DESC:FIELD OF THE INVENTION
[001] The present disclosure relates to a synergistic fungicidal composition and a process for preparation thereof.

BACKGROUND OF THE INVENTION
[002] Enhancement of agricultural products requires the protection of the crops and its produce from pest damage. Various chemicals and their formulations have been developed and are in use currently for the effective management of fungi. Due to the excessive use of fungicides, the pests/fungi gain resistance and become hard to kill. Physically compatible pesticide mixtures exhibit better pest management. These mixtures show multifaceted advantages than when applied individually and provide a synergistic effect. Various fungicidal compositions have been developed to control various fungi/pests. However, fungicides that are safer, that have excellent performance, lower dosages, easier to use, are economical and ecologically safe resulting in enhanced activity, are still being sought.

[003] Multiple fungicide chemistry has been used to control wider variety of undesirable fungal diseases. However, no one particular fungicide is useful in all situations and repeated usage of a single fungicide frequently leads to the development of resistance to the fungicides. Accordingly, research is being performed to produce fungicides and combinations of fungicides that are safer, that have excellent performance, that having lower dosages, that are easier to use, and that cost less. Combinations are also being studied that produce synergism, i.e., the activity of two, or more, compounds exceeds the activities of the compounds when used alone.

[004] However, it is challenging to develop stable formulations comprising active content of two or more active ingredients and maintaining the stability of the formulation after long periods of storage. Mixtures of fungicides can provide significantly better disease control than would be expected based on the activity of the individual components. This synergy has been described as “cooperative action of two components of the mixture such that the overall effect is greater or longer than the sum of the two (or more) effects used independently” (PML Tames, Neth. J. Plant Pathology 1964, 70, 73-80).

[005] Therefore, there is required a stable fungicidal composition combining more than one active ingredient that has a synergistic effect and thereby reduce the need for multiple individual applications while providing better fungicidal activity.

[006] In view of this, there is a need to develop novel combination products having synergistic effect which can be extensively applied in the field of agriculture for controlling wide spectra of fungi and which also exhibits good physical and chemical stability.
SUMMARY OF THE INVENTION
[007] In one aspect, the present invention provides a synergistic fungicidal composition comprising:
a) at least one multi-site contact fungicide,
b) at least one quinone outside inhibitors (QOI) fungicide,
c) at least one phenylamide fungicide; and
d) at least one agrochemically acceptable excipient.

[008] In another aspect, the present invention provides a method for controlling fungi comprising the steps of applying the synergistic fungicidal composition to the fungi and/or their habitat.

[009] In still another aspect, the present invention provides for the use of the synergistic fungicidal composition for controlling fungi.

DETAILED DESCRIPTION OF THE INVENTION
[010] The present invention is directed towards a fungicidal composition and a process for preparation thereof. Further, use of this synergistic composition reduces the number of applications of various individual fertilizers components thus providing a cost-effective solution and overcomes the pesticidal/insecticidal resistance created for the individual component.

[011] In one aspect of the present invention, the synergistic fungicidal composition comprises:
a) at least one multi-site contact fungicide,
b) at least one quinone outside inhibitors (QOI) fungicide,
c) at least one phenylamide fungicide, and
d) at least one agrochemically acceptable excipient.

[012] In an embodiment of the invention, the multi-site contact fungicides inhibit fungal growth through multiple sites of action and have contact and preventive activity. Suitable multi-site contact fungicides can be selected from, such as but not limited to, inorganic fungicide, dithiocarbamate fungicide, phthalimide fungicide, chloronitrile fungicide, sulfamide fungicide, bis-guanidine fungicide, quinone and anthra-quinone fungicide, quinoxaline fungicide, maleimide fungicide, and thiocarbamate fungicide. The multi-site contact fungicide can be a mixture of the fungicides described in the list hereinabove.

[013] Suitable inorganic fungicides can be selected from copper fungicides including copper (II) hydroxide, copper oxychloride, copper (II) sulfate, basic copper sulfate, Bordeaux mixture, copper salicylate, cuprous oxide; or sulphur. Suitable dithiocarbamate fungicides can be selected from amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, manam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet, etem, milneb, mancopper, mancozeb, maneb, metiram, propineb, polycarbamate, zinc thiazole, zineb, and ziram. Suitable phthalimide fungicides contain a phthalimide molecular moiety and can be selected from captan, captafol, and folpet. Suitable chloronitrile fungicides comprise an aromatic ring substituted with chloro- and cyano-substituents, for example chlorothalonil. Suitable sulfamide fungicides can be selected from dichlofluanid, and tolylfluanid. Suitable bis-guanidine fungicides can be selected from guazatine, and iminoctadine. Suitable quinone fungicide is dithianon and anthra-quinone fungicide is anilazine. Suitable quinoxaline fungicide is chinomethionat, also known as quinomethionate. Suitable maleimide fungicide is fluoroimide. Suitable thiocarbamate fungicide is methasulfocarb.

