DESC:FIELD OF THE INVENTION:
The present invention relates to synergistic fungicidal composition of bioactive amounts of (A) a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; (B) Sulphur and (C) at least one further active compound or a salt or adduct thereof. The present invention further relates to the mentod of preparation of the said composition is specific weight and formulation thereof. More particularly, the present invention relates to a suspo-emulsion fungicidal formulation for the said fungicidal composition.

BACKGROUND OF THE INVENTION:
Fungal disease are one of the worst enemies of crops. They causes severe damages to the crops resulting in reduced crop productivity and yields. In heavily infested areas 70 to 90 percent crop damages has been reported. In agrarian countries like India it have bad impacts the economy of the country. Controlling crop fungal diseases has been a major issue and various traditional and advanced means are being used to minimize the damage caused by fungi. Most frequently and widely used method to control fungal disease use of fungicides. Continuous use of fungicide years after years, in uncontrolled and unscientific manner has resulted in development of resistance in the fungi and this resistance continues to broaden in spectrum against the number of fungi. Continuous high intensity use of fungicide has given rise to some other critical issues like presence of high quantity of fungicide residues in agricultural products, increasing environmental pollution and damage to ecological balance and deteriorating health of consumers.
Therefore, there is a need for a fungicidal formulation that is highly efficient, has low toxicity, covers a broader spectrum of fungi and is environment friendly and economical to the end user.
The present invention relates to agrochemical compositions based on suspo-emulsion formulation; their use for application in crop protection flowable formulations for controlling agricultural fungal diseases and reducing the wash-off of active ingredients by rainfall. Biological efficacy of fungicides is influenced by many factors, particularly the residence time of the fungicides on the treated surface, which is often a plant leaf surface. For example, emulsified oil or water insoluble polymers prepared as emulsions have been used to improve liquid formulation.
A number of chemical agents have been used for controlling plant fungal diseases control. However, the problem that plant fungi have acquired resistance to the chemical agents becomes remarkable due to frequent use or excessive application, etc., of the chemical agents having similar structures and same functions for controlling the same kinds of fungal disease.
Fungicidal compounds are often applied in the form of a dilute aqueous composition in order to achieve a good interaction with the target organism, such as plants, and fungi. As most active compounds that are used as fungicides, in particular fungicidal active compounds, are only sparingly or even insoluble in water, in most of the cases, formulators are often confronted with difficulties in formulating fungicide compounds in stable formulations.
On the other hand, consumer’s needs for agricultural chemical-reduced crops and social needs to reduce environmental loads due to increased use of agricultural chemicals have now increased. Also, in a farmer's field where the chemicals have been actually used, when two or more kinds of chemicals are used in admixture for the treatment by the tank mix method, there are many risks to lower the effect of the other chemical to be mixed with each other or possibilities to cause chemical damages against plant materials depending on a combination of chemicals where they are not well-suited to each other.
Propamocarb hydrochloride has low toxicity to humans and mammals. Furthermore, it is systemic fungicide with protective action, used to control soil born and leaf diseases in vegetables and ornamental plants. The product is high effective when applied as soil disinfectant and foliar spray, it reduces mycelial growth and development of sporangia and spores, influences the biochemical synthesis of membranes. Absorbed by the leaves, roots and transported acropettaly.
The conventional formulation of Propamocard hydrochloride fungicides is available in market, the fungicide formulation are often prepared by use of toxic organic solvents, more conventional single product formulations disadvantages. A conventional formulations when stored under severe environment conditions at high temperature or low temperature, oil droplets and particles (dispersoids) dispersed in water may sometimes cause a change such as particle growth, separation of an aqueous layer and formation of a hard cake due to aggregation and precipitation of dispersoids, or a change in appearance such as creaming of the formulation, and thus the conventional formulations was not necessarily sufficient in storage stability.
Sulfur is a natural bio-pesticide particularly used as fungicide and insecticide on hundreds of food and feed crops, turf, ornamentals and residential sites. It is also used as a fertilizer. It is effective for reclamation of alkaline soils.
Generally>90% of soil sulfur is present in the organic matter of the soil. Therefore, soils with less organic matter are deficient in sulfur. Moreover, the available sulfate form of sulfur gets leached from such soils.The challenge involved in developing commercially acceptable products containing agriculturally active Sulphur and fungicides compounds in combination continues to increase due to the rapid emergence of more complex customer and regulatory requirements. These agricultural compositions must exhibit excellent chemical stability and must also maintain a high level of physical stability under a severe range of storage and use conditions especially when used in combination.
Fungicides are chemical substances that were developed for controlling fungi, which are the main causative agents of diseases in plants. Owing to the increase in diseases and their intensity, there is a constant need to develop new fungicides, as well as increase their concentration in commercial formulations. This increase in concentration, associated with adverse environmental conditions, may lead to phytotoxicity (collateral effects on the plants), since the disease-causing fungi and the plants parasitized by them share much physiology in common.
However, sulphur is difficult to formulate into a formulation either alone or in combination. Problems associated with sulphur formulations include formation of unsightly residue on ornamentals and the tendency of sulphur to settle down when in liquid form (Olkowski, W. et al, Common Sense Pest Control, p. 109). Some plants are sensitive to sulphur and plant damage can occur when temperatures during application are greater than 30°C. Sulphur is available in particulate form. It is difficult to combine sulphur with a fungicide.
Further the environmental and economic requirements imposed on modern-day crop protection compositions are continually increasing, with regard, for example, to the spectrum of action, toxicity, selectivity, application rate, formation of residues, and favourable preparation ability, and since, furthermore, there may be problems, for example, with resistances, a constant task is to develop new compositions, in particular fungicidal agents, which in some areas at least help to fulfil the abovementioned requirements.
There are many combinations of fungicide known in the art for the control of fungi. For example, US9161541B2 relates to a pesticide composition intended for protecting plants, crops or seeds against phyto-pathogenic fungi or damaging insects, and the corresponding methods of treatment using the said composition. More precisely, the subject of the present invention is a pesticide composition based on propamocarb-HCl, an insecticide active substance and optionally a further fungicide active substance.
WO2013180589A1a fungicidal composition comprising a mixture of dimethomorph (compound I) and propamocarb hydrochloride (compound II) in the form of a suspension concentrate containing 72 g/L to 90 g/L of dimethomorph and 400 g/L to 500 g/L of propamocarb-HCl. The present invention also relates to a method to treat crops by applying 144 g/ha to 180 g/ha of dimethomorph and 800 g/ha to 1000 g/ha of propamocarb hydrochloride. The composition is preferably used for treating potato late blight (Phythophtora infestans), tomato downy mildew (Phythophtora infestans) and lettuce downy mildew (Bremia lactucae).
There is however a need for improvement of these combinations. With the onset of resistance to certain fungi and isnsects, there is a need in the art for a combination of actives that decreases chances of resistance and improves the spectrum of controlling fungal disease and insect pests.
However still there is a need of fungicidal composition comprises of a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; Sulphur; and at least one further active compound or a salt or adduct thereof which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.
In general use, the fungicidal actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target weed. However, most active fungicidal compounds that are used as pesticides are only sparingly or even insoluble in water. The low solubility of such compounds present the challenges and difficulties to formulator in formulating fungicidal compounds in stable formulations that can be easily stored for a long time and which still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compound is present in the composition.
Therefore, one object of the present invention is to provide improved fungicidal combination for fungal disease and insect pest. Another object of the present invention is to provide a method and a composition for improving the crop yield by controlling the fungi and insect pests.
Embodiment of the present invention can ameliorate one or more of the above mentioned problems.
Inventors of the present invention have surprisingly found that a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; Sulphur; and at least one further active compound or a salt or adduct thereof as described herein which can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION
Accordingly, in a first aspect of the present invention provides synergistic fungicidal composition of bioactive amounts of (A) a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; (B) Sulphur and (C) at least one further active compound or a salt or adduct thereof.
Accordingly, in a second aspect, the present invention provides a method of preparing synergistic composition of bioactive amounts a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; Sulphur; and at least one further active compound or a salt or adduct thereof with one or more inactive excipient.
Yet another aspect of the present invention provides the synergistic fungicidal composition comprises component (A) a fungicide present in an amount of 50% to 70% (w/w) (preferably 50% to 57%) of the formulation; component (B) Sulphur present in an amount 10% to 30% (w/w) (preferably 19% to 21%) of the formulation.
In further aspect of the present invention the formulation for the synergistic fungicidal composition with one or more inactive excipients is suspo emulsion formulation.
It is an object of the present invention to provide a process for the preparation of the suspo-emulsion combination formulation of the present fungicidal composition.
It is further an object of the present invention to provide a synergistic fungicidal composition and suspo-emulsion formulation thereof protects crop from fungal disease.
Accordingly, in a further aspect, the present invention provides a synergistic fungicidal compositions comprising bioactive amounts of (A) a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; (B) Sulphur and (C) at least one further active compound or a salt or adduct thereof and one or more customary formulation adjuvants; show excellent storage stability and biological efficacy for use in plant fungal disease control.
Accordingly, in a further aspect, the present invention provides a synergistic fungicidal compositions comprising bioactive amounts of (A) a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; (B) Sulphur and (C) at least one further active compound or a salt or adduct thereof and one or more customary formulation adjuvants; shows synergistic activity.
Accordingly, in another aspect, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pathogenic damage or pest damage by applying to the plant propagation material a composition comprising a formulated mixture defined in the first aspect.

