Claims:
1. A fungicidal composition comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide, wherein said composition is a solid formulation meant for direct use.

2. The composition as claimed in claim 1 wherein said dithiocarbamate fungicide and benzimidazole fungicide or a benzimidazolylcarbamate fungicide are present in a ratio of 10.08: 1.92.

3. An improved fungicidal composition for crop protection comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide characterized in that said composition is a solid formulation meant for direct use.

4. The composition as claimed in claim 1 and 3 wherein said dithiocarbamate fungicide is mancozeb.

5. The composition as claimed in claim 1 and 3 wherein said benzimidazole fungicide or a benzimidazolylcarbamate fungicide is carbendazim.

6. The composition as claimed in claim 1 wherein carbendazim is present in an amount of 1.92% by weight of the composition.

7. The composition as claimed in claim 1 wherein mancozeb is present in an amount of 10.08% by weight of the composition.

8. The composition as claimed in any of the preceding claims further comprising agrochemically acceptable carriers and fillers.

9. The composition as claimed in claim 8 wherein said agrochemically acceptable carrier is selected from at least one dispersing agent; at least one wetting agent, at least one antifoam, at least one surfactant and combinations thereof.

10. The composition as claimed in claim 9 wherein said wetting agent is selected from the group consisting of a salt of the ester of the substituted phenol, and sulfosuccinate.

11. The composition as claimed in claim 8 wherein said fillers are selected from one or more of precipitated silica, china clay and kaolin.

12. The composition as claimed in claim 1 wherein said crop diseases is disease in rice.

13. The composition as claimed in claim 1 wherein said crop diseases is selected from blast, Helminthosporium leaf spot, sheath blight, and bakanae disease.

14. The composition as claimed in claim 1 wherein said crop diseases is selected from blast and sheath blight.

15. The composition as claimed in claim 1, wherein said a solid formulation meant for direct use is selected from a dustable powder (DP), powder for dry seed treatment (DS), granules (GR), or a tablet for direct dispersion (DT).

16. The composition as claimed in claim 15, wherein said a solid formulation meant for direct use is granules (GR).
, Description:Field of the Invention
The present invention relates to an improvement in the fungicidal composition. The present invention relates to a fungicide composition based on dithiocarbamate and another fungicide compound and a method for protecting plants against fungal diseases using said composition.

Background of the invention
Fungicides are chemical compounds used to prevent, control or eradicate the spread of fungi on crop or plants in the gardens or in nursery, ornamental plants, etc. This can cause serious damage resulting in the loss of yield and thus quality as well as profit from the crop plants. Fungicides are also used to fight fungal infections. Fungicides can either be contact or systemic fungicides. A contact fungicide kills fungi when sprayed on the infected its surface; and a systemic fungicide has to be absorbed by the plant.

CARBENDAZIM chemically known as methyl benzimidazol-2-ylcarbamate with molecular formula as C9H9N3O2

Carbendazim is a systemic benzimidazole fungicide that plays a very important role in plant disease control. It was first reported in 1973 and was developed by BASF, Hoeschst (now part of Bayer) and Dupont. Pure carbendazim is a colourless, white crystaline, odourless solid which decomposes on melting at approximately 250ºC. Technical grade is >98% pure (FAO specification). Carbendazim is not corrosive. Carbendazim is used to control a broad range of diseases on arable crops (cereals, oilseed rape), fruits, vegetables and ornamentals. It is also used in post-harvest food storage, and as a seed pre-planting treatment.

MANCOZEB chemically known as [[2-(dithiocarboxy)amino]ethyl] carbamodithioato]] (2-)-?S,?S']manganese mixture with [[2-[(dithiocarboxy)amino]ethyl]carbamodithioato]](2-)-?S,?S']zinc with molecular formula as :
-SCSNHCH2CH2NHCSSMn- (Zn)

Mancozeb is a dithiocarbamate non-systemic agricultural fungicide with multi-site, protective action on contact. The mixture controls many fungal diseases in a wide range of field crops, fruits, nuts, vegetables, and ornamentals.

As regards fungicide activity, in particular for the protection of crops, various compounds have been applied that shown good fungicide activity. However, the research continues for improvement of performances, in particular in terms of fungicide activity and in particular in terms of maintaining this fungicide activity over time. It has been known that application of ‘Carbendazim and Mancozeb’ in the composition, the saprophytic fungi are controlled and due to the plant’s undiseased state the nutritional requirement is fulfilled and the biomass of the plants is increased.