[014] In an embodiment, the multi-site contact fungicide is present in an amount in between 1 wt.% to 90 wt.% based on the total weight of the synergistic fungicidal composition. In an embodiment, the multi-site contact fungicide is present in an amount in between 10 wt.% to 70 wt.% based on the total weight of the synergistic fungicidal composition.

[015] In another embodiment of the invention, the quinone outside inhibitors (QOI) fungicide can be selected from, such as but not limited to, strobilurins, methoxy- acrylates, methoxy-acetamide, methoxy carbamates, oximino-acetates, oximino- acetamides, oxazolidine-diones, dihydro-dioxazines, imidazolinones, and benzyl-carbamates.

[016] Suitable QOI fungicides can be selected from azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, famoxadone, fluoxastrobin, fenamidone, and pyribencarb.

[017] In an embodiment, the QOI fungicide is present in an amount in between 0.1 wt.% to 70 wt.% based on the total weight of the synergistic fungicidal composition. In an embodiment, the QOI fungicide is present in an amount in between 0.1 wt.% to 50 wt.% based on the total weight of the synergistic fungicidal composition.

[018] In yet another embodiment of the invention, the phenylamide fungicide in the present disclosure can be selected from, such as but not limited to, acylalanines, oxazolidinones, butyrolactones, hydroxy- (2-amino-) pyrimidines, isoxazoles, and carboxylic acids.

[019] Suitable acylalanines can be selected from benalaxyl, benalaxyl-M (or kiralaxyl), furalaxyl, metalaxyl, and metalaxyl-M (or mefenoxam), pefurazoate, valifenalate.
Suitable oxazolidinone includes oxadixyl.
Suitable butyrolactone includes ofurace.
Suitable hydroxy-(2-amino-) pyrimidines can be selected from bupirimate, dimethirimol, and ethirimol.
Suitable isoxazoles include isothiazolones.
Suitable carboxylic acids include oxolinic acid.
[020] In an embodiment, the phenylamide fungicide is present in an amount in between 0.1 wt.% to 70 wt.% based on the total weight of the synergistic fungicidal composition. In an embodiment, the phenylamide fungicide is present in an amount in between 0.1 wt.% to 50 wt.% based on the total weight of the synergistic fungicidal composition.

[021] Suitable agrochemically acceptable excipients can be selected from, such as but not limited to, wetting agents, dispersing agents, surfactants, binders, adjuvants, vegetable oils, fillers and/or diluents, polysaccharide polymeric materials, defoamers, stabilisers, thickening agents, preservatives, and antifreeze agents. The agrochemically acceptable excipients, as described herein, can be used alone or in combination.

[022] In an embodiment of the present invention the wetting agent is selected from the group consisting of N - methyl - N – oleyl taurate Na salt, akylarylsulfonates, akylbenzene sulfonates, akylnaphthalene sulfonates and salts thereof and salts of ligninsulfonic acid, aryl sulfonates (such as sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate), fatty alcohol sulfates salts of aliphatic monoesters of sulphuric acid including sodium lauryl sulphate, sulfoakylamides and salts thereof , alkyl sulfates, alkyl polyoxyethylene alcohol ether sulfate, polyoxyethylene alkyl phenol ether sulfate, polyoxyethylene alkyl phenol ether formaldehyde condensate sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates succinic, single polyoxyethylene alkylphenyl ether sodium succinate, ethylene oxide adducts of fatty alcohol sulfonates and alkylphenol formalin condensates of ethylene oxide adduct sulfonates.

[023] In an embodiment of the present invention dispersing agent is selected from the group consisting of graft co-polymer base dispersing agent, phenol polyoxyethylene aryl sulfonate succinate, EO/PO block copolymers, polyoxyethylene octyl phenol ether sulfates, polycarboxylates, lignin sulfonates, alkaline earth metal and ammonium salts of aromatic sulfonic acids, alkyl naphthalene sulfonate, bis (alkyl) naphthalene sulfonate formaldehyde condensates, naphthalene sulfonic acid formaldehyde condensates, such as lignin sulfonic acid polyoxyethylene alkyl phenol formaldehyde condensate ethyl sulfates, alkylbenzene calcium sulfonate, naphthalene sulfonate formaldehyde condensates sodium salts, polyoxyethylene alkylphenol ethyl, ethyl polyoxyethylene fatty amine, polyoxyethylene fatty acid esters, Lignosulfonic acid, sodium salt, sulfomethylated and polyoxyethylene esters of ethylene-ethyl.