DETAILED DESCRIPTION OF THE INVENTION:
Therefore an aspect of the present invention provides synergistic fungicidal composition of bioactive amounts of (A) a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; (B) Sulphur and (C) at least one further active compound or a salt or adduct thereof.
Accordingly further aspect of the present invention provides a method of preparing synergistic fungicidal composition of bioactive amounts a fungicide selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Cyflufenamid, Benalaxyl-M, Carpropamid, Amisulbrom, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof; Sulphur; and at least one further active compound or a salt or adduct thereof with one or more inactive excipient.
It is an object of the present invention to provide a formulation of Sulphur and fungicides selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Amisulbrom Cyflufenamid, Benalaxyl-M, Carpropamid, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or salts thereof and at least one agrochemically acceptable excipient, with a view to effective resistance management and effective control of harmful fungi, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful fungi (systemic mixtures) and minimize risk of phytotoxicity.
Fungicides are chemical substances that were developed for controlling fungi, which are the main causative agents of diseases in plants. Owing to the increase in diseases and their intensity, there is a constant need to develop new fungicides, as well as increase their concentration in commercial formulations. This increase in concentration, associated with adverse environmental conditions, may lead to phytotoxicity (collateral effects on the plants), since the disease-causing fungi and the plants parasitized by them share much physiology in common.
Propamocarb:
Propamocarb is a carbamate ester that is the propyl ester of 3-(dimethylamino)propylcarbamic acid. It is a systemic fungicide, used (normally as the hydrochloride salt) for the control of soil, root and leaf diseases caused by oomycetes, particularly Phytophthora and Pythium species. It has a role as a xenobiotic, an environmental contaminant and an antifungal agrochemical. It is a carbamate ester, a tertiary amino compound and a carbamate fungicide. It derives from a propan-1-ol. It has IUPAC name as propyl N-[3-(dimethylamino)propyl]carbamate having chemical structure as below:

