preferably of at least 1000 mPa*s, at 25°C, and usually below 50,000 mPa*s, preferably below 20,000 mPa*s, at 25°C.

Once formulated, an OD or OS formulation produced by the method of the present invention would be expected to show stability on storage at temperatures of 54°C for up to 2 weeks and also stability at ambient temperature for up to 2 years.

The agrochemical oil dispersion or oil suspension can be diluted with water or water solutions of agronomic compounds before use to produce a sprayable composition which is used in treating plants or increasing plant growth, Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the agrochemical active ingredient at a concentration of at least 0.001 g/l.

The active compound combinations according to the invention have potent fungicidal activity and can be employed for controlling phytopathogenic fungi, in crop protection and in the protection of materials.

The fungicidal compositions according to the present invention possess advantageous curative, preventive and antisporulant fungicidal activity to protect plants, fruit and seeds. The present composition can be used to protect plants or parts of plants, e.g. fruit, blossoms, flowers, foliage, stems, roots, cuttings, tubers of plants or culture plants infected, harmed or destroyed by micro-organisms, whereby later-growing parts of plants are protected against such micro-organisms. Application may be made by ground or aerial spray equipment.

As examples of the wide variety of culture plants in which the combinations of present invention can be used, there may be named for example cereals, e.g. wheat, barley, rye, oats, rice, sorghum and the like; beets, e.g. sugar beet and fodder beet; pome and stone fruit and berries, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries; leguminous plants, e.g. beans, lentils, peas, soy beans; oleaginous plants, e.g. rape, mustard, poppy, olive, sunflower, coconut, castor-oil plant, cocoa, ground-nuts; cucurbitaceae, e.g. pumpkins, gherkins, melons, cucumbers, squashes; fibrous plants, e.g. cotton, flax, hemp, jute; citrus fruit, e.g. orange, lemon, grapefruit, mandarin; vegetables, e.g. spinach, lettuce, asparagus, brassicaceae such as cabbages and turnips, carrots, onions, tomatoes, potatoes, hot and sweet peppers; laurel-like plants, e.g. avocado, cinnamon, camphor tree; or plants such as maize, tobacco, nuts, coffee, sugar-cane, tea, vines, hops, bananas, rubber plants, as well as ornamental plants, e.g. flowers, shrubs, deciduous trees and evergreen trees such as conifers. This enumeration of culture plants is given with the purpose of illustrating the invention and not to delimiting it thereto.

A particular mode of administering an antifungal composition of the present invention is the administration to the aboveground parts of plants, in particular to the leaves thereof (leaf-application). The number of applications and the administered doses are chosen in accordance with the biological and climatic conditions of life of the causative agent. The antifungal compositions though, can also be applied to the soil and get into the plants through the root system (systemic activity), in case the locus of the plants is sprayed with a liquid composition or if the components are added to the soil in a solid formulation e.g. in the form of granulate (soil application).

The fungicidal compositions of the present invention can also be used for protecting seed against fungi. To that effect the present fungicidal compositions can be coated on seed, in which case the seed grains are drenched consecutively with a liquid composition of the active ingredients or if they are coated with a previously combined composition. The compositions can also be sprayed or atomized onto the seed.

When using the active compound combinations according to the invention, the application rate can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active-compound combination application rates are generally between 0.1 and 10 000 g/ha, preferably between 100 and 2500 g/ha. For seed dressing, the active compound combination application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 20 g per kilogram of seed. For the treatment of the soil, the active-compound combination application rates are generally between 0.1 and 10 000 g ha preferably between 1 and 5000 g/ha.

The good fungicidal activity of the oil dispersion or oil suspension formulation of two active-compound combinations according to the invention demonstrated by the examples below, whereas, the WG, WDG and SC formulations exhibit weaknesses in fungicidal activity. To test for protective activity, young plants are sprayed with the active compound preparator at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthorainfestans. The plants are then placed in an incubation cabin at about 20°C and 100% relative atmospheric humidity. Evaluation is carried out 3 days after inoculation. Here, 0% means an efficacy which corresponds to that of the control; whereas an efficacy of 100% means that no infection is observed. The enhanced effect found is surprisingly clearly pronounced for the formulations of two fungicidal active ingredients in oil dispersion or oil suspension, according to the invention, which has, on application of plant surface, good adhesion, no bounce back of droplet, good penetrations and good surface area coverage.

Although the invention has been described above with reference to the disclosed embodiments, those skilled in the art will readily appreciate that the specific embodiments detailed are only illustrative of the invention. It should be understood that various modifications can be made without departing from the spirit of the invention. Accordingly, the invention is limited only by the following claims.