[024] In an embodiment of the present invention the anti-freeze agent can be selected from the group comprising of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, polyethylene glycol.

[025] In an embodiment of the present invention the defoamers can be selected from the group comprising of polydimethylsiloxane powder and polydimethylsiloxane liquid, Silicon base antifoam.

[026] In an embodiment of the present invention the preservatives can be isothiazolinone, isothiazolinone mixture, methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone or combination thereof.

[027] In an embodiment of the present invention the thickening agent can be selected from the group comprising of Xanthan gum, carboxy methyl cellulose, Hydroxymethyl propyl cellulose, Hydroxy ethyl cellulose.

[028] In an embodiment of the present invention the stabilizer can be selected from the group comprising of phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid mono- and di-ester mixture, sodium phosphates, Hexamethylene tetramine, sodium metabisulfite, butylated hydroxytoluene, castor oil ethoxylate, ethoxylated hydrogenated castor oil, vegetable oil and epoxidized soyabean oil or combinations thereof.

[029] In an embodiment of the present invention the surfactant can be selected from the group comprising of group comprising of nonionic, anionic surfactant or combination of both.

[030] In an embodiment of the present invention the water is used as a diluent to dilute the active ingredient to a desired concentration. The water used is purified water and selected from the group consisting of deionized water and distilled water.

[031] In an embodiment, the agrochemically acceptable excipients are present in an amount in between 0.1 wt.% to 90 wt.% based on the total weight of the synergistic fungicidal composition.

[032] In an embodiment, the agrochemically acceptable excipients are present in an amount in between 0.1 wt.% to 70 wt.% based on the total weight of the synergistic fungicidal composition.

[033] In an embodiment of the present invention, the synergistic fungicidal composition comprises:
e) at least one multi-site contact fungicide in an amount between 1 wt.% to 90 wt.% based on the total weight of the synergistic fungicidal composition,
f) at least one quinone outside inhibitors (QOI) fungicide is present in an amount in between 0.1 wt.% to 70 wt.% based on the total weight of the synergistic fungicidal composition,
g) at least one phenylamide fungicide is present in an amount in between 0.1 wt.% to 70 wt.% based on the total weight of the synergistic fungicidal composition, and
h) at least one agrochemically acceptable excipient.

[034] In an embodiment, each of the multi-site contact fungicide, QOI fungicide, and phenylamide fungicide are stable agrochemical liquid formulation.

[035] In an embodiment, each of the multi-site contact fungicide, QOI fungicide, and phenylamide fungicide are stable agrochemical liquid formulation including but not limited to soluble (liquid) concentrates, suspension concentrates, oil in water emulsion, water in oil emulsion, emulsifiable concentrates, capsule suspensions, ZC formulations, oil dispersions or other known formulation types.

[036] In an embodiment, each of the multi-site contact fungicide, QOI fungicide, and phenylamide fungicide are stable solid formulation including but not limited to wettable powders, water dispersible granule, granules, dusts.

[037] In another embodiment, the synergistic fungicidal composition of the present disclosure comprises the abovementioned ingredients (a), (b), (c), and (d) in synergistic amounts.

[038] Another aspect of the present disclosure relates to a process for preparing the synergistic fungicidal composition, as described hereinabove.

[039] In an embodiment, the process comprises at least the following steps:
a) wet milling a first phase comprising water, dispersing agents, wetting agents, adjuvants, defoaming agent, and QOI fungicide, to obtain particles ranging between 1 to 5 micron,
b) preparing a second phase comprising vegetable oil and phenylamide fungicides,
c) mixing the first phase of step (A) and the second phase of step (B) to obtain an oil-in-water suspension, and
d) mixing the oil-in-water suspension of step (C) with the multi-site contact fungicides, defoaming agent, thickening agents, and preservatives to obtain the synergistic fungicidal composition.
[040] In yet another embodiment, the present invention relates to a method for controlling fungi comprising the steps of applying the synergistic fungicidal composition to the fungi and/or their habitat.

[041] Effective application rates of the present composition cannot generally be defined, as it varies depending upon various conditions such as the type of pesticide, target pest, weather conditions, nature of the soil, and the type of crop. The application rates can be varied within a relatively wide range, depending on the kind of application.

[042] In an embodiment of the present invention, the fungicidal composition may be used for foliar application, ground application or application to plant propagation materials. These application rates are merely by way of example and are not limiting for the purposes of the invention.