Sulphur:
Sulphur is a natural bio-fungicide particularly used as fungicide and insecticide on hundreds of food and feed crops, turf, ornamentals and residential sites. It is also used as a fertilizer. It is effective for reclamation of alkaline soils.
Sulphur is as important as nitrogen for synthesis of amino acids and chlorophyll. It is also essential for utilization of phosphorus and other nutrients. Sulphur plays a vital role in optimizing crop yield and quality. It increases size and weight of grain crops, particularly crops which have high nitrogen requirement, as Sulphur enhances nitrogen utilization in plants. Plants do not respond to applied nitrogen in absence of adequate Sulphur.
Sulphur is present in soil in both, organic and inorganic forms. It is not available to plants in organic form. As microorganisms present in soil decompose organic matter, the organic Sulphur slowly gets converted into sulfate form, which is available to plants.
Generally >90% of soil sulphur is present in the organic matter of the soil. Therefore, soils with less organic matter are deficient in Sulphur. Moreover, the available sulfate form of Sulphur gets leached from such soils.
The challenge involved in developing commercially acceptable products containing agriculturally active Sulphur and fungicides compounds in combination continues to increase due to the rapid emergence of more complex customer and regulatory requirements. These agricultural compositions must exhibit excellent chemical stability and must also maintain a high level of physical stability under a severe range of storage and use conditions especially when used in combination.
Sulphur is the chemical element with atomic number 16. In the periodic table, it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulphur atoms form cyclic octatomic molecules with chemical formula S8. At room temperature elemental sulphur is a bright yellow crystalline solid. Chemically, sulphur can react as either an oxidizing or reducing agent. It oxidizes most metals and several non-metals, including carbon, which leads to its negative charge in most organosulphur compounds, but it reduces several strong oxidants, such as oxygen and fluorine. It is also the lightest element to easily produce stable exceptions to the octet rule.
However, sulphur is difficult to formulate into a formulation either alone or in combination. Problems associated with sulphur formulations include formation of unsightly residue on ornamentals and the tendency of sulphur to settle down when in liquid form (Olkowski, W. et al, Common Sense Fungal diesease Control, p. 109). Some plants are sensitive to sulphur and plant damage can occur when temperatures during application are greater than 30°C. Sulphur is available in particulate form. It is difficult to combine sulphur with a fungicide.
Further the environmental and economic requirements imposed on modern-day crop protection compositions are continually increasing, with regard, for example, to the spectrum of action, toxicity, selectivity, application rate, formation of residues, and favourable preparation ability, and since, furthermore, there may be problems, for example, with resistances, a constant task is to develop new compositions, in particular fungicidal agents, which in some areas at least help to fulfil the abovementioned requirements.
In describing the embodiments of the invention, specific terminology is resorted for the sake of clarity. However, it is not intended that the invention be limited to the specific terms so selected and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
As used herein, the term "systemic effect" or grammatical variations thereof means and includes a cooperative action encountered in a combination of two or more active compounds in which the combined activity of the two or more active compounds exceeds the sum of the activity of each active compound alone.
The term "systemically effective amount," as used herein, means and includes an amount of two or more active compounds that provide a systemic effect defined above.
The term "fungicidal effective amount," as used herein, means and includes an amount of active fungicidal that causes an adverse effect to the at least one fungal disease, wherein the adverse effect may include deviations from natural development, killing, regulation, or the like.
As used herein, the term "control" or grammatical variations thereof means and includes regulating the number of living fungi or regulating the number of viable eggs of the fungi or both.
A suspo-emulsion formulation of systemic fungicidal composition comprising (i) at least one compound selected from Propamocarb hydrochloride and Sulphur, wherein droplets of a liquid fungicidal ingredient and particles of a solid fungicidal ingredient are dispersed together in water, and these ingredients are stably dispersed together in water.
The present inventors have studied in view of these circumstances and found that a suspo-emulsion containing a Propylene Glycol ( Anti freezing agent), Jemol D-425, J 1269, Agrilan 788 (emulsifier), Ethylin 500 LQ ( emulsifier) is a formulation having excellent storage stability, which suppresses the particle growth of dispersoids, namely, oil droplets of a liquid fungicidal ingredient and particles of a solid fungicidal ingredient, and also cause neither aggregation nor separation of dispersoids, nor formation of a hard cake, nor a change in appearance, during storage at high temperature and low temperature. Thus, the present invention has been completed. Namely, the present invention will be shown.
The active and inert ingredients in formulation of present invention are dispersed in aqueous solution, preferably water, to compose a stable and safe fungicidal suspension.
The inert ingredients include wetting agents and dispersing agents, anti-freeze agents, anti-foam agents.
The present invention contains two active chemical compounds that mutually complement each other when used together and exhibit systemic plant fungal disease control capabilities that is greater than the individual compound’s capability to control the plant fungal disease when used alone.
The present invention provides the fungicidal composition with active ingredients and inactive excipients in the said suspo-emulsion formulation as:

Table-1:
Name of Content in Composition Range of component (%)
Propamocarb hydrochloride 50-70%
Sulphur 10-30%
Propylene Glycol (P.G.) 0.1-10%
Polymerization inhibitor 0.1-5%
Emulsifier 0.1-5%
Dispersing agent/emulsifier 0.1-5%
Filler (water ) 5-80% or Q.S
Deforming agent 0.1-10%
Stabilizer 0.1-5%
Viscosity agent 0.1-10%

