CLIAMS:1. An oil based antifungal formulation with enhance uptake and activity comprising of combination of:-
a. a strobilurin fungicide as first active ingredient and
b. a polymeric dithiocarbamate fungicide complex with zinc salt
2. The formulation as claimed in claim 1 is comprising of
a. first active ingredient which is methyl (2E)-2-{2-[6-(2-cyanophenoxy) primidin-4-yloxyl] phenyl}-3-methoxyacrylate and
b. the second active ingredient which is manganese ethylenebis (dithiocarbamte) a polymeric complex with zinc salt.
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 in the range about 0.1% to 40% of the total weight of the formulation but more preferably 5 to 15 % of the total weight of the formulation.
5. The formulation as claimed in claim 1 to claim 3 wherein the second active ingredient is in is in the range about 5 % to 60% of the total weight of the formulation but more preferably the range of about 30 to 50% of the total weight of the formulation.
6. The formulation as claimed in claim 1 to claim 5 wherein the formulation may include adjuvants in the range of 0.5 – 35% weight.
7. The formulation as claimed in claim 1 to 6 the thickener is based on natural polymers.
8. The formulation as claimed in claim 7 wherein the preferred range of thickener is 0.01 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, kapokmoil, castor 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 transesterification products thereof or mixture thereof.
11. The formulation as claimed in claim 1 to claim 10 wherein the formulation may include vegetable oil in the range of 5% – 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 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 may be 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 15 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 15 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 15 wherein cationic and ampholytic surfactants may be quanternary 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 of steps:
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.
d. Adding thickener to treated mixture at a temperature above 40° C.
21. The use of the plant protection formulation according to any of the preceding claims for controlling harmful fungi on crop plants.
22. The use according to claim 21 for controlling the harmful fungi in fruit crops, vegetable crops, Cereals crops, oil seed crops and grapevines.
23. A method of controlling harmful fungi in plant crops, comprising the application of an aqueous dilution of the plant protection formulation according to any of claims 1 to 22 to the crop plants. ,TagSPECI:Field of Invention:

The following specification describes the invention and discloses a environmentally safe stable oil based fungicidal combination comprising (a) methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and (b) manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt which are at weight ratio of 0.1:20-10: 1 molar ratio of first active ingredient to the second active ingredient, more preferably in the ratio of 1.14 : 10.0. More particularly, the invention relates to oil- based suspension formulations comprising an agriculturally active solid having improved storage stability and enhanced performance in term of uptake, spreading, rainfastness and curativity. The fungicidal combination can be prepared to oil suspension (OS), also referred to as oil dispersion (OD) formulation as per the abbreviation and terminology used. 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

Background of the Invention:

Despite negative perception of the public, fungicides are still going to be used for many years to ensure food supply and safety for the ever growing world population. 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. In general, fungicidal active substances are not employed in their pure form, but in the form of a formulation. 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. 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).

Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate is a strobilurin fungicide active substance with protective and curative action, which are effective against a number of diseases caused by Oomycetes sp. Ascomycetes sp., Basidiomycetes sp. and Deuteromycetes sp. Is commercially available (see, for example, "The Pesticide Manual" 14th edition pages 54 to 56). It is commercially available in SC and WDG formulations either in singly or in combinations with various other fungicidal active ingredients to control various kind of disease on different agricultural crops. Oil suspension and oil dispersion formulations of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and its combinations with other fungicidal active ingredient are not known so for Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt is a dithiocarbamate fungicides salts with protective action which is widely used in grape, potato, tomato sugar beet, cabbage, kale, celery, peppers, beans, beans, eggplant, melons, cotton, peanuts, wheat, corn, rice, tea, rubber, citrus, mango, banana, litchi, pear, peach, rose, rose, tobacco and so on to control fungal disease caused by Oomycetes sp. Ascomycetes sp., Basidiomycetes sp. and Deuteromycetes sp . It is commercially available (see, for example, "The Pesticide Manual" 14th edition (2006), The British Crop Protection Council, pages 646-649). Combinations of manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt with other fungicidal active substance, specially strobilurins, in oil suspension (OS) or Oil dispersion (OD) formulation are not known so far.

Most of the formulations of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt, either in individual or in combinations, are generally designed based on customer needs and physic-chemical properties of the active ingredients but formulations of these fungicidal active ingredient, particularly in combinations, with good application properties, environment and user friendliness, having good biological activity and enhanced efficacy combined with high selectivity are overlooked.

There are two major categories of formulations of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt are available in market.

Firstly formulations using petroleum based solvent or water based include emulsifable concentrates (EC), suspension concentrates (SC), soluble liquids (SL), etc. which are either unsafe to the environment or not give the 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 hence loses of the active ingredient. Further these types of the formulations are tends to wash off or run off from the plant surface after application resulted 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 deposits on plant surface in 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.