[043] In yet another embodiment, the methods of the present invention may be applied to any crop plants, including but not limited to tomato, potato, soybean, fruit crops such as grapes, mango, pomegranate, cereals rice, wheat maize and Pulses Blackgram, Green gram, beans.

[044] In another embodiment, of the present invention can be used in the agricultural sector and related fields of use for preventing and/or treating diseases caused by fungal pathogens for example, but not limited to the phytopathogenic fungi are one or more of the classes including to Lateblight, Alternaria, Anthracnose, Pythium seedlig blights, Phaeosphaeria maydis, Septoria, damping-off, soybean rust, target spot, Cereal smuts, Common smut, cercospora leaf spot and blight, rhizoctonia aerial, foliage, and web blight, phytophthora rot.

[045] The present invention compositions herein may be applied to a desired locus by any methods include coating, spraying, dipping, soaking, injection and irrigation. The means such as airplane spray tanks, knapsack spray tanks, cattle dipping vats, farm equipment used in ground spraying (e.g., boom sprayers, hand sprayers), and the like. The desired locus may be soil, plants, and the like.

[046] Another embodiment of the present invention relates to the use of the synergistic fungicidal composition for controlling fungi.

[047] The synergistic fungicidal composition when used in the above described combination exhibit fungicidal activity that exceeds the sum of the fungicidal activities of the individual components when used alone. Further, the synergistic fungicidal composition is capable of preventing or curing, or both of diseases caused by fungi and improve the quality and quantity of yield. The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one agrochemically acceptable excipients can be selected from, such as but not limited to, wetting agents, dispersing agents, surfactants, binders, adjuvants, vegetable oils, fillers and/or diluents, polysaccharide polymeric materials, defoamers, stabilisers, thickening agents, preservatives, and antifreeze agents. Depending on the formulation type to be prepared further processing steps are necessary, e.g. wet grinding, dry grinding and granulation.

EXAMPLE
[048] The following example is illustrative of the invention but not limitative of the scope thereof:
Example 1: Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl -M 1.4% w/w
Ingredients Amount (gms)
Mancozeb tech (dithioccarbamate) 110.61
Azoxystrobin tech (QOI) 4.4
Metalaxyl -M tech (acylalanines) 4.7
Acrylic copolymer surfactant (Dispersing agent 1) 3
Oleic acid methyl tauride, sodium salt (Dispersing agent 2) 0.3
Vegetable oil (Ant freezing agent) 9
Polysaccharide (Thickening agent) 0.4
antifoam emulsion (Defoamer) 0.3
Hexamethylene tetramine (stabilizer) 0.1
Water QS (Filler) 0.5

Example 2: Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w
Ingredients Amount (gms)
Mancozeb tech (dithioccarbamate) 83.00
Azoxystrobin Tech (QOI) 3.80
Metalaxyl -M (acylalanines) 4.10
Acrylic copolymer surfactant (Dispersing agent 1) 3
Sodium Methyl Oleoyl Taurate (Wetting agent) 0.3
Vegetable oil (Ant freezing agent) 9
Polysaccharide (Thickening agent) 0.87
antifoam emulsion (Defoamer) 0.3
benzisothiazolin-3-one (Preservative) 0.1
Hexamethylene tetramine (stabilizer) 0.5
Water QS (Filler) 195.03

Bio-efficacy for Inventive examples 1 and 2
The synergistic fungicidal compositions of the present invention, prepared in accordance with Examples 1 and 2, were tested to study the efficacy of three way combination of fungicide (Mancozeb, Azoxystrobin and Metalaxyl-M) against Early blight, Late blight and Anthracnose diseases of Tomato. The study was conducted to test the comparative efficacy of the inventive fungicides with market standards- Azoxystrobin 25% SC, Mancozeb 75%WP and Metalaxyl-M 25% WP and their two way possible tank mix combinations against Early blight, Late blight and Anthracnose diseases of Tomato. The fungicides were applied as foliar spray with Knapsack Sprayer fitted with solid cone nozzle. Application was initiated with initiation of disease in the field. The sprayings were done at 15 days interval.
The appearance of the visible symptom of the diseases was recorded before 1st spray and subsequent observations were recorded after each spray. Phyto-toxicity was determined - 0, 1, 3, 5, 7, 10 & 15 days after application.

