DESC:FIELD OF THE INVENTION:
The present invention relates to novel synergistic composition of bioactive amounts of, Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide along with one or more inactive excipients. The present invention also relates to process for preparing the said composition comprising bioactive amounts of Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide with one or more inactive excipients.

BACKGROUND OF THE INVENTION

Thifluzamide was first disclosed in US5045554. Chemically Thifluzamide is known as 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1,3-thiazole-5-carboxanilide. Chemical structure of Thifluzamide is as below;

Thifluzamide is highly active against Basidiomycete fungi, in particular Rhizoctonia solani, primarily in rice, potatoes, and turf markets.

Metalaxyl M was first disclosed in US 4151299 A. Chemically Metalaxyl M N-(2,6-Dimethylphenyl)-N-(methoxyacetyl)-DL-alanine methyl ester. Chemical Structure of Metalaxyl M is as below;

Metalaxyl is a phenylamide fungicide with systemic function. It can be used to control Pythium in a number of vegetable crops, and Phytophthora in peas.

EP 2109366 A2 relates to mixtures comprising, as active components, 1) fipronil and ethiprole; and 2) azoles, strobilurins, carboxamides, heterocylic compounds, carbamates, and optionally 3) metalaxyl, thifluzamide and more.

CN 104137842 A discloses sterilization combination containing initium and thifluzamide. The mass ratio of initium and thifluzamide is 1-50:50-1.

CN 103563922 A discloses a bactericidal composition containing thifluzamide and chlorothalonil and application thereof. The Weight ratio of the thifluzamide to the chlorothalonil is (1-70) :(1-50).

CN 103053555 A discloses a bactericide composition of thifluzamide and fluazinam. The mass ratio of the thifluzamide to the fluazinam is (10 to 1) to (1 to 15), and the preferred ratio is (6 to 1) to (1to 9).

CN 102077831 A discloses sterilizing composition ceftiofur amide (A) and (B) is selected from maneb fungicides zineb, propineb, metiram, mancozeb any of one for the active ingredients of two are mixed.

However still there is a need for a composition of specific fungicides which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.

Inventors of the present invention have surprisingly found that the novel composition of Thifluzamide, Metalaxyl M and one or more fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide as described herein in can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION

Accordingly, in a first aspect, the present invention provides a synergistic fungicidal composition comprising Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb and Zoxamide and at least one inactive excipients.

Accordingly, in a second aspect, the present invention relates to process for preparing the fungicidal compositions comprising Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb and Zoxamide and at least one inactive excipient.

According to another aspect of the present invention is synergistic fingicidal composition comprising Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide, where Thifluzamide is in the range of 1-10% w/w, Metalaxyl is in the range of 1-20% w/w and one of the additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide is in the range of 1-70% w/w.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides synergistic fungicidal composition comprising bioactive amounts of Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide and one or more inactive excipients.

"Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to Kill fungus and there by to control disease caused by it.

The Synergistic fungicidal composition Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide are
WP – Wettable powders: A solid pesticide formulation – micronized to powder form and typically applied as suspended particles after dispersion in water. WG or WDG – Water dispersible granule: A pesticidal formulation consisting of granules to be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques. It can also be termed as water soluble granules (WSG) or soluble granules (SG).

Liquid Sprayable (LS) – Soluble Concentrate: A soluble concentrate is in powder form intended for dilution with water or directly in solution from. In both the case, the end result will be clear solution of the insecticide in the water without any visible un-dissolved particles. SC – Suspension Concentrate: A stable suspension of solid pesticide(s) in a fluid usually intended for dilution with water before use. For a good formulation or ideal SC formulation, it should be stable and do not sediment over time. EC – Emulsifiable Concentrate: A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form an emulsion when added to water. In most of the case it is oil in water type emulsion to make it easy for application. EC formulation should be storage stable without any visible cracking of emulsion. ME – Microemulsion: A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form a solution/emulsion when added to water. The difference between EC and ME is the particle size of the actives in the final form.

OD – Oil Dispersion: Oil dispersions (OD) are one type of liquid formulation which is stable suspensions of active ingredients in a water-immiscible fluid which may contain other dissolved active ingredients and is intended for dilution with water before use.

CS – Capsule Suspension: Suspension of micro-encapsulated active ingredient in an aqueous continuous phase, intended for dilution with water before use.

SE- Suspension emulsion: A suspension emulsion or suspo emulsion (SE) consists of an organic phase with a dissolved active ingredient and an aqueous suspension phase, in which the active ingredient is dispersed in water.

Dispersible concentrate (DC): Dispersible concentrate (DC) is a liquid homogeneous formulation to be applied as a solid dispersion after dilution in water. There are many formulations which contains the part characteristics of EC and part characteristics of DC.

Dry – Spreadable Granule: Dry spreadable granules are dry granules which can be applied with a dry spreader to a target area and later when such granules get exposed to water via, for example, rain or irrigation, will not only readily disintegrate, but actively spread on solid substrates so as to achieve disintegration area diameter to original granule diameter ratios. Dry spreadable granules should possess good hardness and an ability to maintain integrity upon normal, commercial handling in a dry spreading operation and yet be capable of quickly disintegrating or scattering upon what may be a minimal exposure to water, such as, for example, a light rain.

GR – Soil applied Granule on inert or fertilizer carrier: This formulation is in the form of granules which can be applied on inert carrier or the carrier which is fertilizer.