Granular formulations offer significant advantages over other formulations such as ease of handling, ease of use, reduced worker exposure, reduced toxicity, and therefore offer a convenient form for delivery of pesticides. These granules flow freely and cleanly from their containers and significantly reduce dust hazards. In order to be effective, the granules are required to maintain their physical integrity until they are delivered to the carrier liquid, where they must disintegrate rapidly into fine particles that can remain suspended in the liquid phase.

Even though the combination of Mancozeb and Carbendazim is known in the art, the same is not known to be synergistically effective in granular formulation combating the fungal diseases.

However, there exists a continuous need in the art for improved compositions that not only helps in controlling the fungal growth but also enhances bioefficacy, having reduced phytotoxicity and an improved stability characteristics and economic significance.

Objects of the Invention:
The various embodiments of the present invention may, but do not necessarily, achieve one or more of the following advantages and/or objects:

An object of the present invention is to provide improved fungicidal composition comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide, in a solid formulation meant for direct use, useful for combating fungal infections.

Another object of the present invention is to provide fungicidal composition comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide in a synergistic ratio for an efficacious fungal control.

Yet another object of the present invention is to provide a solid fungicidal composition comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide that is useful for effectively controlling sheath blight, blast fungal diseases and also enhances the vigor/yield of the plant, wherein said solid formulation is meant for direct use.

Another object of the present invention is to provide a solid fungicidal formulation which is having good suspensibility and dispersibility.

These and the other advantages may be realized by reference to the remaining portions of the specification.

Summary of the invention
In an aspect the present invention provides that a fungicidal composition comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide was synergistic only when presented as a a solid formulation meant for direct use.

In another aspect the present invention provides an improved composition of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide in the form of a solid formulation meant for direct use.

In another aspect the present invention provides a fungicide composition comprising fungicidally effective amount of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide and at least one agriculturally acceptable adjuvant/ agriculturally acceptable excipient.

In another aspect the present invention provides a method for controlling fungi at a locus, said method comprising treating the locus with a composition comprising fungicidally effective amount of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide in a solid formulation meant for direct use.

In another aspect the present invention provides a kit comprising a fungicide composition comprising of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide by weight of the composition, wherein the kit comprises at least one component comprising the fungicidal composition as a solid formulation meant for direct use.

Additional features and advantages of the proposed invention will be apparent from the detailed description that follows, which illustrates by way of example, the most preferred features of the proposed invention which are not to be construed as limiting the scope of the invention described herein.

Detailed description of the invention

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It must be noted that, as used in this specification, the singular forms “a,” “an” and “the” include plural referents unless the content clearly dictates otherwise.

The term "about" used to qualify the amounts of mancozeb and carbendazim shall be interpreted to mean "approximately" or "reasonably close to" and any statistically insignificant variations therefrom.

As used herein, the terms “comprising” “including,” “having,” “containing,” “involving,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. The terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances.

In an embodiment, the aspects and embodiments described herein shall also be interpreted to replace the clause “comprising” with either “consisting of” or with “consisting essentially of” or with “consisting substantially of”.

The term ‘locus’ as used herein shall denote the vicinity of a desired crop in which fungal control is desired. The locus includes the vicinity of desired crop plants wherein the fungal infestation has occurred or is expected to occur. The term crop shall include a multitude of desired crop plants or an individual crop plant growing at a locus.

The term ‘control’ indicates eradication of the investigated fungi. A 100% control signifies total eradication of the fungi under investigation.

The term “fungicidally effective amount” of active components, as used herein, shall denote an amount that can be used to control harmful fungi when used together.

It has been surprisingly found by the present inventors that a fungicidal combination comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide was synergistic only when presented as a solid formulation meant for direct use .

It was further found that the fungicidal combination of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide was best only additive, and more frequently antagonistic, when presented as a solid formulation meant for dispersion or dissolution.

Without wishing to be bound by theory, the present inventors believe that when administered as a solid formulation meant for direct use, the dithiocarbamate fungicide and the benzimidazole fungicide or a benzimidazolylcarbamate fungicide interact more intimately thus exhibiting a synergistic correlation, which was not seen in a solid formulation meant for dissolution or dispersion.