Thirdly, most of the plant disease specially late blight of Potato caused by Phytophthora spp and downy mildew of grape caused by Parenospora spp. are tends to occurs and progress faster under higher humidity in environment and retention of water on leaf surface during frequent precipitation which 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), soluble liquids (SL), WP and WDG are tend to wash off or run off from the plant surface after application resulted 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 CropLife 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, which ingredients some time 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 to higher active ingredient strength formulations than would otherwise be possible. Formulation based on oil also enhanced the performance of active ingredient in combinations in term of uptake, spreading on plant surface, rainfastness and curativity.
Unfortunately, a major limitation on an oil-based agricultural formulation, such as an OD and 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 two primary goals in the mind: (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.

It was surprisingly and unexpectedly found by the present inventors that a selective combination of two fungicidal active ingredient comprising (a) Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and (b) Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt 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 WP and WDG formulation. The economic factor should of course not be overlooked in the search for novel fungicidal compounds

OBJECTIVE OF THE INVENTION

The present invention attains at least to achieve one of the following objectives.

It is an object of the present invention to provide a fungicidal combination of methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt.

Another objective of the present invention is to provide broad spectrum control of wide range of diseases caused by phytopathogenic fungi on various commercial crops.

Another objective of the present invention is to provide an environmentally safer novel formulation in oil suspension or oil dispersion formulations of methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt.

Another object of the present invention is to provide storage stable formulation of oil suspension and oil dispersion combinations Another objective of the present inventions is to provide enhance 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 inventions is to improve rain-fastness activity of the product and enhance the adhesion to the plant surface Still further object of the present invention is to provide a fungicidal composition containing lower concentration of methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt as compared to the known fungicide formulations containing individual ingredients.

Yet another objective of the present invention is to provide a fungicidal composition which is non-phytotoxic and results in high yield of various economically important crops such as paddy, rice, vegetables, grape, etc.

Another objective of the present inventions is to provide combination formulations 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.

Still further object of the present invention is to provide a fungicidal composition of bis-dithiocarbamate and a triazole fungicide to overcome the problems faced by the farmers of physically mixing the individual, commercially available formulations at the field.

SUMMARY OF THE INVENTION

According to an aspect of the present invention, a selective combination of two fungicidal active ingredient comprising (a) Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and (b) Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt formulated in environmentally safer oil suspension or oil dispersion formulation, is possesses enhanced efficacy, improved penetration and long duration control of phyto-pathogenic 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 WP and WDG formulation. The economic factor should of course not be overlooked in the search for novel fungicidal compounds

DETAIL DESCRIPTION

There is a constant need in the art for the fungicidal combination compositions that fungicidal active ingredients in combination are formulated in such a way that it possess enhanced efficacy, improved penetration in plant, long duration control of phytopathogenic fungi, have less residue deposit on plant surface, possess no or less adverse impact on photosynthetic activity of plants, a greater spectrum of diseases controlled caused by phyto-pathogenic fungi, reduced cost, user friendly, reduced residue problems and such formulations also possess storage stability. However, the underlying mechanism by which a combination of fungicides results in stable novel soil suspension or oil dispersion formulation is unknown to a person skilled in the art.

The present inventors have unexpectedly and surprisingly found that selective combination of Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate and (b) Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt, formulated in oil dispersion or oil suspension, is possess enhanced efficacy, improved penetration in plant, long duration control of phytopathogenic fungi, have less residue deposit on plant surface, user friendly, possess no or less adverse impact on photosynthetic activity of plants, a greater spectrum of diseases controlled caused by phyto-pathogenic fungi, reduced cost, reduced residue problems and such formulations also possess storage stability. A person skilled in the art would not expect that stable oil suspension or oil dispersion formulation of fungicidal combinations, selecting Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate selecting from known strobilurins fungicide and Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt selecting from known dithiocarbamate fungicides and combining the same can provide enhanced efficacy, improved penetration in plant, long duration control of phytopathogenic fungi, have less residue deposit on plant surface, possess no or less adverse impact on photosynthetic activity of plants, a greater spectrum of diseases controlled caused by phyto-pathogenic fungi, reduced cost, reduced residue problems and such formulations also possess storage stability.

Thus, the invention provides active compound combinations with stable oil- suspension or oil dispersion formulations which, in some aspects at least, achieve the stated objectives.

Therefore, in one aspect, the present invention provides a novel and stable oil suspension or oil dispersion formulation of fungicidal combination 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.

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.

In an embodiment, Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate comprises from about 0.1% to 40% of the total weight of the formulation but more preferably 5 to 15 % of the total weight of the formulation of the compositions according to the present invention.