Disease Ratings:
EARLY BLIGHT & LEAF SPOTS:
Take observation on percent disease severity/ PDI on 10 plants tagged plants per plot at Pre-treatment and 3, 5, 7 and 10 days after each application by adopting 0-5 scale. Where,
0 - Leaves free from infection
1 - Small irregular spots covering <5% leaf area
2 - Small irregular brown spots with concentric rings covering 5.1-10% leaf area
3 - Lesions enlarging, irregular brown with concentric rings covering 10.1-25% leaf area
4 - Lesions coalease to form irregular and appears as a typical blight symptom covering 25.1-50% leaf area
5 - Lesions coalesce to form irregular and appears as a typical blight symptom covering >50% leaf area
LATE BLIGHT:
Scale (Grade) Percent disease Intensity reaction
0 No disease = Immune
1 1 – 5 % infection = Mild
3 6 – 10 % infection = Moderate
5 11 – 25 % infection = Alarming
7 26 – 50 % infection = Severe
9 >50 % infection = highly severe

Percent disease index (PDI) was calculated using the following formula:
Sum of all numerical ratings
PDI = --------------------------------------------------------------------- X 100
Total plants observed X Maximum rating scale

The PDI values were transformed by angular transformation and analyzed statistically. The disease control DC (%) was calculated by the following formula.

Disease % in control - Disease % in treatment
DC (%) = ------------------------------------------------------------- X 100
Disease % in control
b) Yield:
Individual plot wise yield was recorded and calculated treatment wise yield and converted into yield per hectare (t/ha) at harvest and statistically analyzed the data.
c) Phytotoxicity:
Observations were taken on damage caused to plants, if any, by the application of different treatments taking into the account phytotoxic symptoms viz. leaf injury on tips and leaf surface, wilting, vein clearing, necrosis, epinasty and hyponasty on ten plants per plot. The observations were recorded before spray and 1, 3, 5, 7, 10 & 15th day after applications. For Phytotoxicity study on leaf injury on tips and leaf surface the Scale (0-10) used is given below.

Phytotoxicity Rating Scale (PRS)
Crop response/ Crop injury Rating
0-00 0
1-10% 1
11-20% 2
21-30% 3
31-40% 4
41-50% 5
51-60% 6
61-70% 7
71-80% 8
81-90% 9
91-100% 10

c) Statistical Analysis: Analysis of variance was calculated by using OPSTAT Computer Software Program.

Table 1: Bio-efficacy of different Fungicide treatments against Early Blight of Tomato
Treatment Details Dose (g a.i./ha) Dose /ha 0 DAA 15 DA1S 15 DA2S 15 DA3S
Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w (Example 1) 2200 + 98.56 + 98.56 7040 g 0.00
(0.00) 0.00
(0.00) 2.67
(6.54) 3.34
(7.34)
Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w (Example 2) 1647.3 + 84.48 +84.48 7040 g 0.00
(0.00) 0.00
(0.00) 6.00
(9.89) 10.00 (12.93)
Mancozeb 75%WP 2250 3000 g 0.00
(0.00) 1.34 (3.83) 17.34
(17.10) 26.67
(21.40)
Azoxystrobin 23% SC 125 500 ml 0.00
(0.00) 0.67
(1.92) 15.34
(16.07) 22.67
(19.65)
Metalaxyl-M 25% WP 125 500 g 0.00
(0.00) 2.00
(4.63) 18.00
(17.45) 35.34
(24.86)
Mancozeb 75%WP + Azoxystrobin 23% SC (Tank mix) 2250 + 125 3000 g + 500 ml 0.00
(0.00) 0.00 (0.00) 10.00
(12.93) 17.34
(17.12)
Mancozeb 75%WP + Metalaxyl M 25% WP (Tank mix) 2250 + 125 3000g + 500 g 0.00
(0.00) 1.34
(3.83) 13.34
(14.96) 31.34
(23.32)
Azoxystrobin 23% SC + Metalaxyl M 25% WP (Tank Mix) 125 + 125 500 ml + 500 g 0.00
(0.00) 0.00
(0.00) 13.07
(14.81) 18.67
(17.79)
Untreated - - 0.00
(0.00) 7.34
(11.02) 22.67
(19.65) 42.00
(27.27)
SEm± NS 1.09 0.86 0.56
CD@ 5% NS 3.24 2.55 1.68
Figures in parenthesis are arcsine transformed values.
PDI- Percent Disease Incidence
PDC- Percent Disease Control
DAA- Days After Application
NS- Non significant

(Table 1) The results presented shows that at the time of initiation of trial there was no Early Blight disease in any treatment which indicates the uniformity of trial plot across all the treatments. At 15 days after first application, the highest Early Blight was recorded in control (7.34%). All the fungicide treatments significantly reduced the disease severity than untreated control, but the significant lowest Early Blight disease was observed in T1, T2, T6 & T8(0.00%).
At 15 days after second application, the highest disease was recorded in control (22.67%). The significant lowest Early Blight disease was observed in T1 (2.67%) which was statistically superior over T2 (6.00%) & T1, T2 were superior to rest of other treatments.
At 15 days after third application also similar trend observed as that off second application. Where, the significant lowest Early Blight disease was observed in T1 (3.34%) which was statistically superior over rest of all treatments, T1 followed by T2(10.00%) and these T1 & T2 were superior to all the other treatments.
The highest percent disease control (PDC) was recorded in treatment T1 (3.34%), followed by T2 (10.00%). The lowest disease control was recorded in treatment T10 ie., untreated control (42.00%).