In accordance with one aspect of the present invention there is provided an improved fungicidal composition comprising a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide, wherein the composition is a solid formulation meant for direct use.

Thus, the present invention provides an improved composition of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide for controlling fungal disease in plants, wherein the improved composition is a solid formulation meant for direct use.

In an embodiment, the present invention provides a composition comprising:
(a) at least one dithiocarbamate fungicide;
(b) at least one benzimidazole fungicide;
(c) at least one agrochemically acceptable excipient;
wherein said composition is a solid formulation meant for direct use.

In an embodiment, the present invention provides a composition comprising:
(a) at least one dithiocarbamate fungicide;
(b) at least one a benzimidazolylcarbamate fungicide;
(c) at least one agrochemically acceptable excipient;
wherein said composition is a solid formulation meant for direct use.

In an embodiment, the term solid formulation meant for direct use includes the class of solid formulations that is meant for direct use as defined by FAO (http://www.fao.org/3/a-y4353e.pdf, page 72). These formulations are typically in solid form, which are applied in dry form using machines. These are solid formulations applied directly in field without dissolution or dispersion into solvents.

Thus, in an embodiment, the composition of the present invention is a dustable powder (DP), powder for dry seed treatment (DS), granules (GR), or a tablet for direct dispersion (DT).

In an embodiment, the composition of the present invention is a granular formulation (GR).

In an embodiment the dithiocarbamate fungicide is selected from amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet etem, milneb, mancopper, mancozeb, maneb, metiram, polycarbamate, propineb and zineb.

In an embodiment, the benzimidazole fungicide or a benzimidazolylcarbamate fungicide include benomyl, carbendazim (MBC), thiophanate-methyl, thiabendazole and fuberidazole, albendazole, benomyl, carbendazim, cypendazole, debacarb and mecarbinzid.

In an embodiment, the present invention provides a composition comprising:
(a) mancozeb;
(b) at least one benzimidazole fungicide;
(c) at least one agrochemically acceptable excipient;
wherein said composition is a solid formulation meant for direct use.

In an embodiment, the present invention provides a composition comprising:
(a) mancozeb;
(b) at least one a benzimidazolylcarbamate fungicide;
(c) at least one agrochemically acceptable excipient;
wherein said composition is a solid formulation meant for direct use.

In an embodiment, the present invention provides a composition comprising:
(a) at least one dithiocarbamate fungicide;
(b) carbendazim;
(c) at least one agrochemically acceptable excipient;
wherein said composition is a solid formulation meant for direct use in the granular form.

In an embodiment the present invention relates to a synergistic solid formulation meant for direct use comprising combination of at least one dithiocarbamate fungicide and at least one benzimidazole fungicide or a benzimidazolylcarbamate fungicide wherein said benzimidazole fungicide or a benzimidazolylcarbamate fungicide and dithiocarbamate fungicide are present in a synergistic ratio of about 1.92:10.08.

In another embodiment the composition comprises a fungicidally effective amount of mancozeb and fungicidally effective amount of cabendazim, wherein said composition is synergistic when presented as a solid formulation meant for direct use.

The term “fungicidally effective amount of mancozeb” includes mancozeb being present in an amount of about 10.08% by weight of the composition.

The term “fungicidally effective amount of carbendazim includes carbendazim being present in an amount of about 1.92% by weight of the composition.

In another embodiment the composition comprises a fungicidally effective amount of mancozeb and fungicidally effective amount of cabendazim, wherein mancozeb and carbendazim are present in a synergistic ratio of about 10.08:1.92.

Preferably however, the specific amounts of mancozeb and carbendazim present within the compositions of the present invention is not particularly limiting as long as the ratio of about 10.08:1.92 is maintained. This preferred ratio is meant to be particularly preferred, although other ratios are not excluded.

In an exemplary embodiment, which is not to be construed as limiting, mancozeb is present in an amount of about 10.08% by weight of the composition and carbendazim is present in an amount of about 1.92% by weight of the composition.

In an embodiment the present invention provides a synergistic composition comprising carbendazim and mancozeb characterized in that the composition is formulated as a solid formulation meant for direct use.