In a preferred embodiment, Methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate comprises still more preferably about 7% of the total weight of the compositions according to the present invention.

In an embodiment, Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt comprises from about 5 % to 60% of the total weight of the formulation but more preferably the range of about 30 to 50% by total weight of the compositions according to the present invention. Most preferably, Manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt comprises about 41% 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 mixing molar ratios are those where 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 those where 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 0.5 : 15 to 10:1. 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 1.4:10.

In preferred embodiment of the present invention the fungicidal composition is an oil dispersion or oil suspension.

In preferred embodiment the said oil dispersion or oil suspension comprising from 0.01 to 60 by weight (wt%) of the active combination fungicidal ingredients, from 5 to 70 wt% of the vegetable oil and from 0.1 to 15 wt% of the thickener.
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. 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.
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 C30 paraffins having 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 cycioaliphatic, which may be unsubstituted or substituted, C7- to Ci8-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, 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 C12 monoalcohols or polyols, for example butanol, n- octanol, i-octanol, dodecanoi, 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 Ci-C3 amines, aikylamines or alkanolamines with C6 - C18 carboxylic acids; or mixtures thereof.
Preferably the oil is obtained from renewable resources and 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 methylated soyabean oil. In an embodiment, methylated vegetable oil comprises from about 5 % to 70% of the total weight of the formulation but more preferably the range of about 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 ethoxyiation 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; aikylpoiyg!ycosides or polyalkoxylated, preferably polyethoxylated, alkylpolyglycosides.
Preferred nonionic surfactants are polyethoxylated alcohols, preferably from renewable resources, such as ethoxylated (4-8 EO) Ci2-Ci4 natural alcohol; polyethoxylated triglycerides which contain hydroxyfatty acids.
Also suitable are anionic surfactants, for example: polyalkoxylated, preferably polyethoxylated, surfactants which are ionically modified, for example by conversion of the terminal free hydroxy! 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 alkylpolygiucoside sulfosuccinate or citrate; sulfosuccinates which are esterified once or twice with linear, or branched aliphatic, cyc!oaliphatic and/or aromatic alcohols, or sulfosuccinates whichare esterifted once or twice with (poly)alkylene oxide adducts of alcohols. Preferred anionic surfactants are, for example, salts of aikylarylsu!fonic and sulfosuccinic acids, and polyelectrolytes from the poiycondensation of naphthalenesuifonate and formaldehyde.
Examples of cationic and ampholytic surfactants are quanternary ammonium salts, alkyl amino acids, and betaine or imidazoline amphotensides.
According to a particular embodiment, the surfactant is preferably polyethoxylated.
The agrochemical oil dispersion of the invention can comprise from 0.1 to 15 % wt of additional thickeners to improve the stability of the composition. Suitable additional thickeners are for example thickeners based on natural polymers, such as cellulose derivatives, natural oils and derivatives thereof, such as hydrogenated castor oil. Natural oils and derivatives thereof, are the preferred additional thickeners.
The oil dispersion or oil suspension as per the abbreviation 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 deflocculat'ton 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.
Because of the high thickening power of the amides of the invention, in the last two embodiments, they shall be added after milling. The thickener can be poured into the liquid as such, preferably heated at a temperature above 40 °C, or can be predispersed or predissolved in the oil and then added to the micronized mixture.
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 oil suspension or oil dispersion formulation of active compound combinations according to the invention have very good fungicidal properties and can be employed for controlling phytopathogenicic fungi, such as Plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes Deuteromycetes, etc. Some pathogens causing fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation: diseases caused by powdery mildew pathogens, such as, for example Blumeria species such as, for example, Blumeria graminis; Podosphaera species such as, for example, Podosphaera leucotricha; Sphaerotheca species such as, for example, Sphaerotheca fuliginea; Uncinula species such as, for example, Uncinula necator; diseases caused by rust pathogens such as, for example, Gymnosporangium species such as, for example, Gymnosporangium sabinae Hemileia species such as, for example, Hemileia vastatrix; Phakopsora species such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species such as, for example, Puccinia recondita; Uromyces species such as, for example, Uromyces appendiculatus; diseases caused by pathogens from the Oomycetene group such as, for example, Bremia species such as, for example, Bremia lactucae; Peronospora species such as, for example, Peronospora pisi or P. brassicae; Phytophthora species such as, for example, Phytophthora infestans; Plasmopara species such as, for example, Plasmopara viticola; Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species such as, for example, Pythium ultimum; leaf spot diseases and leaf wilts caused by, for example, Alternaria species such as, for example, Alternaria solani; Cercospora species such as, for example, Cercospora beticola; Cladiosporum species such as, for example, Cladiosporium cucumerinum; Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium); Colletotrichum species such as, for example, Colletotrichum lindemuthanium; Cycloconium species such as, for example, Cycloconium oleaginum; Diaporthe species such as, for example, Diaporthe citri; Elsinoe species such as, for example, Elsinoe fawcettii; Gloeosporium species such as, for example, Gloeosporium laeticolor; Glomerella species such as, for example, Glomerella cingulata; Guignardia species such as, for example, Guignardia bidwelli; Leptosphaeria species such as, for example, Leptosphaeria maculans; Magnaporthe species such as, for example, Magnaporthe grisea; Mycosphaerella species such as, for example, Mycosphaerella fijiensis; Phaeosphaeria species such as, for example, Phaeosphaeria nodorum; Pyrenophora species such as, for example, Pyrenophora teres; Ramularia species such as, for example, Ramularia collo-cygni; Rhynchosporium species such as, for example, Rhynchosporium secalis; Septoria species such as, for example, Septoria apii; Typhula species such as, for example, Typhula incarnata; Venturia species such as, for example, Venturia inaequalis; root and stem diseases caused by, for example, Corticium species such as, for example. Corticium graminearum; Fusarium species such as, for example, Fusarium oxysporum; Gaeumannomyces species such as, for example, Gaeumannomyces graminis; Rhizoctonia species such as, for example, Rhizoctonia solani; Tapesia species such as, for example, Tapesia acuformis; Thielaviopsis species such as, for example, Thielaviopsis basicola; ear and panicle diseases (including maize cobs), caused by, for example, Alternaria species such as, for example., Alternaria spp.; Aspergillus species such as, for example, Aspergillus flavus; Cladosporium species such as, for example, Cladosporium spp.; Claviceps species such as, for example, Claviceps purpurea; Fusarium species such as, for example, Fusarium culmorum; Gibberella species such as, for example, Gibberella zeae; Monographella species such as, for example, Monographella nivalis; diseases caused by smuts such as, for example, Sphacelotheca species such as, for example, Sphacelotheca reiliana; Tilletia species such as, for example, Tilletia caries; Urocystis species such as, for example, Urocystis occulta; Ustilago species such as, for example, Ustilago nuda; fruit rots caused by, for example, Aspergillus species such as, for example, Aspergillus flavus; Botrytis species such as, for example, Botrytis cinerea; Penicillium species such as, for example, Penicillium expansum; Sclerotinia species such as, for example, Sclerotinia sclerotiorum; Verticilium species such as, for example, Verticilium alboatrum; seed- and soil-borne rot and wilts, and seedling diseases, caused by, for example, Fusarium species such as, for example, Fusarium culmorum; Phytophthora species such as, for example, Phytophthora cactorum; Pythium species such as, for example, Pythium ultimum;