Table 2: Bio-efficacy of different Fungicide treatments against Late blight of Tomato
Treatment Details Dose (g a.i./ha) Dose /ha 0 DAA 15 DA1S 15 DA2S 15 DA3S
Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w (Example 1) 2200 + 98.56 + 98.56 7040 g 0.00
(0.00) 0.00
(0.00) 1.34 (3.83) 3.34 (7.15)
Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w (Example 2) 1647.3 + 84.48 + 84.48 7040 g 0.00
(0.00) 0.00
(0.00) 2.67 (6.54) 5.33
(10.50)
Mancozeb 75%WP 2250 3000 g 0.00
(0.00) 1.34
(3.83) 7.34
(11.02) 17.34 (17.12)
Azoxystrobin 23% SC 125 500 ml 0.00
(0.00) 0.67
(1.92) 8.00 (11.54) 13.34 (14.80)
Metalaxyl-M 25% WP 125 500 g 0.00
(0.00) 2.67 (6.54) 11.34 (13.76) 24.00 (20.24)
Mancozeb 75%WP + Azoxystrobin 23% SC (Tank mix) 2250 + 125 3000 g + 500 ml 0.00
(0.00) 0.00
(0.00) 5.74 (9.75) 12.14 (14.26)
Mancozeb 75%WP + Metalaxyl M 25% WP (Tank mix) 2250 + 125 3000g + 500 g 0.00
(0.00) 0.67
(1.92) 6.67 (10.50) 12.67
(14.57)
Azoxystrobin 23% SC + Metalaxyl M 25% WP (Tank Mix) 125 + 125 500 ml + 500 g 0.00
(0.00) 0.00
(0.00) 5.60 (9.63) 12.00
(14.15)
Untreated - - 0.00
(0.00) 6.67
(10.50) 28.67 (22.24) 42.67
(27.51)
SEm± NS 1.04 1.02 0.73
CD@ 5% NS 3.09 3.05 2.18
(Table 2) The results presented shows that at the time of initiation of trial the Late Blight was not observed when initiated. At 15 days after first application, the highest disease was recorded in control ie., 6.67%. The significant lowest disease was observed in T1 & T2 (0.00%) and T7 & T9 (0.00%), which were at par with all the treatments and superior over untreated control.
At 15 days after second application, there was good disease progression in treatments T4 to T6 and the highest disease was recorded in control (28.67%). The significant lowest disease was observed in T1 (1.34%) which was superior over all the treatments, followed by T2 (2.67%) and these were superior over rest of the treatments.
At 15 days after third application, significant lowest disease was observed in treatment T1 (3.34%) and T1 was statistically superior over all the treatments and T2 (5.33%), which was significantly superior over rest of the treatments. The highest disease was observed in untreated control (42.67%).

Table 3: Bio-efficacy of different Fungicide treatments against Anthracnose of Tomato
Treatment Details Dose (g a.i./ha) Dose /ha 0 DAA 15 DA1S 15 DA2S 15 DA3S
Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w (Example 1) 2200 + 98.56 + 98.56 7040 g 0.00
(0.00) 0.00
(0.00) 0.00
(0.00) 4.67 (8.75)
Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w (Example 2) 1647.3 + 84.48 +84.48 7040 g 0.00
(0.00) 0.00
(0.00) 2.67 (6.54) 6.67 (10.50)
Mancozeb 75%WP 2250 3000 g 0.00
(0.00) 0.00
(0.00) 13.34 (14.96) 22.00
(19.36)
Azoxystrobin 23% SC 125 500 ml 0.00
(0.00) 0.00
(0.00) 9.34 (12.46) 15.34 (16.07)
Metalaxyl-M 25% WP 125 500 g 0.00
(0.00) 0.00
(0.00) 17.74 (17.33) 34.67 (24.60)
Mancozeb 75%WP + Azoxystrobin 23% SC (Tank mix) 2250 + 125 3000 g + 500 ml 0.00
(0.00) 0.00
(0.00) 5.34 (9.36) 9.34
(12.46)
Mancozeb 75%WP + Metalaxyl M 25% WP (Tank mix) 2250 + 125 3000g + 500 g 0.00
(0.00) 0.00
(0.00) 9.34 (12.46) 14.94 (15.85)
Azoxystrobin 23% SC + Metalaxyl M 25% WP (Tank Mix) 125 + 125 500 ml + 500 g 0.00
(0.00) 0.00
(0.00) 7.34
(11.02) 14.67 (15.71)
Untreated - - 0.00
(0.00) 0.00
(0.00) 34.00
(24.34) 43.34 (27.74)
SEm± NS NS 0.94 0.48
CD@ 5% NS NS 2.80 1.46
(Table 3) The results presented shows that at the time of initiation of trial the Anthracnose was not initiated. At 15 days after first application, the disease was not observed in any of the treatments as fruits were small and unripen.
At 15 days after second application, the highest disease was recorded in control (34.00%). The significant lowest disease was observed in T1 (0.00%) and T2 (2.67%) which were superior over individual & two-way combinations.
At 15 days after third application, the significant lowest disease was observed in treatment T1 (4.67%), which was significantly superior over rest of all treatments.
The highest percent disease control (PDC) was recorded in treatment T1 (4.67%) which was followed by T2 (6.67%) and these three-way combinations were superior over rest of the treatments & the next best treatments were T6 (9.34%), T8 (14.67%) in two way tank mix combinations. The lowest disease control was recorded in treatment T9 (43.34%).