The compositions according to the present invention is effective for the following plant diseases:

Disease in rice: Blast (Pyricularia Oryzae), Helminthosporium leaf spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani) , and bakanae disease (Gibberella fujikuroi).

Diseases in wheat: powdery mildew (Erysiphe graminis) , Fusariuin head blight (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale) , rust (Puccinia striiformis, P. graminis, P. recondita) , pink snow mold (Micronectriella nivale), Typhula snow blight (Typhula sp . ) , loose smut (Ustilago tritici) , bunt (Tilletia caries) , eyespot (Pseudocercosporella herpotrichoides) , leaf blotch 3h, (Mycosphaerella graminicola) , glume blotch (Stagonospora nodorum) , septoria, and yellow spot (Pyrenophora tritici-repentis) .

Diseases of barley: powdery mildew (Erysiphe graminis), Fusarium head blight (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust - (Puccinia striiformis, P. graminis, P. hordei) , loose smut (Ustilago nuda) , scald (Rhynchosporium secalis) , net blotch (Pyrenophora teres), spot blotch (Cochliobolus sativus), leaf stripe (Pyrenophora graminea) , and Rhizoctonia damping-off (Rhizoctonia solani) .

Diseases in corn: smut (Ustilago maydis), brown spot (Cochliobolus heterostrophus), copper spot (Gloeocercospora sorghi), southern rust (Puccinia polysora), gray leaf spot (Cercospora zeae-maydis), white spot (Phaeosphaeria mydis and/or Pantoea ananatis) and Rhizoctonia damping-off (Rhizoctonia solani).

Diseases of citrus: melanose (Diaporthe citri), scab (Elsinoe fawcetti), penicillium rot (Penicillium digitatum, P.italicum), and brown rot (Phytophthora parasitica, Phytophthora citrophthora) .

Diseases of apple: blossom blight (Monilinia mali), canker (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), Alternaria leaf spot (Alternaria alternata apple pathotype) , scab (Venturia inaequalis) , powdery mildew, bitter rot (Colletotrichum acutatum), crown rot (Phytophtora cactorum), blotch (Diplocarpon mali) , and ring rot (Botryosphaeria berengeriana) .

Diseases of pear: scab (Venturia nashicola, V. pirina), powdery mildew, black spot (Alternaria alternata Japanese pear pathotype) , rust (Gymnosporangium 3h, haraeanum) , and phytophthora fruit rot (Phytophtora cactorum).

Diseases of peach: brown rot (Monilinia fructicola), powdery mildew, scab (Cladosporium carpophilum), and phomopsis rot (Phomopsis sp.).

Diseases of grape: anthracnose (Elsinoe ampelina), ripe rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), botrytis, and downy mildew (Plasmopara viticola) .

Diseases of Japanese persimmon: anthracnose (Gloeosporium kaki), and leaf spot (Cercospora kaki, Mycosphaerella nawae) .

Diseases of gourd: anthracnose (Colletotrichum lagenarium) , powdery mildew (Sphaerotheca fuliginea), gummy stem blight (Mycosphaerella melonis), Fusarium wilt (Fusarium oxysporum) , downy mildew (Pseudoperonospora cubensis) tA Phytophthora rot (Phytophthora sp.) , and damping-off (Pythium sp .).

Diseases of tomato: early blight (Alternaria solani) , leaf mold (Cladosporium fulvum) , and late blight (Phytophthora infestans) .

Diseases of eggplant: brown spot (Phomopsis vexans) , and powdery mildew 3 (Erysiphe cichoracearum) Diseases of cruciferous vegetables: Alternaria leaf spot (Alternaria japonica) , white spot (Cercosporella brassicae) , clubroot (Plasmodiophora brassicae) , and downy mildew (Peronospora parasitica) .

Diseases of onion: rust (Puccinia allii), and downy mildew (Peronospora destructor).

Diseases of soybean: purple seed stain (Cercospora kikuchii) , sphaceloma scad (Elsinoe glycines) , pod and stem blight (Diaporthe phaseolorum var. sojae) , septoria brown spot (Septoria glycines), frogeye leaf spot (Cercospora sojina), rust (Phakopsora pachyrhizi) , Yellow rust, brown stem rot (Phytophthora sojae), and - Rhizoctonia damping-off (Rhizoctonia solani) .