ZC Formulation (Mix of CS and SC): “ZC formulation” is the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations) to designate "stable aqueous suspension of microcapsules and solid fine particles". ZC is a mixed formulation of CS and SC and is a stable aqueous suspension of microcapsules and solid fine particles, each of which contains one or more active ingredients. The formulation is intended for dilution into water prior to spray application. Formulating the active ingredients together eliminates the need for tank mixing, which can lead to incompatibility, and facilitates control of a wider range of pests with fewer applications. Like other aqueous liquid formulations, ZC formulations are easy to handle and measure, dust free, non-flammable and offer good miscibility with water.

The fungicidal formulation or composition can be classified as below:
The formulation can be in various physical forms, for example in the form of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier) or an impregnated polymer film

Preferably, the formulation is in the form wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG), an emulsifiable concentrate (EC), a microemulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO), an aqueous dispersion (e.g. aqueous suspension concentrate (SC), an oily dispersion (OD), a soluble liquid, or a water-soluble concentrate (wherein the water-soluble concentrate is with water or a water-miscible organic solvent as carrier). More preferably, the formulation is in the form of an emulsifiable concentrate (EC).

The formulation of the present invention is to be considered for application by any means selected from foliar spray, seed treatment, soil application, drenching, through drip irrigation, preferably by means of foliar spray.

Formulation of the present invention can be in any of the form described above.

Advantageous invention relates to a composition of Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide, where Thifluzamide is in the range of 1-10% w/w, Metalaxyl is in the range of 1-20% w/w and one of the additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide is in the range of 1-70% w/w and one or more inactive excpient.
The composition of present invention can be applies on the GMO and non GMO derivative of Cotton (Gossypium spp.), Jute (Corchorus oliotorus), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusine coracana), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus).
As per preferred embodiment, synergistic fungicidal composition useful in GMO and Non GMO varieties of Cotton (Gossypium spp.), Maize (Zea mays), Sorghum (Sorghum bicolor), Pearl millet (Pennisetum glaucum), Peanut (Arachis hypogeal), Mustard (Brassica juncea), Rape seed (Brassica napus), Green gram (Vigna radiate), Black gram (Vigna mungo), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Carrot (Dacus carota subsp. sativus), Grape (Vitis vinifera), Guava Papaya (Carica papaya), Turmeric (Curcuma longa), Ginger (Zingiber officinale).
The fungicidal composition of the present invention is having curative, preventive and systemic fungicidal properties for protecting cultivated plants. As has been mentioned, said active ingredient mixtures can be used to inhibit or destroy the pathogens that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops or useful plants, while at the same time those parts of plants which grow later are also protected from attack by such pathogens. Active ingredient mixtures have the special advantage of being highly active against diseases in the soil that mostly occur in the early stages of plant development

Composition of the present invention can be in any of the form described above.

The novel compositions of Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide is effective for management of mixed infestation of fungal diseases.
The compositions according to the invention have very good fungicidal properties and can be employed for controlling phytopathogenic fungi such as Ascomycetes, Basidiomycetes, Chytridiomycetes, Deuteromycetes, Oomycetes, Plasmodiophoromycetes, Zygomycetes, and the like. Examples which may be mentioned, but not by limitation, are some pathogens of fungal diseases which come under the above generic terms:
Diseases caused by pathogens causing powdery mildew 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; Leveillula species such as, for example Leveillula taurica, Erysiphe species such as for example Erysiphe polygoni, diseases caused by pathogens of rust diseases 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 graminis, Puccinia recondita or Puccinia triticina, Puccinia striiformis; Uromyces species such as, for example, Uromyces phaseoli; diseases caused by pathogens of smut diseases such as, for example, Sporisorium species such as , for example, Sporisorium scitamineum; Ustilago species such as, for example Ustilago maydis, Tilletia species such as for example Tilletia tritici, Ustilaginoidea species such as , for example Ustilaginoidea virens, diseases caused by pathogens of ergot diseases such as, for example Claviceps species, Claviceps purpurea; diseases caused by pathogens from the group of the Oomycetes 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 wilt 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 graminicola; 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 stalk 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 rot 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 rots 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; Rhizoctonia species such as, for example, Rhizoctonia solani; Sclerotium species such as, for example, Sclerotium rolfsii; cankers, galls and witches' broom diseases, 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; flower and seed diseases, caused by, for example, Botrytis species such as, for example, Botrytis cinerea; diseases of 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; by preference, the following diseases of soya beans can be controlled: fungal diseases on leaves, stems, pods and seeds caused by, for example, alternaria leaf spot (Alternaria spec, atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines); rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi), scab; (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora cassiicola) fungal diseases on roots and the stem base caused by, for example, black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmopspora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown 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), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
As per preferred embodiment, synergistic fungicidal composition is useful against Late blight caused by Phytophtora spp in Potato, Tomato, Damping off caused by Pythium spp, in tomato, Chilli, Brinjal, Pulses and Cereals, Downy milew in Grapes, Onion and Cucurbits, Root rot caused by Rhizoctonia spp in Peanut, Tomato, Chilli, Onion, Cotton.
The novel composition of the present invention in addition to Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide further comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

Dispersants are added to agrochemical compositions 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 re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder compositions, the most common dispersants are sodium lignosulphonates. 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 alkylarylethylene 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 lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate 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, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.

Water-based compositions 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 anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane 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 compositions: 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 compositions include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; 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 anti-microbial 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, parahydroxy benzoates or mixtures thereof.

Thickeners or gelling agents are used mainly in the composition 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 compositions 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, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), 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(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), 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 esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potasium 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 composition 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, tert-butanol, 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.