An aqueous suspo-emulsion composition is a mixture of water-insoluble active ingredients dispersed in an aqueous solution, where one (or more) of the active ingredients is in suspension form and one (or more) of the active ingredients is in emulsion form. The formulation is intended for dilution into water prior to spray application. Mixtures of active ingredients are often used to provide a broader spectrum of fungal disease control. Formulating the active ingredients together eliminates the need for tank mixing (which can lead to incompatibilities). Like other aqueous liquid formulations, suspo-emulsions are easy to handle and measure, dust free, non-flammable and offer good miscibility with water.
According to second embodiment of the present invention, there is also a process provided for the preparation of suspo-emulsion composition for controlling plant fungal disease.
The selection of fungicide, quantity of each contents of additives/auxiliaries, particle size of insecticide compounds in the said suspo-emulsion composition plays an important role in treating plant fungal disease control.
Detailed embodiment on Best mode of experiment, Suspo-emulsion fungicidal composition, selection of particle size of one or more contents of the composition and process for preparing the said fungicidal composition and other supporting information along with results if any, may be described in detail at the time of filing complete application.
The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health, yield, plant vigor, quality and tolerance to abiotic or biotic stress are increased. Noteworthy, the health of a plant when applying the method according to the invention, is increased independently of the fungicidal properties of the active ingredients used because the increase in health is not based upon the reduced fungal disease pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defense system. As a result, the health of a plant is increased even in the absence of fungal disease pressure.
Accordingly, in an especially preferred embodiment of the method according to the invention, the health of a plant is increased both in the presence and absence of biotic or abiotic stress factors.
The above identified indicators for the health condition of a plant may be interdependent or they may result from each other. An increase in plant vigor may for example result in an increased yield and/or tolerance to abiotic or biotic stress. One indicator for the condition of the plant is the yield. "Yield" is to be understood as any plant product of economic value that is produced by the plant such as grains, fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants) or even flowers (e.g. in the case of gardening plants, ornamentals). The plant products may in addition be further utilized and/or processed after harvesting.
In an especially preferred embodiment of the invention, the yield of the treated plant is increased.
In another preferred embodiment of the invention, the yield of the plants treated according to the method of the invention, is increased systemically.
According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the mixture according to the invention.
A further indicator for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects such as the general visual appearance. The vitality of plants is a function soil, climate and biotic factors, but also of the genetic composition of the individual. The vitality of the plants and their subsequent performance are therefore a function of its health, fire effects and competition from other plants.
In another especially preferred embodiment of the invention condition of the plant by treatment with formulation of Sulphur and fungicides selected from Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Amisulbrom Cyflufenamid, Benalaxyl-M, Carpropamid, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole, the plant Vitality of the treated plant is increased. In another preferred embodiment of the invention, the plant vigor of the plants treated according to the method of the invention, is increased systemically.
The improvement of the plant vigor according to the present invention a formulation of Sulphur and selected fungicides particularly improves any one or several or all of the above mentioned plant characteristics are improved independently of the fungicides Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Amisulbrom, Cyflufenamid, Benalaxyl-M, Carpropamid, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or the mixture.
Another indicator for the condition of the plant is the "quality" of a plant and/or its products.
In another preferred embodiment of the invention, the quality of the plants treated according to the method of the invention, is increased systemically.
According to the present invention, enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the mixtures of the present invention. Enhanced quality can be characterized, among others, by following improved properties of the plant such as increased nutrient content, increased amount of essential amino acids, improved or optimal fruit color, improved leaf color, higher storage capacity, and higher process ability of the harvested products.
In another preferred embodiment of the invention relates to a formulation of,
1) Fungicide selected from the group consisting of Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Amisulbrom Cyflufenamid, Benalaxyl-M, Carpropamid, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole or mixture thereof;
2) Sulphur;
3) at least one or more inactive excipient.
In another preferred embodiment of the invention relates to a method for controlling harmful fungi using a formulation of (A) fungicide selected from the group consisting of Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Amisulbrom Cyflufenamid, Benalaxyl-M, Carpropamid, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole, (B) Sulphur and or mixture thereof and (C) at least one or more inactive excipient.
In another preferred embodiment of the invention relates to a process for preparation formulation of (A) fungicide selected from the group consisting of Oxathiapiprolin, Mandipropamid, Meptyldinocap, Penflufen, Fluopyram, Ametoctradin, Amisulbrom Cyflufenamid, Benalaxyl-M, Carpropamid, Fluopicolide, Fluxapyroxad, Propamocarb hydrochloride, Tricyclazole, (B) Sulphur and (C) at least one or more inactive excipient.
It is an object of the present invention to provide a process for the preparation of the suspo-emulsion combination formulation of the present fungicidal composition, comprising the step of:
a) Forming the aqueous solution comprising of wetting and dispersing agent or emulsifier;
b) An aqueous dispersion (suspo emulsion, SE) of at least one compound selected from Propamocarb hydrochloride in amount of 50% to 70 % (w/w) (preferably 50% to 57%); Sulphur in a range between 10% to 30% (w/w) (preferably 19% to 21%);
c) addition of anti-freeze agent
d) addition of antifoam agent
e) an emulsion polymer system comprising I) hydrophobically modified copolymeric Acrylate copolymer; and II) non-ionic surfactant, polyalkoxylated butyl ether; and
f) one or more additives selected from the group consisting of non-ionic or anionic surfactants or dispersing aids.
g) Wet grinding of the suspension in pressurized bead mill to reduce particle size of the suspension up to D90 less than 20 micron.
h) Mixing of compounds / components to prepare suspo-emulsion (SE) Formulation.
i) Finally adding the stabilizing agent /viscosity agent & preservative to the suspo-emulsion (SE) to enhance viscosity
In above objective suspo-emulsion formulation according to the invention may additionally comprise penetration promoters, wetting agents, spreading agents and/or retention agents.
It is an object of the present invention to provide improved a suspo-emulsion formulation, of systemic and protective fungicidal composition is which stable and ready to use, and has superior properties compared to prior art formulations or mixtures or compositions.
It is further an object of the present invention to provide a fungicidal composition and suspo-emulsion formulation that will protect crop from fungal disease and insect pests.
In another preferred embodiment of the invention composition of present invention can be in form of Suspension Concentrate (SC), Suspo emulsion (SE), Water dispersible granules (WDG), Dispersible powder (DP), Emulsifiable concentrate (EC), Wettable Powders (WP), Granule (GR), Powder for dry seed treatment (DS), Emulsion, oil in water (EW), Flowable concentrate for seed treatment (FS).