Diseases of kidney bean: anthracnose (Colletotrichum lindemthianum). Diseases of peanut: leaf spot (Cercospora personata), brown leaf spot (Cercospora arachidicola) and southern blight (Sclerotium rolfsii).

Diseases of garden pea: powdery mildew (Erysiphe pisi) , and root rot (Fusarium solani f. sp. pisi) .

Diseases of potato: early blight (Alternaria solani), late blight (Phytophthora tA infestans), pink rot (Phytophthora erythroseptica), and powdery scab (Spongospora subterranean f. sp. subterranea).

Diseases of strawberry: powdery mildew (Sphaerotheca humuli), and anthracnose (Glomerella cingulata).

Diseases of tea: net blister blight (Exobasidium reticulatum), white scab (Elsinoe 3 leucospila), gray blight (Pestalotiopsis sp.), and anthracnose (Colletotrichumtheae sinensis) .
Diseases of tobacco: brown spot (Alternaria longipes) , powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew 4h, (Peronospora tabacina) , and black shank (Phytophthora nicotianae).

Diseases of rapeseed: sclerotinia rot (Sclerotinia sclerotiorum) , and Rhizoctonia damping-off (Rhizoctonia solani) . Diseases of cotton: Rhizoctonia damping-off (Rhizoctonia solani) .

Diseases of sugar beat: Cercospora leaf spot (Cercospora beticola) , leaf blight (Thanatephorus cucumeris), Root rot (Thanatephorus cucumeris), and Aphanomyces root rot (Aphanomyces cochlioides) .

Diseases of rose: black spot (Diplocarpon rosae) , powdery mildew (Sphaerotheca pannosa) , and downy mildew (Peronospora sparsa) . Diseases of chrysanthemum and asteraceous plants: downy mildew (Bremia lactucae), leaf blight (Septoria chrysanthemi-indici) , and white rust (Puccinia horiana).

A Diseases of various groups: diseases caused by Pythium spp. (Pythium aphanidermatum, Pythium debarianum, Pythium graminicola, Pythium irregulare, Pythium ultimum), gray mold. (Botrytis cinerea), and Sclerotinia rot (Sclerotinia sclerotiorum).

Disease of Japanese radish: Alternaria leaf spot(Alternaria brassicicola).

Diseases of turfgrass: dollar spot (Sclerotinia homeocarpa), and brown patch and large patch (Rhizoctonia solani).

Disease of banana: Black sigatoka (Mycosphaerella fijiensis), Yellow sigatoka 4h, (Mycosphaerella musicola).

Disease of sunflower: downy mildew (Plasmopara halstedii) .

Seed diseases or diseases in the early stages of the growth of various plants caused - by Aspergillus spp., Penicillium spp., Fusarium spp., Gibberella spp., Tricoderma spp., Thielaviopsis spp., Rhizopus spp., Mucor spp., Corticium spp., Phoma spp., Rhizoctonia spp. and Diplodia spp.

Viral diseases of various plants mediated by Polymixa spp. or Olpidium spp. and so on.

In an embodiment the solid formulation comprising a combination of mancozeb and carbendazim in a synergistic ratio is provided for controlling disease in rice preferably Blast (Pyricularia Oryzae), Helminthosporium leaf spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani) , and bakanae disease (Gibberella fujikuroi).

In an embodiment the solid formulation of the present invention is provided for controlling plant diseases selected from Blast (Pyricularia Oryzae) and sheath blight (Rhizoctonia solani).

In another embodiment the solid formulation of the present invention is provided for controlling Blast (Pyricularia Oryzae).

In another embodiment the solid formulation of the present invention is provided for controlling sheath blight (Rhizoctonia solani).

The compositions of the present invention can be used in agricultural lands such as fields, paddy fields, lawns and orchards or in non-agricultural lands. The present invention may be used to control diseases in agricultural lands for cultivating the plants without any phytotoxicity to the plant.

Examples of the crops on which the present compositions can be used include but are not limited to corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, etc.; vegetables: solanaceous vegetables such as eggplant, tomato, pimento, pepper, A potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, 4h, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, Swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc, strawberry, sweet potato, Dioscorea japonica, colocasia, etc., flowers, foliage plants, turf grasses, fruits: pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, - nectarine, Prunus mume, cherry fruit, apricot, prune, etc., citrus fruits such as orange, lemon, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, cashew nuts, macadamia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., grape, kaki fruit, olive, plum, banana, coffee, date palm, coconuts, etc., trees other than fruit trees; tea, mulberry, flowering plant, trees such as ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidate, etc.