EXAMPLES
Example 1: Thifluzamide 2% + Metalaxyl-M 5% + Ametoctradin 17% SC (Suspension Concentrate)
Composition Percent (w/w)
Thifluzamide (97% purity) 2.27
Metalaxyl-M (95% purity) 5.47
Ametoctradin (96 % purity) 17.92
Polyalkoxylated butyl ether 1.50
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
MonoEthylen Glycol 7.00
Polysaccharides 0.20
Water 61.44
TOTAL 100.00

Procedure:
Step 1 Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenise, then slowly add gum powder to it and stir till complete dissolution.
Step 2 Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 3 Add required quantity of Wetting agent, antifreezing agent,dispersing agent & suspending agents and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 4 Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenised to get uniform slurry ready for grinding.
Step 5 Before grinding half the quantity of antifoam was added and then material was subjected to grinding in Dyno mill till desired particle size is achieved.
Step 6 Half quantity of the antifoam was added after grinding process completes and before sampling for in process analysis.
Step 7 Finally add gum solution to this formulation and send to QC for quality check.

Storage stability Study-Thifluzamide 2% + Metalaxyl-M 5% + Ametoctradin 17% SC (Suspension Concentrate)
Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white liquid Complies Complies Complies
Thifluzamide content 1.9-2.1 2.09 2.01 2.08
Metalaxyl-M 4.75-5.5 5.19 5.03 5.17
Ametoctradin content 16.15-17.85 17.33 17.02 17.29
Thifluzamide suspensibility Mini 80% 94.52 92.14 94.44
Metalaxyl-M suspensibility Mini 80% 94.81 92.12 93.78
Ametoctradin suspensibility Mini 80% 92.95 91.07 92.8
pH 5.5 to7.5 6.8 6.6 6.8
Particle size D50 <3, D90 <10 2.4, 7.9 2.6, 8.3 2.7, 8.9
Pourability 95 % min 98.3 97.6 97.2
Specific gravity 1.05 – 1.15 1.03 1.05 1.05
Viscosity 350 -800 cps 510 525 530

Room temperature storage data
Specification Study Duration
Parameters In House 1 month 6 month 12 months 24 months
Description Off-white liquid Complies Complies Complies Complies
Thifluzamide content 1.9-2.1 2.08 2.06 2.03 2.01
Metalaxyl-M content 4.75-5.5 5.18 5.17 5.11 5.03
Ametoctradin content 16.15-17.85 17.31 17.28 17.19 17.07
Thifluzamide suspensibility Mini 80% 94.4 94.21 94.01 93.24
Metalaxyl-M suspensibility Mini 80% 94.8 94.65 94.02 92.5
Ametoctradin suspensibility Mini 80% 92.95 92.81 92.13 91.11
pH 5.5 to7.5 6.78 6.74 6.71 6.61
Particle size D50 <3, D90 <10 2.4, 7.9 2.5, 8 2.6, 8.1 2.7, 8.2
Pourability 95 % min 98.3 98.2 98 97.7
Specific gravity 1.05 – 1.15 1.03 1.04 1.04 1.05
Viscosity 350 -800 cps 510 512 518 524

Example 2: Thifluzamide 4% + Metalaxyl-M 6% + Fluazinam 10% SC (Suspension Concentrate)
Composition Percent (w/w)
Thifluzamide (97% purity) 4.33
Metalaxyl-M (95% purity) 6.52
Fluazinam (97% purity) 10.52
Fatty Alcohol Ethoxylate 1.50
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
MonoEthylen Glycol 7.00
Polysaccharides 0.20
Water 65.73
TOTAL 100.00

Procedure: As per Example 1

Storage stability Study-Thifluzamide 4% + Metalaxyl-M 6% + Fluazinam 10% SC (Suspension Concentrate)
Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white liquid Complies Complies Complies
Thifluzamide content 3.8-4.2 4.16 4.02 4.14
Metalaxyl-M content 5.7-6.3 6.22 6.09 6.18
Fluazinam content 9.5-10.5 10.25 10.13 10.22
Thifluzamide suspensibility Mini 80% 94.58 92.17 94.45
Metalaxyl-M suspensibility Mini 80% 95.54 93.95 95.42
Fluazinam suspensibility Mini 80% 93.92 92.31 93.79
pH 5.5 to7.5 6.7 6.4 6.6
Particle size D50 <3, D90 <10 2.3, 7.7 2.4, 8.5 2.6, 8.7
Pourability 95 % min 98.8 98.1 98.3
Specific gravity 1.05 – 1.15 1.03 1.035 1.03
Viscosity 350 -800 cps 510 528 532

Room temperature storage data
Specification Study Duration
Parameters In House 1 month 6 month 12 months 24 months
Description Off-white liquid Complies Complies Complies Complies
Thifluzamide content 3.8-4.2 4.14 4.09 4.06 4.02
Metalaxyl-M content 5.7-6.3 6.21 6.18 6.16 6.10
Fluazinam content 9.5-10.5 10.23 10.21 10.17 10.11
Thifluzamide suspensibility Mini 80% 94.51 94.44 94.13 93.09
Metalaxyl-M suspensibility Mini 80% 95.49 95.19 94.59 94.01
Fluazinam suspensibility Mini 80% 93.85 93.71 92.98 92.50
pH 5.5 to7.5 6.7 6.66 6.59 6.49
Particle size D50 <3, D90 <10 2.3, 7.7 2.4, 7.8 2.5, 8 2.6, 8.2
Pourability 95 % min 98.70 98.60 98.40 98.10
Specific gravity 1.05 – 1.15 1.03 1.031 1.032 1.035
Viscosity 350 -800 cps 510 515 521 527