The present fungicidal composition and formulation thereof may be used to control fungi such as Late Blight, Downy mildew, Powdery mildew, Seed borne & soil borne diseases (Black scurf, False smut, Sheath blight), Sigatoka disease, Blast disease, Rust, Alternaria blight, cercospora leaf spot & Rhizoctoniasolani in cotton, Late blight, Root rot, Damping off; Downy mildew (Bremialactucae), Mildew Blast disease.
The present synergistic fungicidal composition and formulation thereof is use in management of the fungal disease in crops like Grapes, Pomegranates, Strawberries, Banana, Cucurbits, Rice, Cotton, Cereals, Fruits, Pulses, Soybean, legumes Crops, Tobacco, Lettuce, Tomato, Potato, Cucumbers, and Vegetables.
The said suspo-emulsion fungicidal composition may be useful but not limited onto the plants such as Potatoes & Tomatoes, Lettuce, Cucumber, Cabbages, Turf, Cotton, Cucurbits, Tomatoes, Pepper, Apples, Pears, Peaches, Fruits, Vines, Cereals, Beet, Hops, Ornamentals, vegetables, Stone fruits, Vines, Eriophyid mites etc.
According to the invention, carrier is to be understood as meaning a natural or synthetic, organic or inorganic substance which is mixed or combined with the active compounds for better applicability, in particular for application to plants or plant parts or seeds. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture.
The process for preparing the present novel formulation can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.
The Suspo-emulsion fungicidal compositions of the present invention may show a broad spectrum activity against various fungal disease (For example Late Blight, Downy mildew, Powdery mildew, Seed borne & soil borne diseases (Black scurf, False smut, Sheath blight), Sigatoka disease, Blast disease, Rust, Alternaria blight, cercospora leaf spot & Rhizoctoniasolani in cotton, Late blight; Root rot; Damping off; Downy mildew (Bremialactucae), Mildew Blast disease), Phycomycetes, Phytophthora infestans (Potatoes & Tomatoes), Bremia lactucae (Lettuce), Pseudoperonospora cubenis(Cucumber), Peronospora spp.(Cabbages), Pythium aphanidermatum(Turf), Pythium spp. & Phytophthora spp.(Cucurbits, Tomatoes, Pepper,e tc.), scab (Apples, Pears and Peaches), Powdery Mildew (Fruits, Vines, Cereals, Beet, Hops, Ornamentals, vegetables), Shot hole (Stone fruits, Acarinoisi (Vines), Mites ( Eriophyid mites) etc. including fungal resistant to chemicals, and shows excellent controlling effects (systemic controlling effects) which could never be expected from a single component alone.
Also, it shows high plant fungal disease controlling effects against existing fungicide resistant to chemicals, and no chemical damage against plants can be admitted.
It also shows activity against (For example Late Blight, Downy mildew, Powdery mildew, Seed borne & soil borne diseases (Black scurf, False smut, Sheath blight), Sigatoka disease, Blast disease, Rust, Alternaria blight, cercospora leaf spot & Rhizoctoniasolani in cotton, Late blight, Root rot; Damping off, Downy mildew (Bremialactucae), Mildew Blast disease), Phycomycetes, Phytophthora infestans (Potatoes & Tomatoes), Bremia lactucae(Lettuce), Pseudoperonospora cubenis(Cucumber), Peronospora spp.(Cabbages), Pythium aphanidermatum(Turf), Pythium spp. & Phytophthora spp. (Cucubits, Tomatoes, Pepper etc.), scab (Apples, Pears and Peaches), Powdery Mildew (Fruits, Vines, Cereals, Beet, Hops, Ornamentals, vegetables), Shot hole(Stone fruits, Acarinoisi (Vines), Mites ( Eriophyid mites) etc.
The present invention of suspo emulsion formulation provides inactive excipients and auxiliary substances for the preparation stable formulation for the present fungicidal composition
At least a one organic / inorganic solvent is selected from water, ethyl acetate, ethylene glycol, glycerine, methanol, heptane, Toluene, Hexamethyl phosphoramide (HMPA), Hexamethylphosphoroustriamide (HMPT), methylt-butyl ether (MTBE), Mix xylene, Acetone, Acetonitrile , solvent C-9, etc.
The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, antimicrobial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.
A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lingo sulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkyl aryl ethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lingo sulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyryl phenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.
Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxy polyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol. Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of antifoam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl poly siloxane while the non-silicone anti-foam agents are water- insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.
A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctyl sulpho succinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates or mixtures thereof.
Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).
Biocides / Microorganisms cause spoilage of formulated products. Therefore antimicrobial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2- benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4- isothiazolin-3-one, potassium sorbate, para hydroxy benzoates or mixtures thereof.
Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e.g. bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.
The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinyl alcohol, vinyl acetate and vinyl pyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymers and mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methyl methacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinyl pyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(ortho esters), alkyd resins, and mixtures of two or more of these.
Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch ester aliphatic polyester blends, modified corn starch, poly capro lactone, poly(namylmethacrylate), wood rosin, poly anhydrides, poly vinyl alcohol, poly hydroxyl butyrate valerate, biodegradable aliphatic polyesters, and poly hydroxyl butyrate or mixtures thereof.
Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
The solvent for the formulation of the present invention may include water, water soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tertbutanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, e.g., polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof.
Anti-foaming agent comprises one or more selected from the group consisting of a fatty acid, a fatty acid ester, a silicone oil, silicon dioxide, an alkyl-substituted silicon dioxide, lecithin, a vegetable oil , propylene glycol mono and diesters of fatty acids, propylene glycol alginate, calcium alginate, mineral oil, odourless light petroleum hydrocarbons, petrolatum, petroleum waxes, synthetic isoparaffinic petroleum hydrocarbons, synthetic petroleum wax, paraffin wax, microcrystalline wax, tallow, oxidized tallow, sulfated tallow, oleomargarine, lard, butter, oxystearin, a fatty acid metal salt, ethylene oxide polymer, copolymer condensates of ethylene oxide and propylene oxide, polyethylene glycol, polypropylene glycol, polyethylene glycol (400) dioleate, sorbitan monostearate, polysorbate 60, polyoxyethylene (20) sorbitan monostearate), polysorbate 65.
Viscosity agent or deformer may be added for adjusting viscosity of the suspo-emulsion composition for example but limited to xanthan gum. The other examples of viscosity agent or deformer is a group comprising polyvinyl alcohols, phenyl naphthalene sulphonate, lignin derivatives, polyvinylpyrrolidone, polyalkylpyrrolidone, carboxymethylcellulose, xanthan gum, polyethoxylated, fatty acids,polyethoxylated fatty alcohols, ethylene oxide copolymer, propyleneoxide copolymer, polyethylene glycols and polyethylene oxides.
The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.
The formulation thus prepared with varying amounts of wetting agents, dispersing agents were subjected to stability study and the optimum dose of the ingredients was selected. Formulation selected after various permutation and combination of ingredients was found to be stable and The best stable formulation was checked for parameters of description, suspensibility, dispersibility, pourability, viscosity, pH, under conditions of ambient temperature, heat stability and cold conditions at 10°C.