Table 4: Effect of different Fungicide treatments on Yield of Tomato
Treatment Dosage (g a.i./ha) Formulation (/ha) Yield (t/ha)
Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w (Example 1) 2200 + 98.56 + 98.56 7040 g 31.13
Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w (Example 2) 1647.3 + 84.48 +84.48 7040 g 29.67
Mancozeb 75%WP 2250 3000 g 25.50
Azoxystrobin 23% SC 125 500 ml 25.87
Metalaxyl-M 25% WP 125 500 g 24.27
Mancozeb 75%WP + Azoxystrobin 23% SC (Tank mix) 2250 + 125 3000 g + 500 ml 27.70
Mancozeb 75%WP + Metalaxyl M 25% WP (Tank mix) 2250 + 125 3000g + 500 g 26.27
Azoxystrobin 23% SC + Metalaxyl M 25% WP (Tank Mix) 125 + 125 500 ml + 500 g 27.13
Untreated - - 20.40
SEm± 0.29
CD@ 5% 0.88
Table 4: All the treatments significantly increase the yield than Untreated Control (20.40 t/ha). The highest yield was observed in treatment T1 (31.13 t/ha) followed by T2 (29.67 t/ha) and these were superior over rest of the treatments. Among them T6 (27.70 t/ha) and T8 (27.13 t/ha) recorded good yields. All test fungicide treatments (T1 to T2) were significantly superior over solo fungicide treatments (T3 to T5) and two way tank mix combination treatments (T6 to T8).

Table 5: Phytotoxicity Treatment Details
Tr. No. Treatment Details
Dose/ha *Phytotoxicity (Based on 0-10 Phytotoxicity Rating Scale)
g a.i. Formulation Before Spray Days after application (DAA)
1 3 5 7 10 15
T1 Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w (Example 1) 2200 + 98.56 + 98.56 7040 g 0 0 0 0 0 0 0
T2 Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w (Example 2) 1647.3 + 84.48 +84.48 7040 g 0 0 0 0 0 0 0
T3 Mancozeb 31.25% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w (Example 1) 4400 + 197.12 + 197.12 14080 g 0 0 0 0 0 0 0
T4 Mancozeb 23.4% + Azoxystrobin 1.2% + Metalaxyl-M 1.2% w/w (Example 2) 3294.6 + 168.96 +168.96 14080 g 0 0 0 0 0 0 0
T5 Untreated - - 0 0 0 0 0 0 0
*For phototoxic symptoms- Leaf injury on tips and Leaf surface, Wilting, Vein Clearing, Necrosis, Epinasty and Hyponasty

e) Phytotoxicity: (Table 6) The three fungicide ready combinations were sprayed at doses X (7040 formulation/ha) and 2X (14080 formulation/ha) to check the phytotoxic effects like leaf injury on tips/surface, vein clearing, wilting, necrosis, hyponasty and epinasty on the Tomato crop. The observations on these phytotoxicity parameters were observed on before spray and at 1, 3, 5, 7, 10 and 15 days after application. But there was no any phytotoxicity observed on Tomato crop after spraying in any treatment. Even there was no any adverse effect noticed on Tomato crop in the field applied with fungicides combinations at highest dose of @14080 g/ha.