Example 3: Thifluzamide 4% + Metalaxyl-M 7.5% + Mandipropamid 12% SC (Suspension Concentrate)
Composition Percent (w/w)
Thifluzamide (97% purity) 4.33
Metalaxyl-M (95% purity) 8.11
Mandipropamid (97 % purity) 12.58
Polyalkoxylated butyl ether 1.50
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
MonoEthylen Glycol 7.00
Polysaccharides 0.20
Water 62.08
TOTAL 100.00

Procedure: As per Example 1
Storage stability Study-Thifluzamide 4% + Metalaxyl-M 7.5% + Mandipropamid 12% SC (Suspension Concentrate)
Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white liquid Complies Complies Complies
Thifluzamide content 3.8-4.2 4.15 4.03 4.14
Metalaxyl-M content 7.125-7.875 7.65 7.59 7.63
Mandipropamid content 11.4-12.6 12.25 12.06 12.25
Thifluzamide suspensibility Mini 80% 93.88 92.15 93.51
Metalaxyl-M suspensibility Mini 80% 95.75 93.49 95.64
Mandipropamid suspensibility Mini 80% 93.57 91.08 93.52
pH 5.5 to7.5 6.8 6.5 6.8
Particle size D50 <3, D90 <10 2.1, 7.1 2.4, 8.1 2.5, 8.2
Pourability 95 % min 98.6 97.95 98.4
Specific gravity 1.05 – 1.15 1.03 1.04 1.04
Viscosity 350 -800 cps 520 565 575

Room temperature storage data
Specification Study Duration
Parameters In House 1 month 6 month 12 months 24 months
Description Off-white liquid Complies Complies Complies Complies
Thifluzamide content 3.8-4.2 4.13 4.11 4.07 4.03
Metalaxyl-M content 7.125-7.875 7.64 7.6 7.55 7.51
Mandipropamid content 11.4-12.6 12.22 12.19 12.15 12.07
Thifluzamide suspensibility Mini 80% 93.8 93.71 93.4 93.06
Metalaxyl-M suspensibility Mini 80% 95.65 95.45 94.89 93.87
Mandipropamid suspensibility Mini 80% 93.45 93.17 92.57 92.11
pH 5.5 to7.5 6.8 6.77 6.71 6.63
Particle size D50 <3, D90 <10 2.2, 7.2 2.3, 7.3 2.4, 7.5 2.5, 8.1
Pourability 95 % min 98.6 98.5 98.3 98.1
Specific gravity 1.05 – 1.15 1.03 1.031 1.035 1.038
Viscosity 350 -800 cps 525 530 540 565

Example 4: Thifluzamide 2.5%+Metalaxyl-M 6.25%+Chlorothalonil 31.25% WG
Compositions Percent (w/w)
Thifluzamide (95% purity) 2.84
Metalaxyl-M (95% purity) 6.79
Chlorothalonil (96 % purity) 32.76
Alkylated naphtalene sulfonate, sodium salt 5.00
Sodium Ligno Sulphonate 2.00
Sodium Lauryl Sulfate 3.00
Silicone antifoam 1.00
Corn starch 20.00
Precipitated silica 2.00
Lactose monohydrate 18.00
China Clay 6.61
TOTAL 100.00

Procedure:
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx 1.5 hr)
Step 3 Finely grinded powder is mixed with required quantity of water to form extrudable dough.
Step 4 Dough is passed through extruder to get granules of required size.
Step 5 Wet granuleas are passed through Fluidised bed drier and further graded using vibrating screens.
Step 6 Final product is sent for QC approval.
Step 7 After approval material is packed in requied pack sizes.

Storage stability Study-Thifluzamide 2.5%+Metalaxyl-M 6.25%+Chlorothalonil 31.25% WG (Water Dispersible Granules)
Parameters Specification Initial Heat stability at 54±2 0C for 14 days Cold storage stability at 0±2 0C for 7 days
Description Off-white to Beige Granules Complies Complies Complies
Thifluzamide content 2.375-2.625 2.58 2.49 2.53
Metalaxyl-M content 5.94-6.56 6.37 6.26 6.34
Chlorothalonil content 29.69-32.81 31.55 31.25 31.51
Thifluzamide suspensibility Mini 70% 94.84 92.18 94.65
Metalaxyl-M suspensibility Mini 70% 96.43 94.55 95.88
Chlorothalonil suspensibility Mini 70% 92.92 90.71 91.92
Wettability 60 s 9 10 10
pH(1% in DM water) 5.5 to7.5 6.65 6.5 6.65
Wet Sieve(45 micron) Mini 98.0% 99.6 99.1 99.6
Bulk Density 0.45-0.85 0.52 0.5 0.52
Moisture Content Max 2.0% 1.2 0.8 1.2

Room temperature storage data
Parameters Specification Study Duration
1 month 6 month 12 months 24 months
Description Off-white to Beige Granules Complies Complies Complies Complies
Thifluzamide content 2.375-2.625 2.56 2.54 2.52 2.5
Metalaxyl-M content 5.94-6.56 6.35 6.31 6.29 6.26
Chlorothalonil content 29.69-32.81 31.51 31.48 31.39 31.27
Thifluzamide suspensibility Mini 70% 94.77 94.69 93.98 92.54
Metalaxyl-M suspensibility Mini 70% 96.40 96.01 95.75 94.71
Chlorothalonil suspensibility Mini 70% 92.88 92.53 92.01 90.87
pH(1% in DM water) 5.5 to7.5 6.65 6.63 6.58 6.51
Wettability Max 60 s 9 10 10 10
Wet Sieve(45 micron) Mini 98.0% 99.6 99.5 99.5 99.3
Bulk Density 0.45-0.85 0.52 0.51 0.51 0.5
Moisture Content Max 2.0% 1.2 1.1 1 0.8