Example 1: Preparation of Propamocarb hydrochloride (55%) + Sulphur bucarb (20%) Suspo-Emulsion (SE) formulation:
Table-2:
S. No. Raw Material Name Inputs Qty (gm.)
1 Propamocarb hydrochloride Technical (Purity 90% w/w) 306.00gm.
2 Sulphur technical (purity 99 % w/w) 102.00gm
3 Propylene Glycol (P.G.) Anti freezing agent 30.00gm.
4 J 1269 (Emulsifier) 10.00gm.
5 Silicon dioxide (Deformer) 5.00gm.
6 Jemol D-425 (Wetting agent) 5.00gm.
7 Formaldehyde (40 % in water) 2.5gm.
8 Gum (Xanthan gum,2% solution in water) 10.00gm
9 Water (Q.S) 29.50gm
Total Qty. 500.00gm

Process of Preparation for Propamocarb hydrochloride (~55% w/w) and Sulphur (~20%w/w) Suspo emulsion (SE) formulation:-
• Charge Water (29.5gm) and Propylene glycol (30.0gm) to reactor stirred well, then add J 1269 (10.0gm) and D-245 (5.0gm) to reactor and stir the mixture well till complete homogenization of the mass.
• Sulphur (102.0gm) added to the above stirred mass and stirred well till mass gets well mixed, this mass is transferred to bed mill for grinding of mass till required particle size (<20µm) achieved.
• Add Propamocard hydrochloride (306.0gm) to above mass in liquid form under stirring and maintain the mass till complete dissolution under stirring.
• Add 2% Xantham gum solution (10.0gm), Defomer (5.0gm) and Formaldehyde (2.5gm) to above stirred mass and maintain for 30 minute.

More preferably the suspo emulsion formulation for the present fungicidal composition comprises and not limited to depict in following table:
Table-3:

Sr. No.
Component /Ingredients
Quantity

1. Propamocarb hydrochloride 50-70 % (w/w)
2. Sulphur 10-30% (w/w)
3. Propylene glycol 0.1-10% (w/w)
4. Methanol 5.0-80%
5. J 1269 0.1-5.0%
6. Silicon dioxide 0.1-5.0%
7. Jemol D-425 0.1-5% (w/w).
8. Formaldehyde 0.1-5.0% (w/w)
9. Xanthan Gum 0.1-10% (w/w).
10. Water q.s.

Storage Stability study:
The stability data of formulation of Propamocarb hydrochloride (~55%) + Sulphur (~ 20%) suspo-emulsion (SE) formulation prepared
Table-4:
Specification Initial Heat Stability study at 54± 2OC for 14 Days Cold Storage stability study at 0 ± 2OC for 14 Days
Parameter In House
Description White to off white colored liquid. Complies Complies Complies
Propamocarb hydrochloride (A.I.Content ) 54 to 56 % w/w
(by HPLC) Complies Complies Complies
Sulphur
(A.I.Content ) 19 to 21 % w/w (by HPLC) Complies Complies Complies
Suspensibility Min 80 % Complies Complies Complies
pH. 5.0-9.0 Complies Complies Complies
Viscosity (cps) 300 to 500 cps Complies Complies Complies
Storage stability study was done for the suspo emulsion formulation prepared comprising Propamocarb hydrochloride (~55%) + Sulphur (~ 20%). The results were found to be satisfactory and this formulation is passing in all physicochemical properties.

Bio-Efficacy field trials:
Evaluation of bio-efficacy and Phytotoxicity of Propamocarb hydrochloride ~55% + Sulphur ~20% SE on Cotton and Tomato for the control of fungi like Phytophthora infestans, Pythium spp., Pyhtophthora spp., Cercospora, Rhizoctoniasolani, Downy mildew and Mildew blast disease.
Propamocarb hydrochloride ~55% + Sulphur ~20% SE (Code:- P+S-01)
Objective:
(i) To determine the bio-efficacy of Propamocarb hydrochloride 55% + Sulphur 20% SE against Phytophthora infestans, Pythium spp., Pyhtophthora spp., Cercospora, Rhizoctoniasolani, Downy mildew and Mildew blast disease.
(ii) To determine Phytotoxicity of Propamocarb hydrochloride 55% + Sulphur 20% SE on Cotton and Tomato crops.
Table-5:
Details of Experiment
a) Test chemical Propamocarb hydrochloride ~55% + Sulphur ~20% SE
b) Crop Cotton and Tomato
C) Target fungi Phytophthora infestans, Pythium spp., Pyhtophthora spp., Cercospora, Rhizoctoniasolani, Downy mildew and Mildew blast disease
d) Plot size 3.0 m × 3.0 m
e) Design RBD (Randomized Block Design)
f) Treatment 7(Seven); Table 1
g) Number of reapplication 03
h) Application method Spray by knapsack sprayer fitted with flat fan nozzle
i) Water volume used 500 liters/ha

Table-6: Treatment details for bio-efficacy of different fungicide:
SR. No. Treatment Dosage Formulation
(A.I. gm/ha)
1. Propamocarb hydrochloride 55% + Sulphur 20% SE (4.0 ml) 25+25= 50
2. Propamocarb hydrochloride 55% + Sulphur 5% SE (3.3 ml) 20+20=40
3. Propamocarb hydrochloride 55% + Sulphur 55% SE (2.0 ml) 15+15=30
4. Propamocarb hydrochloride 55% + Sulphur 5% SE (4.2 ml) 30+30=60
5. Propamocarb hydrochloride 55% SE 30
6. Sulphur 20% SE 50
7. Untreated control (water only) -