The formulation of the present invention composition of working in bench scale is given below:
EXAMPLES
Example 1: Pesticide composition with using silica rheology modifier:
S.No Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Tech Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 8.23
2. Mancozeb tech [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 47.05
3. Lutensol TO 5 Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol FBPP Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil R816 Silanehexadecyltrimethoxy hydrolysis product withsilica 1.0
6. Banana oil Hydro-treated base oil 34.74
Total 100

Example 2: Pesticide composition with using rheology modifier:
S. No. Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Technical (95%) Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 8.33
2. MancozebTechnical (85%) [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 49.41
3. Lutensol Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil-R816 Silanehexadecyltrimethoxy hydrolysis product with silica 1.0
6. Banana oil Hydro-treated base oil 32.26
Total 100.0

Example 3: Pesticide composition with using silica rheology modifier:
S. No. Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Technical (95%) Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 10.33
2. Mancozeb Technical (85%) [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 47.41
3. Lutensol Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil-R816 Silanehexadecyltrimethoxy hydrolysis product with silica 1.0
6. Banana oil Hydro-treated base oil 32.26
Total 100.0

Example 4: Pesticide composition with using silica rheology modifier:
S. No. Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Technical (95%) Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 12.33
2. Mancozeb Technical (85%) [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 45.41
3. Lutensol Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil-R816 Silanehexadecyltrimethoxy hydrolysis product with silica 1.0
6. Banana oil Hydro-treated base oil 32.26
Total 100

Example 5: Pesticide composition with using silica rheology modifier:
S. No. Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Technical (95%) Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 14.33
2. Mancozeb Technical (85%) [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 43.41
3. Lutensol Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil-R816 Silanehexadecyltrimethoxyhydrolysis product with silica 1.0
6. Banana oil Hydro-treated base oil 32.26
Total 100.0

Example 6:Pesticide composition with using silica rheology modifier:
S. No. Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Technical (95%) Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 16.33
2. Mancozeb Technical (85%) [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 41.41
3. Lutensol Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil-R816 Silanehexadecyltrimethoxy hydrolysis product with silica 1.0
6. Banana oil Hydro-treated base oil 32.26
Total 100.0

Example 7: Pesticide composition without using rheology modifier:
S No Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Technical Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 8.23
2. MancozebTechnical [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 47.05
3. Lutensol TO 5 Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol FBPP Condensation product of naphthalene sulphonic acid 1.0
5. Banana oil Hydro-treated base oil 35.74
Total 100

Example 8: Pesticide composition with using silica rheology modifier:
S.No Ingredients/Raw Materials Chemical Name Quantity (in %)
1. Azoxystrobin Tech Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 8.23
2. Mancozeb tech [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 47.05
3. Lutensol TO 5 Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol FBPP Condensation product of naphthalene sulphonic acid 1.0
5. Aerosil R816 Silanehexadecyltrimethoxy hydrolysis product withsilica 1.0
6. Kyros oil mineral oil based 34.74
Total 100

Example 9: Pesticide composition with using organic rheology modifier:
S.No Ingredients/Raw Materials Chemical Name Quantity (in %)
1. AzoxystrobinTech Methyl (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate 8.23
2. Mancozeb tech [1,2-Ethaznediybis (carbamodithio)(2-)] manganese zinc salt 47.05
3. Lutensol TO 5 Ethoxylate of alkyl polyethylene glycol ether 8.0
4. Tamol FBPP Condensation product of naphthalene sulphonic acid 1.0
5. Surfom ESP 8105 Blend of solvent and organic compound 3.2
6. Banana oil Hydro-treated base oil 32.54
Total 100

The pesticide composition without using rheology modifier was tested for the stability and the final composition becomes solid hard paste and it was observed that it loses its flowability and cannot be removed from containerafter 14 days.

The pesticide composition using the silica or organic rheology modifier is in the form of light yellow colour liquid and it was free from sedimentation at bottom after 14 days.
Accelerated Heat Stability Data (AHS)- pesticide composition with using silica rheology modifier:
S.No Test Specification RT Sample 14 Day
Accelerated heat stability data (AHS)
1.0 Appearance The material shall in the form of light yellow colour liquid free from sedimentation The material shall in the form of light yellow colour liquid free from sedimentation The material shall in the form of light yellow colour liquid free sedimentation at bottom.
2.0 pH 6.5-7.5 7.60 6.95
3.0 Azoxystrobin Content(%w/w) 6.65 -7.7 7.6 7.47
4.0 Mancozeb Content(%w/w) 38-42 41.65 41.12
5.0 Suspensibility (% m/m) (Min) 75 91.0 85
6.0 Wet sieve test
(Min %w/w through 75µ sieve) 2% retained 99.95 99.46
7.0 Viscosity (cp) 800-1400 998 1200
8.0 Particle size analysis (D90µ) < 25-30 15.889 27.619

Accelerated Heat Stability Data (AHS)- pesticide composition with using organic rheology modifier:
S.No Test Specification RT Sample 14 Day
Accelerated heat stability data (AHS)
1.0 Appearance The material shall be in the form of light yellow colourliquid free from sedimentation The material shall be in the form of light yellow colour liquid free from sedimentation The material shall in the form of light yellow colour liquid free sedimentation at bottom.
2.0 PH 6.5-7.5 7.20 7.16
3.0 Azoxystrobin Content(%w/w) 6.65 -7.7 7.62 7.40
4.0 Mancozeb Content(%w/w) 38-42 41.65 41.12
5.0 Suspensibility (% m/m) (Min)
75 90.0 8.0
6.0 Wet sieve test
(Min %w/w through 75µ sieve) 2% retained 99.85 99.00
7.0 Viscosity (cp) 800-1400 995 1200
8.0 Particle size analysis (D90µ) <25-30 15.889 27.619