Example 5: Thifluzamide 2%+Metalaxyl-M 5%+Propineb 35% WG (Water Dispersible Granules)
Compositions Percent (w/w)
Thifluzamide (95% purity) 2.32
Metalaxyl-M (95% purity) 5.47
Propineb (97% purity) 36.29
Alkylated naphtalene sulfonate, sodium salt 5.00
Polyacrylate copolymer 4.00
Sodium ligno sulphonate 2.00
Sodium Lauryl Sulfate 1.00
Silicone antifoam 1.00
Lactose monohydrate 15.00
Precipitated silica 2.00
China Clay 2.92
Corn starh 23.00
TOTAL 100.00

Procedure: As per Example 4
Storage stability Study-Thifluzamide 2%+Metalaxyl-M 5%+Propineb 35% WG (Water Dispersible Granules)
Parameters Specification Initial Heat stability at 54±2 0C for 14 days Cold storage stability at 0±2 0C for 7 days
Description Off-white to Beige Granules Complies Complies Complies
Thifluzamide content 1.9-2.1 2.09 2.01 2.07
Metalaxyl-M content 4.75-5.25 5.17 5.05 5.15
Propineb content 33.25-36.75 35.47 35.09 35.4
Thifluzamide suspensibility Mini 70% 95.85 93.12 95.11
Metalaxyl-M suspensibility Mini 70% 94.58 92.29 94.15
Propineeb suspensibility Mini 70% 94.25 92.02 93.98
pH(1% in DM water) 5.5 to7.5 6.85 6.65 6.8
Wettability Max 60 s 10 11 11
Wet Sieve(45 micron) Mini 98.0% 99.6 99.3 99.4
Bulk Density 0.45-0.85 0.6 0.62 0.61
Moisture Content Max 2.0% 1.4 1.1 1.2

Room temperature storage data
Parameters Specification Study Duration
1 month 6 month 12 months 24 months
Description Off-white to Beige Granules Complies Complies Complies Complies
Thifluzamide content 1.9-2.1 2.08 2.06 2.04 2.01
Metalaxyl-M content 4.75-5.25 5.15 5.13 5.09 5.05
Propineb content 33.25-36.75 35.45 35.39 35.34 35.11
Thifluzamide suspensibility Mini 70% 95.72 95.26 94.78 93.57
Metalaxyl-M suspensibility Mini 70% 94.35 94.17 93.89 93.05
Propineb content Mini 70% 94.08 93.57 93.49 92.66
pH(1% in DM water) 5.5 to7.5 6.85 6.82 6.76 6.71
Wettability Max 60 s 10 11 11 11
Wet Sieve(45 micron) Mini 98.0% 99.6 99.5 99.4 99.3
Bulk Density 0.45-0.85 0.6 0.6 0.61 0.61
Moisture Content Max 2.0% 1.4 1.3 1.1 1

Example 6: Thifluzamide 4%+ Metalaxyl-M 7.5%+Folpet 50% WP (Wettable Powder)
Compositions Percent (w/w)
Thifluzamide (95% purity) 4.42
Metalaxyl-M (95% purity) 8.11
Folpet (95% purity) 52.84
Alkylated naphtalene sulfonate, sodium salt 5.00
Sodium alkyl naphthalene sulfonate blend 2.00
Silicone based antifoam 0.50
PPT Silica 7.00
China Clay 20.13
TOTAL 100.00

Procedure:
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is then grinded through Jet mill / air classifier mill. Finely grinded material is blended in post blender till it becomes homogeneous.
Step 3 Final product is sent for QC approval.
Step 4 After approval material is packed in requied pack sizes.

Storage Stability-Thifluzamide 4%+ Metalaxyl-M 7.5%+Folpet 50% WP (Wettable Powder)
Parameters Specification Initial Heat stability at 54±2 0C for 14 days Cold storage stability at 0±2 0C for 7 days
Description off-white powder Complies Complies Complies
Thifluzamide content 3.8-4.2 4.13 4.05 4.1
Metalaxyl-M content 7.125-7.875 7.71 7.52 7.68
Folpet content 47.5-52.5 50.82 50.27 50.69
Thifluzamide suspensibility Mini 70% 96.66 94.35 96.1
Metalaxyl-M suspensibility Mini 70% 95.71 94.11 95.64
Folpet suspensibility Mini 70% 94.13 92.64 94.05
pH(1% in DM water) 5.5 to7.5 6.75 6.56 6.72
Wettability Max 120 s 40 42 41
Wet Sieve(45 micron) Mini 98.0% 99.5 99.2 99.3
Bulk Density 0.3-0.8 0.4 0.39 0.4
Moisture Content Max 2.0% 1.5 1.1 1.3

Room temperature storage data
Parameters Specification Study Duration
1 month 6 month 12 months 24 months
Description off-white powder Complies Complies Complies Complies
Thifluzamide content 3.8-4.2 4.12 4.1 4.08 4.04
Metalaxyl-M content 7.125-7.875 7.7 7.67 7.6 7.53
Folpet content 47.5-52.5 50.79 50.72 50.65 50.26
Thifluzamide suspensibility Mini 70% 96.52 96.06 95.73 94.93
Metalaxyl-M suspensibility Mini 70% 95.62 95.27 94.87 94.24
Folpet suspensibility Mini 70% 93.89 93.58 93.21 92.74
pH(1% in DM water) 5.5 to 7.5 6.75 6.71 6.66 6.54
Wettability Max 120 s 40 41 41 42
Wet Sieve(45 micron) Mini 98.0% 99.5 99.4 99.3 99.2
Bulk Density 0.3-0.8 0.4 0.4 0.39 0.39
Moisture Content Max 2.0% 1.5 1.4 1.3 1.1