Example-4: Bio-efficacy of Propamocarb hydrochloride ~55% + Sulphur ~20% SE against Cotton fungal diseases (Leaf spot and Blight).
Table-7:
Treatments DOSE
Gm/ha Observed Value Before Spray Observed Value After Spray % Fungal disease control
Mean of No. of Leaf spot & Blight (15 leaves/ 5 Plants/ treatment)
1st 2nd 3rd 4th 5th
1 day 3 day 5 day 7 day 10 day
Propamocarb hydrochloride 55%+ Sulphur 20% SE (F=4.0ml/L) 25 + 25 25 18.13 5.75 3.10 3.53 3.30 83.5%
Propamocarb hydrochloride 55%+ Sulphur 20% SE (F=3.3ml/L) 20 + 20 21 15.20 5.90 4.80 4.20 5.30 76%
Propamocarb hydrochloride 55%+ Sulphur 20% SE (F=2.0ml/L) 15 + 15 21 18.00 8.50 8.50 5.50 6.5 62%
Propamocarb hydrochloride 55%+ Sulphur 20% SE (F=4.2ml/L) 30 + 30 30 13.50 4.50 3.10 1.30 3.01 86.5%
Propamocarb hydrochloride 55% SE 30 23 19.50 9.25 6.86 8.32 7.51 61%
Sulphur 20% SE 50 21 19.50 12.25 15.86 8.32 9.51 35%
Untreated control - 22.5 23.00 22.10 23.00 23.5 5%

Results:
Propamocarb hydrochloride 55% + Sulphur 20% SE @ 50 gm (a.i./ha) and Propamocarb hydrochloride 55% + Sulphur 20% SE @ 60 gm (a.i./ha) dose were at as per they exhibited fungal disease control 88, 93 per cent after 7 days and 85, 87 per cent after 10 days of spray.
Propamocarb hydrochloride 55% + Sulphur 20% SE @ 50 gm (a.i./ha) and Propamocarb hydrochloride 55% + Sulphur 20% SE @ 60 gm (a.i./ha) dose showed systemic effect and significantly superior or standard check by separately Propamocarb hydrochloride 55% SE @ 30 and Sulphur 20% SE @ 50 for control of fungal diseases after 7 and 15 days of spray.

Example 5: Bio-efficacy of Propamocarb hydrochloride ~55% + Sulphur ~20% SE against Tomato fungal diseases (Leaf spot and Blight).
Table-8:
Treatments DOSE
Gm/ha Observed Value Before Spray Observed Value After Spray % Fungal disease control
Mean of No. of Leaf Spot & Blight (15 leaves/ 5 Plants/ treatment)
1st 2nd 3rd 4th 5th
1 day
3 day 5 day 7 day 10 day
Propamocarb hydrochloride 55%+ Sulphur 20% SE (F=4.0ml/L) 25 + 25 29 17.50 7.80 4.80 3.40 4.50 87%
Propamocarb hydrochloride 55%+ Sulphur 20% SE (F=3.3ml/L) 20 + 20 27 14.35 6.15 3.05 2.55 3.19 81%
Propamocarb hydrochloride 55%+ Sulphur 20% SE
(F=2.0ml/L) 15 + 15 29 21.56 14.4 9.52 9.10 10.53 72%
Propamocarb hydrochloride 55%+ Sulphur 20% SE
(F=4.2ml/L) 30 + 30 30 11.65 4.70 2.25 1.48 2.54 92.5%
Propamocarb hydrochloride 55% SE 30 28 19.15 9.01 7.56 4.32 5.15 69%
Sulphur 20% SE 50 27 24.5 22.95 21.31 20.50 21.52 25%
Untreated control - 29 25.50 22.91 20.87 20.10 21.46 5%

Results:
Propamocarb hydrochloride 55% + Sulphur 20% SE @ 50 gm (a.i./ha) and Propamocarb hydrochloride 55% + Sulphur 20% SE @ 60 gm (a.i./ha) dose were at as per they exhibited fungal disease control 90, 96 per cent after 7 days and 88, 91 per cent after 10 days of spray.
Propamocarb hydrochloride 55% + Sulphur 20% SE @ 50 gm (a.i./ha) and Propamocarb hydrochloride 55% + Sulphur 20% SE @ 60 gm (a.i./ha) dose showed systemic effect and significantly superior or standard check by separately Propamocarb hydrochloride 55% SC @ 30 and Sulphur 20% SE @ 50 for control of fungal disease after 7 and 15 days of spray.

Report of Phyto-Toxicitty evaluation on tomato cotton crop
Evaluation of phyto-toxicity effect of suspo-emulsion formulation of fungicidal composition of Propamocarb hydrochloride ~55% and Sulphur ~20% SE on 50,40,30 & 60 gm/ha on cotton & tomato crop.
TABLE-9: Symptoms of Leaf injury, Epinasty, Hyponasty, Necrosis, Vein clearing, Wilting before and after spraying of CLSL sample P+S-01 on Cotton crop:
Treatment DAS of observation
Before spray 1 DAS 3 DAS 5 DAS 7 DAS 10 DAS
R1 R2 R3 R1 R2 R3 R1 R2 R3 R1 R2 R3 R1 R2 R3 R1 R2 R3
T1 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0
T2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
T3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
T4 0 0 0 0 1 1 0 0 0 0 0 0 0 0 0 0 0 0
T5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Whereas, DAS= Days After spray
P+S-01=Propamocarb hydrochloride ~55% + Sulphur ~20% SE
Treatment:
T1= P+S-01 (25+25) F=4.0ml/L
T2= P+S-01 (20+20) F=3.3ml/L
T3= P+S-01 (15+15) F=2.0ml/L
T4= P+S-01 (30+30) F=4.2ml/L
T5 =Untreated control (Water only)