Rhizoetonia species such as, for example, Rhizoctonia solani; Sclerotium species such as, for example, Sclerotium rolfsii; cankers, galls and witches' broom disease, caused by, for example, Nectria species such as, for example, Nectria galligena; wilts caused by, for example, Monilinia species such as, for example, Monilinia laxa; deformations of leaves, flowers and fruits, caused by, for example, Taphrina species such as, for example, Taphrina deformans; degenerative diseases of woody species, caused by, for example, Esca species such as, for example, Phaemoniella clamydospora;

diseases of inflorescences and seeds, caused by, for example, Botrytis species such as, for example, Botrytis cinerea; diseases of the plant tubers, caused by, for example, Rhizoctonia species such as, for example, Rhizoctonia solani; diseases caused by bacterial pathogens such as, for example: Xanthomonas species such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species such as, for example, Erwinia amylovora; The following diseases of soybeans can preferably be controlled: Fungal diseases on leaves, stems, pods and seeds caused by, for example, altemaria leaf spot (Altemaria spec, atrans tenuissima), anthracnose (Colletotrichurr gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot am: blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispor; (syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospor; manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojinai leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola i powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines i rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi), scat (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spo (Corynespora cassiicola)
fungal diseases on roots and the stem base caused by, for example,
black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium bligh or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusariun semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmc spora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem cankc (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), browi stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotini; southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

The fungicidal compositions according to the present invention possess advantageous curative, preventive and antisporulant fungicidal activity to protect plants, fruit and seeds. The present combination 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 a 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 generaly 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 5 000 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 preparatior at the stated application rate. After the spray coating has dried on, the plants are inoculatec with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in ai 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 t; that of the control, whereas an efficacy of 100% means that no infection is observed. The table below shows clearly that the activity found for the active compound combination formulated in oil suspension or oil dispersion according to the present invention is greater than the WG. WP and SC formulations i.e. an enhanced effect is present. 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.