In most preferred embodiment, the present invention relates to a solid formulation meant for direct use comprising Carbendazim and Mancozeb that enables not only a simultaneous reduction of fungal diseases in the crop plant, grain, fruits and vegetable field and but also enhancing the crop yield.

In an embodiment, the composition further comprises filler selected from a group consisting of silica, kaoline, and clay.

In an embodiment, the composition further comprises stabilizing dye for example Stabmet XE Blue (SXB), a stabilized copper phthalocyanine pigment.

The compositions of the present invention further comprise an agriculturally acceptable excipient or adjuvants. These adjuvants may be organic or inorganic material which may be combined with the active ingredients so as to facilitate better spreadability as well as enable better contact with the target fungi. These carriers are agriculturally acceptable and environmentally friendly. Adjuvants may include such dispersing agents, antifoaming agents, pH modifiers, surfactants, stabilizers and other fillers which may be added into a composition.

The composition content of these adjuvants is not particularly limiting and may be determined by a skilled technician in the art according to the conventional protocols.

In one embodiment, the composition may contain ionic and nonionic dispersing agents to enable disintegration of granules in water with ease, such as salts of polystyrene sulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid/formaldehyde condensates, salts of condensates of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid, polyethylene oxide/polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, furthermore polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone and copolymers of (meth)acrylic acid and (meth)acrylic esters, furthermore alkyl ethoxylates and alkylarylethoxylates. The preferred dispersing agents include sodium naphthalene sulfonate-formaldehyde condensate, alkyl naphthalene sulfonate or a combination thereof. The dispersing agent is present in an amount of 2-20% w/w.

In an embodiment, the compositions of the present invention comprise at least one wetting agent selected from soaps; salts of aliphatic monoesters of sulphuric acid including but not limited to sodium lauryl sulphate; sulfoalkylamides and salts thereof including but not limited to N-methyl-N-oleoyltaurate Na salt; alkylarylsulfonates including but not limited to alkylbenzenesulfonates; alkylnaphthalenesulfonates and salts thereof and salts of ligninsulfonic acid. In an embodiment, the wetting agent includes a blend comprising an alkali metal salt of alkylnaphthalenesulfonate or an alkali metal salt of ligninsulfonic acid or a combination thereof. The wetting agent is present in an amount of 0.1 to 10% w/w.

In a preferred embodiment, the composition of the present invention comprises a wetting component comprising a wetting blend selected from an alkali metal salt of alkylnaphthalenesulfonate or an alkali metal salt of ligninsulfonic acid or a combination thereof.

In an embodiment, the compositions of the present invention comprise at least one pH modifier selected from organic and inorganic components that are usually employed in agrochemical compositions to modify the pH. In a non-limiting embodiment, the pH modifier may be selected from potassium carbonate, potassium hydroxide, sodium hydroxide and sodium dihydrogen phosphate. However, the choice of a pH modifier is not particularly limiting. The pH modifier is present in an amount of 0.1-2.0% w/w.

In an embodiment, the compositions of the present invention comprise at least one further surfactant selected from salts of polystyrenesulphonic acids; salts of polyvinylsulphonic acids; salts of naphthalenesulphonic acid/formaldehyde condensates; salts of condensates of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde; salts of lignosulphonic acid such as sodium lignosulphonate; polyethylene oxide/polypropylene oxide block copolymers; polyethylene glycol ethers of linear alcohols; reaction products of fatty acids with ethylene oxide and/or propylene oxide; polyvinyl alcohol; polyvinylpyrrolidone; copolymers of polyvinyl alcohol and polyvinylpyrrolidone; copolymers of (meth)acrylic acid and (meth)acrylic esters; and alkyl ethoxylates and alkylarylethoxylates. . The surfactant is present in an amount of 0.1 to 25% w/w.

In another aspect the present invention provides a process for preparation of synergistic composition of present invention.

The process comprises the steps of : 1) Mixing all the ingredients in required quantity in a blender to have Pre-blended mixture in the form of homogenous powder; 2) Micronize/grind the preblended mixture through a suitable micronizer. This micronized material is later post-mixed to have homogenous powder; 3) Admixing water, with the post- mixed mixture, to obtain the homogenous wet dough; 4) granulating the dough to obtain granules and 5) drying and sieving the granules through desired sieves and 6) packing the dried granules.