Conclusion:
Results of phyto-toxicity evaluation trial are given in table-8. As per results we are concluded that different doses of Propamocarb hydrochloride 55% + Sulphur 20% SE were cause minor phytotoxic symptoms on Cotton plant after the spraying, however plants are recover within 7-10 days of application. It may be due to phytotonic effect and weather effect Hence, it may be concluded that Propamocarb hydrochloride 55% + Sulphur 20% SE is safe to use on Tomato at the dosage from 50, 40, 30 & 60 gm/ha.
Table-10 : Symptoms of Leaf injury, Epinasty, Hyponasty, Necrosis, Vein clearing, Wilting before and after spraying of CLSL sample P+S-01 on Tomato crop:
Treatment DAS of observation
Before spray 1 DAS 3 DAS 5 DAS 7 DAS 10 DAS
R1 R2 R3 R1 R2 R3 R1 R2 R3 R1 R2 R3 R1 R2 R3 R1 R2 R3
T1 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0
T2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
T3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
T4 0 0 0 0 0 1 1 0 0 0 0 0 0 0 0 0 0 0
T5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Whereas DAS= Days After spray
P+S-01=Propamocarb hydrochloride ~55% + Sulphur ~20% SE
Treatment:
T1= P+S-01 (25+25) F=4.0ml/L
T2= P+S-01 (20+20) F=3.3ml/L
T3= P+S-01 (15+15) F=2.0ml/L
T4= P+S-01 (30+30) F=4.2ml/L
T5 =Untreated control (Water only)
Conclusion:
Results of phyto-toxicity evaluation trial are given in table-9. As per results we are concluded that different doses of Propamocarb hydrochloride ~55% + Sulphur ~20% SE were cause minor phytotoxic symptoms on Tomato plant after the spraying, however plants are recover within 7-10 days of application. It may be due to phytotonic effect and weather effect Hence, it may be concluded that Propamocarb hydrochloride ~55% + Sulphur ~20% SE is safe to use on Cotton & Tomato at the dosage from 50, 40, 30 & 60 gm/ha.
,CLAIMS:We claim;
[CLAIM 1]. A suspo-emulsion formulation of stable and systemic fungicidal composition comprises:
a. a fungicide Propamocarb hydrochloride in a range of 50% to 70% (w/w/);
b. Sulphur in a range between 10% to 30% (w/w);
c. anti-freeze agent in an amount of 0.1-10% w/w;
d. Solvent ( organic / inorganic) in a range between 5.0-80%
e. Emulsifier in an amount of 0.1-5% w/w;
f. antifoam agent in an amount of 0.1-5% w/w;
g. stabilizing agent in an amount of 0.1-5% w/w;
h. viscosity agent in an amount of 0.1-10% w/w;
i. filler in an amount of quantity sufficient (q.s.);
j. one or more other inactive excipients are penetration promoters; wetting agents; spreading agents and/or retention agents or mixture thereof

[CLAIM 2]. The suspo-emulsion formulation as claimed in claim 1, wherein organic or inorganic solvent is selected from water, ethyl acetate, ethylene glycol, glycerine, heptane, hexamethyl phosphoramide (HMPA), Hexamethyl phosphoroustriamide (HMPT), methanol, methylt-butyl ether (MTBE), Toluene, xylene, Acetone, Acetonitrile, Solvent C-9, etc.

[CLAIM 3]. The suspo-emulsion formulation as claimed in claim 1, wherein emulsifier is selected from Jemol D-425, J 1269, Agrilan 788, 500L.

[CLAIM 4]. The suspo-emulsion formulation as claimed in claim 1, wherein anti-freezing agent is selected from a group comprising of propylene glycol, polyol, polyvinyl alcohols, phenyl naphthalene sulphonate, lignin derivatives, polyvinyl pyrrolidone, polyalkylpyrrolidone, carboxymethylcellulose, xanthan gum, polyethoxylated, fatty acids, polyethoxylated fattyalcohols, ethylene oxide copolymer, propylene oxide copolymer, polyethylene glycols and polyethylene oxides.

[CLAIM 5]. The suspo-emulsion formulation as claimed in claim 1, wherein viscosity agent is selected from the group consisting of natural polysaccharides preferably Xanthan Gum.

[CLAIM 6]. The suspo-emulsion formulation as claimed in claim 1, wherein anti-foam/deforming agent is silicon or alcohol based antifoam agent

[CLAIM 7]. The suspo-emulsion formulation as claimed in claim 1, wherein filler is water.

[CLAIM 8]. The suspo-emulsion formulation as claimed in claim 1, wherein systemic Propamocarb hydrochloride (~55%) and Sulphur (~20%) and particle size is not more than 20 micron.

[CLAIM 9]. The suspo-emulsion formulation as claimed in claim 1, wherein Particle size of the formulation is not more than 20 micron.

[CLAIM 10]. The suspo-emulsion formulation as claimed in claim 1, wherein viscosity of the formulation is 300cps to 500cps

[CLAIM 11]. The suspo-emulsion formulation as claimed in claim 1, wherein the process for the preparation of the suspo-emulsion formulation comprising step off:
a) Forming the aqueous solution comprising of wetting and dispersing agent or emulsifier;
b) An aqueous dispersion (suspo emulsion, SE) of Propamocarb hydrochloride in amount of 50% to 70% (w/w), mixture of Propamocarb hydrochloride with of anti-freezing agent, antifoam agent and emulsifier in water; Sulphur in a range between 10% to 30% (w/w) with organic / inorganic solvent and emulsifier;
c) one or more additives selected from the group consisting of non-ionic or anionic surfactants or dispersing aids.
d) Wet grinding of the suspension in pressurized bead mill to reduce particle size of the suspension up to D90 less than 20 micron.
e) Mixing of component / compounds / formulation into formulation to prepare suspo-emulsion (SE) Formulation.
f) Finally adding the stabilizing agent /viscosity agent & preservative to the suspo-emulsion (SE) to enhance viscosity

[CLAIM 12]. The suspo-emulsion formulation as claimed in claim 1, wherein the formulation comprises:
i. Propamocarb hydrochloridein a range 50-70 % (w/w)
ii. Sulphur a range of 10-30% (w/w)
iii. Propylene glycol in a range of 0.1-10% (w/w)
iv. Methanol in a range of 5.0-80%
v. J 1269 in a range of 0.1-5.0%
vi. Silicon dioxide in range of 0.1-5.0%
vii. Jemol D-425 in a range of 0.1-5% (w/w).
viii. Formaldehyde in a range of 0.1-5.0% (w/w)
ix. Gum, Xanthan in a range of 0.1-10% (w/w).
x. water Q.S

Dated this 24th day of August 2020