Example 7: Thifluzamide 2%+ Metalaxyl-M 5%+Propineb 35% WP (Wettable Powder)
Compositions Percent (w/w)
Thifluzamide (95% purity) 2.32
Metalaxyl-M (95% purity) 5.47
Propineb ( 97% purity) 36.60
Alkylated naphtalene sulfonate, sodium salt 5.00
Sodium alkyl naphthalene sulfonate blend 2.00
Silicone based antifoam 0.50
PPT Silica 10.00
Lactose 12.00
China Clay 26.11
TOTAL 100.00

Procedure: As per Example 6

Storage Stability-Thifluzamide 2%+ Metalaxyl-M 5%+Propineb 35% WP (Wettable Powder)
Parameters Specification Initial Heat stability at 54±2 0C for 14 days Cold storage stability at 0±2 0C for 7 days
Description off-white powder Complies Complies Complies
Thifluzamide content 1.9-2.1 2.07 2.01 2.06
Metalaxyl-M content 4.75-5.25 5.15 5.06 5.12
Propineb content 33.25-36.75 35.49 35.07 35.41
Thifluzamide suspensibility Mini 70% 94.77 92.19 93.85
Metalaxyl-M suspensibility Mini 70% 91.58 89.18 90.32
Propineb suspensibility Mini 70% 93.82 91.74 92.74
pH(1% in DM water) 5.5 to7.5 6.53 6.42 6.51
Wettability Max 120 s 38 40 39
Wet Sieve(45 micron) Mini 98.0% 99.6 99.1 99.5
Bulk Density 0.3-0.7 0.35 0.34 0.35
Moisture Content Max 2.0% 1.3 1 1.1

Room temperature storage data
Parameters Specification Study Duration
1 month 6 month 12 months 24 months
Description off-white powder Complies Complies Complies Complies
Thifluzamide content 1.9-2.1 2.06 2.05 2.04 2.01
Metalaxyl-M content 4.75-5.25 5.14 5.12 5.09 5.06
Propineb content 33.25-36.75 35.47 35.46 35.38 35.12
Thifluzamide suspensibility Mini 70% 94.52 94.23 93.85 93.05
Metalaxyl-M suspensibility Mini 70% 91.32 91.02 90.15 89.56
Propineb suspensibility Mini 70% 93.59 93.24 92.46 91.81
pH(1% in DM water) 5.5 to7.5 6.53 6.51 6.48 6.44
Wettability Max 120 s 38 39 39 40
Wet Sieve(45 micron) Mini 98.0% 99.6 99.5 99.4 99.1
Bulk Density 0.45-0.85 0.35 0.34 0.34 0.34
Moisture Content Max 2.0% 1.3 1.1 1.1 1

Example 8: Fied efficacy trials
The synergistic fungicidal action of the inventive mixtures can be demonstrated by the experiments below. A synergistic effect exists wherever the action of a combination (ready-mix) of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticide activity than the sum of the pesticide activities of the individual components. In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:
Colby’s Formula:

To study the synergistic effect of Thifluzamide+ Metalaxyl-M+ one more fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide, in laboratory as well as field trial were carried out on different crops.
Trial 1
Laboratory screening of mixtures of Thifluzamide + Metalaxyl-M + one more fungicide selected from the group of Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide were carried out to evaluate their efficacy against various fungi causing fungal diseases in crop plants. The synergistic effects of Thifluzamide + Metalaxyl-M + Ametoctradin, Thifluzamide + Metalaxyl-M + Chlorothalonil, Thifluzamide + Metalaxyl-M + Metiram and Thifluzamide + Metalaxyl-M + Propineb on growth of the pathogen in vitro were studied by poison food technique. Different concentrations of active ingredient were prepared by dissolving the requisite quantity of each active ingredient in warm potato dextrose agar medium before autoclaving. After autoclaving the medium was then dispensed uniformly into 90 mm diameter petriplate and inoculated at the 2 mm mycelial discs of pathogen taken from 7 to 10 days old culture. Pathogen inoculated in unamended medium served as control. Each treatment was maintained in four replications. The inoculated plates were incubated at 30± C for 3 days and the diameter of the fungal colony was measured by measuring the two opposite circumference of the colony growth at 3 days interval for 15 days. The growth of fungus was monitored by measuring the radial growth (in mm) every 72 h till the fungus covers the plate completely in control plates. The percent inhibition (PI) of the fungus over the control was calculated using the following formula :
PI = A-B X 100/A
Where A= Colony diameter of fungus in control plates (mm)
B= Colony diameter of fungus in treated plates (mm)
The synergistic pesticidal action of the inventive mixtures calculated as per the Colby’s formula given above by using percent inhibition (PI) data.
Table 1: Effect on mycelial growth of Phytophthora infestans
Active Ingredient Concentrations (ppm) Phytophthora infestans
Mycelial growth (mm) % Inhibition over control
Thifluzamide+Metalaxyl-M+Ametoctradin 5+12.5+50 0.0 100.00
Thifluzamide+Metalaxyl-M+Metiram 5+12.5+100 0.0 100.00
Thifluzamide+Metalaxyl-M 5+12.5 37.4 57.79
Thifluzamide+Ametoctradin 5+50 42.6 51.92
Thifluzamide+Metiram 5+100 45.2 48.98
Metalaxyl-M+Ametoctradin 12.5+50 33.2 62.53
Metalaxyl-M+Metiram 12.5+100 35.6 59.82
Thifluzamide 5 51.2 42.21
Metalaxyl-M 12.5 45.6 48.53
Ametoctradin 50 48.8 44.92
Metiram 100 56.4 36.34
Untreated Check (UTC) 0 88.6 0.00