The formulation described above is a fungicidally efficacious and stable formulation.

In an embodiment, the combination product of “Carbendazim, Mancozeb” is found effective in controlling the fungal diseases in paddy, wheat, black gram, chilli, and tomato. The commonly observed fungal diseases in these crops are sheath blight, sheath rot, brown spot of rice, blast of rice, root rot, leaf rust, stem rust, alternarial leaf blight, cercospora leaf spot, powdery mildew, corynespora leaf spot, rust, anthracnose, cercospora leaf spot, alternaria leaf spot, die back of chilli, anthracnose, powdery mildew, septoria leaf blight, anthracnose, early blight, late blight, fusarium wilt which are successfully controlled by the combination product of “Carbendazim, Mancozeb”. The invention disclosed in this specification is not limited to these crops and diseases but can also extended to the crops or diseases known to the person skilled in the art.

In another aspect the present invention provides a method for controlling fungi at a locus, said method comprising treating the locus with a composition comprising fungicidally effective amount of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide, wherein said composition is a solid formulation meant for direct use.

In an embodiment, the present invention provides a method for controlling fungi at a locus, said method comprising treating the locus with a composition comprising fungicidally effective amount of mancozeb and carbendazim in a solid formulation meant for direct use .

In another aspect the present invention provides a kit comprising a fungicide composition comprising of a dithiocarbamate fungicide and a benzimidazole fungicide or a benzimidazolylcarbamate fungicide, wherein the kit comprises at least one component comprising these fungicides as a solid formulation meant for direct use.

In an embodiment, the present invention provides a kit comprising a fungicide composition containing mancozeb and carbendazim in a synergistic amount wherein said composition is formulated as a solid formulation meant for direct use.

However, it should be understood that the scope of the present invention is not limited by the examples in any manner. It will be appreciated by any person skilled in this art that the present invention includes aforesaid examples and further can be modified and - altered within the technical scope of the present invention.

While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, its combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention.

The invention will be illustrated with reference to the following examples.

EXAMPLES
Example 1
Preparation of synergistic combination of Mancozeb and carbendazim

Ingredients Amount (%)
Mancozeb 10.08
Carbendazim 1.92
clay 8.00
Kaolin QS
100.00

Process of manufacture of Granular formulation:
The process involves following steps:
1) Mixing :
All the ingredients were mixed in required quantity in a blender to have Pre-blended mixture in the form of homogenous powder.
2) Micronizing and post mixing : -
The preblended mixture was micronize/grinded through a suitable micronizer. This micronized material was later post-mixed to have homogenous powder.
3) Dough preparation/Wet mixing: -
Water was admixed with the post- mixed mixture (obtained in step 2 above), to obtain the homogenous wet dough.
4) Granulation/Extrusion: -
The dough obtained in step 3 was granulated to obtain the granules.
5) Drying :
The granules obtained in step 5 were dried such that the moisture content in the dried granules should be below 3.0 % by mass.
6) Sieving:
The granules obtained in step 5 were sieved through desired sieves and packed in desired pack.

Example 2
Field trials:

Treatment with composition of present invention was given to crops in different season and evaluated the disease control.

Percentage of disease control with the composition of the present invention was calculated using Colby equation.

The following equation was used to calculate the expected activity of mixtures containing two active ingredients, for example A and B:
Expected=A+B-(A×B/100)

A=observed efficacy of active component A at the same concentration as used in the mixture;
B=observed efficacy of active component B at the same concentration as used in the mixture.

Treatments evaluated, application rate employed, pathogens evaluated and resulting disease control are presented in the following Tables 1-5.

Table 1
Sr. No. Ingredient Dose Method of application
Active ingredient (g a.i./ha) Product
(kg or L/ha)
1. Carbendazim + Mancozeb (GR) 240+1260 12.5 Broadcasting
2. Carbendazim + Mancozeb (GR) 288+1512 15.0 Broadcasting
3. Mancozeb 75% (WP) 1500 2.0 Spray (500L/ha)
4. Carbendazim 50% (WP) 250 0.5 Spray (750L/ha)
5. Carbendazim 12% +Mancozeb 63% (WP) 563 0.75 Spray (750L/ha)
6. Untreated/control - - -

The comparative formulation was a solid formulation meant for dispersion/dissolution prior to being sprayed, according to the FAO definition of such solid formulations. Such a formulation is typically available commercially as a wettable powder (WP), which was used as a comparative formulation.