Table 2: Synergistic activity on mycelial growth of Phytophthora infestans
Active Ingredient Concentrations (ppm) % Growth Inhibition of Phytophthora infestans
Obs. Value Exp. Value Ratio O/E
Thifluzamide+Metalaxyl-M+Ametoctradin 5+12.5+50 100.00 83.62 1.20
Thifluzamide+Metalaxyl-M+Metiram 5+12.5+100 100.00 81.07 1.23
Thifluzamide+Metalaxyl-M 5+12.5 57.79 70.26 0.82
Thifluzamide+Ametoctradin 5+50 51.92 68.17 0.76
Thifluzamide+Metiram 5+100 48.98 63.21 0.77
Metalaxyl-M+Ametoctradin 12.5+50 62.53 71.65 0.87
Metalaxyl-M+Metiram 12.5+100 59.82 67.24 0.89
Thifluzamide 5 42.21
Metalaxyl-M 12.5 48.53
Ametoctradin 50 44.92
Metiram 100 36.34

In vitro studies indicated the suppressive effect of Thifluzamide + Metalaxyl-M + Ametoctradin and Thifluzamide + Metalaxyl-M + Metriam fungicides on the radial growth of the mycelium of Phytophthora infestans (Table 1). It can be seen that the synergism was observed between Thifluzamide + Metalaxyl-M + Ametoctradin and Thifluzamide + Metalaxyl-M + Metriam in terms of excellent suppressive effect on radial growth of Phytophthora infestans (Table 2).
Table 3: Composition of samples
Sample Code Active Ingredient Concentrations (ppm)
Sample 1 Thifluzamide+Metalaxyl-M+Chlorothalonil 10+25+125
Sample 2 Thifluzamide+Metalaxyl-M+Propineb 10+25+175
Sample 3 Thifluzamide+Metalaxyl-M 10+25
Sample 4 Thifluzamide+Chlorothalonil 10+125
Sample 5 Thifluzamide+Propineb 10+175
Sample 6 Metalaxyl-M+Chlorothalonil 25+125
Sample 7 Metalaxyl-M+Propineb 25+175
Sample 8 Thifluzamide 10
Sample 9 Metalaxyl-M 25
Sample 10 Chlorthalonil 125
Sample 11 Propineb 175
Sample 12 Untreated Check (UTC) 0

Table 4: Effect on mycelial growth of Pythium aphanidermatum and Rhizoctonia solani
Sample Code Pythium aphanidermatum Rhizoctonia solani
Mycelial growth (mm) % Inhibition over control Mycelial growth (mm) % Inhibition over control
Sample 1 0.0 100.00 0.0 100.00
Sample 2 0.0 100.00 0.0 100.00
Sample 3 49.6 31.49 38.2 57.56
Sample 4 54.8 24.31 39.6 56.00
Sample 5 60.2 16.85 37.8 58.00
Sample 6 43.8 39.50 48.2 46.44
Sample 7 45.2 37.57 47.6 47.11
Sample 8 60.4 16.57 41.4 54.00
Sample 9 50.4 30.39 56.2 37.56
Sample 10 53.8 25.69 62.8 30.22
Sample 11 60.2 16.85 66.4 26.22
Sample 12 72.4 0.00 90.0 0.00

Table 5 : Synergistic activity on mycelial growth of Phytophthora infestans
Sample Code % Growth Inhibition of Pythium aphanidermatum % Growth Inhibition of Rhizoctonia solani
Obs. Value Exp. Value Ratio O/E Obs. Value Exp. Value Ratio O/E
Sample 1 100.00 56.84 1.76 100.00 79.96 1.25
Sample 2 100.00 51.71 1.93 100.00 78.81 1.27
Sample 3 31.49 41.92 0.75 57.56 71.28 0.81
Sample 4 24.31 38.01 0.64 56.00 67.90 0.82
Sample 5 16.85 30.63 0.55 58.00 66.06 0.88
Sample 6 39.50 48.27 0.82 46.44 56.43 0.82
Sample 7 37.57 42.12 0.89 47.11 53.93 0.87
Sample 8 16.57 54.00
Sample 9 30.39 37.56
Sample 10 25.69 30.22
Sample 11 16.85 26.22
Sample 12 0.00 0.00

The mixture of Thifluzamide + Metalaxyl-M + Chlorothalonil and Thifluzamide + Metalaxyl-M + Propineb shows synergism in terms of their efficacy against Pythium aphanidermatum and Rhizoctonia solani by suppressing mycelia growth.
Trial 2 : Disease control in Potato
The synergistic mixtures of Thifluzamide+Metalaxyl-M+Ametoctradin, Thifluzamide+Metalaxyl-M+Chlorothalonil, Thifluzamide+Metalaxyl-M+Metiram and Thifluzamide+Metalaxyl-M+Propineb were also evaluated in potato (Solanum tuberosum) crop.
Details of Experiment:
a) Experiment design : Randomized Block Design
b) Replication : Three
c) Treatments : Twenty including untreated check.
d) Plot size : 20 sq. m.
e) Spacing : Row to Row 60 cm, Plant to platn 25 cm
f) Test Crop & Variety : Potato, Kufri Badshah
g) Time of application : Two spray at 10 days interval
h) Spray Volume : 500 l/h
i) Method of application : Foliar spray with knap sack sprayer
The Potato crop was raised in the field as per the standard agronomic practices. The spraying was done as preventive spray and second spray at 10 days after first spray. The observations on disease severity and incidence of late blight were recorded at 7 days after second application.

1) Late blight disease:
Record the number of healthy and infected leaves from 100 leaves per plot and calculate the percent disease incidence.
The disease severity recorded on 100 leaves by following 0-9 scale described as below;
Grade Percent branches & foliage infected per plant
0 No infection to branches and leaves
1 1-10% leaves infected
3 11-25% leaves infected
5 26-50% leaves infected
7 51-75% leaves infected
9 >75% leaves infected.

% Disease Incidence on leaves = No. of leaves infected X 100.
No. of leaves observed

Late Blight PDI = ____Sum of numerical disease rating X 100 _
(Severity %) Total no. of samples X Max. of disease rating scale

Table 6: Bioefficacy of synergistic mixtures against Late blight of Potato, Phytophthora infestans
Treatment details g.a.i./h Late Blight, Phytophthora infestans
Incidence (%) PDI / Severity (%)
Thifluzamide 2%+Metalaxyl-M 5%+Ametoctradin 17% SC 50+125+425 4.28 1.07
Thifluzamide 2%+Metalaxyl-M 5%+Chlorothalonil 25% SC 50+125+625 3.68 1.82
Thifluzamide 2%+Metalaxyl-M 5%+Metiram 40% WG 50+125+1000 2.93 0.84
Thifluzamide 2%+Metalaxyl-M 5%+Propineb 35% WG 50+125+875 5.63 2.63
Thifluzamide 2%+Metalalxyl-M 5% SC 50+125 42.83 35.72
Thifluzamide 2%+Ametoctradin 17% SC 50+425 38.82 40.28
Thifluzamide 2%+Chlorothalonil 25% SC 50+625 48.39 52.38
Thifluzamide 2%+Metiram 40% WG 50+1000 52.38 52.38
Thifluzamide 2%+Propineb 35% WG 50+875 58.48 62.38
Metalaxyl-M 5%+Ametoctradin 17% SC 125+425 28.82 32.28
Metalaxyl-M 5%+Chlorothalonil 25% SC 125+625 30.18 28.73
Metalaxyl-M 5%+Metiram 40% WG 125+1000 26.73 24.83
Metalaxyl-M 5%+Propineb 35% WG 125+875 30.72 30.18
Thifluzamide 2% SC 50 82.93 70.38
Metalaxyl-M 5% SC 125 68.25 44.28
Ametoctradin 17% SC 425 70.73 46.83
Chlorothalonil 25% SC 625 77.82 48.92
Metiram 40% WG 1000 74.18 52.38
Propineb 35% WG 875 81.28 60.38
Untreated Check (UTC) 0 100.00 77.38
SC Susupension Concentrate, WG Water Dispersible Granules

The field efficacy observations of synergistic mixtures of Thifluzamide+Metalaxyl-M+Ametoctradin, Thifluzamide+Metalaxyl-M+Chlorathalonil, Thifluzamide+Metalaxyl-M+Metiram and Thifluzamide+Metalaxyl-M+Propineb shows excellent control of late blight of Potato caused by Phytophthora infestans under field conditions compared to the prior art samples.

,CLAIMS:
1. A synergistic fungicidal composition comprising Thifluzamide, Metalaxyl M and at least one additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb and Zoxamide and at least one inactive excipients.
2. The synergistic fungicidal composition according to claim 1, wherein where Thifluzamide is in the range of 1-10% w/w, Metalaxyl is in the range of 1-20% w/w and one of the additional fungicide selected from Ametoctradin, Chlorothalonil, Fluazinam, Fluopicolide, Folpet, Mancozeb, Mandipropamid, Metiram, Propineb, Zoxamide is in the range of 1-70% w/w.
3. The synergistic fungicidal composition according to claim 1 or 2, wherein inactive excipients can be selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents and buffering agent.
4. The synergistic fungicidal composition according to claims 1-3, wherein formulation is selected from wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG), an emulsifiable concentrate (EC), a microemulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO), an aqueous dispersion (e.g. aqueous suspension concentrate (SC), an oily dispersion (OD), a soluble liquid, or a water-soluble concentrate.

5. The synergistic fungicidal composition according to claim 1 or 2 wherein the composition is applied as foliar spray, seed treatment, soil application, drenching, through drip irrigation.

6. The synergistic fungicidal composition according to any preceding claims, wherein the said composition is be useful in GMO and Non GMO varieties of Cotton (Gossypium spp.), Maize (Zea mays), Sorghum (Sorghum bicolor), Pearl millet (Pennisetum glaucum), Peanut (Arachis hypogeal), Mustard (Brassica juncea), Rape seed (Brassica napus), Green gram (Vigna radiate), Black gram (Vigna mungo), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Carrot (Dacus carota subsp. sativus), Grape (Vitis vinifera), Guava Papaya (Carica papaya), Turmeric (Curcuma longa), Ginger (Zingiber officinale).

7. The synergistic fungicidal composition according to any preceding claims, wherein the said composition is be useful against Late blight caused by Phytophtora spp in Potato, Tomato, Damping off caused by Pythium spp, in tomato, Chilli, Brinjal, Pulses and Cereals, Downy milew in Grapes, Onion and Cucurbits, Root rot caused by Rhizoctonia spp in Peanut, Tomato, Chilli, Onion, Cotton.
Dated this day 2nd of May, 2017