Table 2- Season I
Disease - Paddy Blast
Treatment Formulation dose (Kg or L/ha) Percentage Control (Observed) Expected Percentage Control calculated by Colby’s formula Difference between observed and expected Control; Conclusion
Mancozeb 75% WP 2.0 33.33 - -
Canbendazim 50% WP 0.5 54.91 - -
Carbendazim 12% + Mancozeb 63% WP 0.75 69.18 - -
Colby’s formula calculation: 69.93 + 0.75; Additive
Carbendazim + Mancozeb (GR) 12.5 72.24 - -
Colby’s formula calculation: 69.93 +2.31; Synergistic
Carbendazim + Mancozeb (GR) 15.0 73.60
Colby’s formula calculation: 69.93 +3.67; Synergistic
Paddy Sheath Blight
Mancozeb 75% WP 2.0 21.31 - -
Canbendazim 50% WP 0.5 37.00 - -
Carbendazim + Mancozeb (GR) 12.5 72.24 50.43 + 21.81; Synergistic
Carbendazim + Mancozeb (GR) 15.0 73.60 50.43 + 23.17; Synergistic

The formulation comprising Carbendazim + Mancozeb (GR) was a composition according to the present invention i.e. a solid formulation meant for direct use. In this embodiment, the formulation was a granular formulation (GR).

In an embodiment, the minimum dosage of above present formulation was maintained at greater than at least 10.0 kg/ha.

Table 3- Season II
Disease- Sheath Blight
Treatment Formulation dose (Kg or L/ha) Percentage Control (Observed) Percentage control Expected calculated by Colby’s formula Difference between observed and expected Control; Conclusion
Mancozeb 75% WP 2.0 27.80 - -
Canbendazim 50% WP 0.5 36.82 - -
Carbendazim 12% + Mancozeb 63% WP 0.75 52.39 - -
Colby’s formula calculation: 54.38 - 1.99; Not synergistic
Carbendazim + Mancozeb (GR) 12.5 64.58 - -
Colby’s formula calculation: 54.38 +10.20; Synergistic
Carbendazim + Mancozeb (GR) 15.0 66.59
Colby’s formula calculation: 54.38 +12.21; Synergistic

In furtherance to the results in above trials, a separate trial was conducted to evaluate the efficacy of a WP formulation comprising these fungicides to reconfirm the merely additive/antagonistic activity of the comparative WP formulation.

Table 4- Season III (Comparative)

Disease - Paddy Sheath Blight
Treatment Formulation dose (Kg or L/ha) Percentage Control (Observed) Percentage Control Expected calculated by Colby’s formula Difference between observed and expected Control; Conclusion
Mancozeb 75% WP 2.0 45.12 - -
Canbendazim 50% WP 0.5 58.80 - -
Carbendazim 12% + Mancozeb 63% WP 0.75 76.87 - -
Colby’s formula calculation: 90.47 - 13.6; Not synergistic

A confirmatory trial was then conducted to reconfirm the unexpected synergy seen with the solid formulation meant for direct use (GR) vis-à-vis the activity of a solid formulation meant for dissolution/dispersion (WP) above. The objective of the present invention was to reassess the findings of the above described trials.

Table 5- Season IV
Disease - Paddy Blast
Treatment Formulation dose (Kg or L/ha) Percentage Control (Observed) Percentage Control Expected calculated by Colby’s formula Difference between observed and expected Control; Conclusion
Mancozeb 75% WP 2.0 19.66 - -
Canbendazim 50% WP 0.5 36.61 - -
Colby’s formula calculation: 49.07 -
Carbendazim + Mancozeb (GR) 12.5 58.94 - + 9.97; Synergistic
Carbendazim + Mancozeb (GR) 15.0 62.02 - + 12.95; Synergistic

It was thus found that the fungicides mancozeb and carbendazim interacted synergistically when presented as a solid formulation meant for direct use, whereas they were merely additive or antagonistic when presented as a solid formulation meant for dispersion/dissolution.