Conclusion:
1. All three-way combination of fungicide (Mancozeb, Azoxystrobin and Metalaxyl-M) effectively controls Early Blight, Anthracnose and Late Blight of Tomato. Among them Mancozeb 33.6% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w is highly effective.
2. Comparative efficacy of test fungicides is far superior to the market standards- Mancozeb 75% WP, Azoxystrobin 25% SC and Metalaxyl-M 25% WP and their two-way possible tank mix combinations.
3. The test fungicides, (Mancozeb 33.6% + Azoxystrobin 1.4% + Metalaxyl-M 1.4% w/w) followed by next best three-way mixture produce higher yield of Tomato.
4. There is no phytotoxicity effect of test fungicides on Tomato even at double the dosage.
5. Overall, the three-way combination test fungicides show synergistic effect for controlling the diseases. Also for prolong the effectiveness of fungicides liable to encounter resistance problems and to limit crop losses, the test fungicides can be used effectively and safely for the management of diseases than solo Mancozeb 75% WP, Azoxystrobin 25% SC and Metalaxyl-M 25% WP and their two way possible tank mix combinations.
Thus, it is clearly shown that the inventive ternary fungicidal composition exhibits high resistance to diseases even after 15 days of application as compared to known compositions. Overall, the three-way combination of test product shows synergistic effect for controlling the diseases. Also it is shown that the inventive three-way fungicidal composition can be used effectively and safely for the management of diseases over the use of individual fungicides as is evident from the Tables 2 and 3.

The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. Since the modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to the person skilled in the art, the invention should be construed to include everything within the scope of the disclosure.
,CLAIMS:WE CLAIM:
1. A synergistic fungicidal composition comprising:
a) at least one multi-site contact fungicide,
b) at least one quinone outside inhibitors (QOI) fungicide,
c) at least one phenylamide fungicide; and
d) at least one agrochemically acceptable excipient.
.
2. The synergistic fungicidal composition as claimed in claim 1, wherein the said multi-site contact fungicide is present in an amount from 1 wt.% to 90 wt.% of the total weight of the synergistic fungicidal composition,
said quinone outside inhibitors (QOI) fungicide is present in an amount in from 0.1 wt.% to 70 wt.% of the total weight of the synergistic fungicidal composition,
said phenylamide fungicide is present in an amount in between 0.1 wt.% to 70 wt.% of the total weight of the synergistic fungicidal composition.

3. The synergistic fungicidal composition as claimed in claim 1, wherein the at least one multi-site contact fungicide is selected from the group comprising of inorganic fungicide, dithiocarbamate fungicide, phthalimide fungicide, chloronitrile fungicide, sulfamide fungicide, bis-guanidine fungicide, quinone and anthra-quinone fungicide, quinoxaline fungicide, maleimide fungicide, and thiocarbamate fungicide.

4. The synergistic fungicidal composition as claimed in claim 3, wherein the inorganic fungicides can be selected from copper fungicides including copper (II) hydroxide, copper oxychloride, copper (II) sulfate, basic copper sulfate, Bordeaux mixture, copper salicylate, cuprous oxide; or sulphur salts thereof; dithiocarbamate fungicides are selected from amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, manam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet, etem, milneb, mancopper, mancozeb, maneb, metiram, propineb, polycarbamate, zinc thiazole, zineb, and ziram; phthalimide fungicides is selected from captan, captafol, and folpet; chloronitrile fungicide is chlorothalonil; sulfamide fungicides is selected from dichlofluanid, and tolylfluanid; bis-guanidine fungicides is selected from guazatine, and iminoctadine; quinone fungicide is dithianon and anthra-quinone fungicide is anilazine; quinoxaline fungicide is chinomethionat or quinomethionate; maleimide fungicide is fluoroimide; and thiocarbamate fungicide is methasulfocarb.

5. The synergistic fungicidal composition as claimed in claim 1, wherein the quinone outside inhibitors (QOI) fungicide is selected from strobilurins, methoxy- acrylates, methoxy-acetamide, methoxy carbamates, oximino-acetates, oximino- acetamides, oxazolidine-diones, dihydro-dioxazines, imidazolinones, and benzyl-carbamates.

6. The synergistic fungicidal composition as claimed in claim 5, wherein the quinone outside inhibitors (QOI) fungicide is selected from the azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, famoxadone, fluoxastrobin, fenamidone, and pyribencarb.

7. The synergistic fungicidal composition as claimed in claim 1, wherein phenylamide fungicide is selected from acylalanines, oxazolidinones, butyrolactones, hydroxy- (2-amino-) pyrimidines, isoxazoles, and carboxylic acids.

8. The synergistic fungicidal composition as claimed in claim 7, wherein the acylalanines are selected from benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, and metalaxyl-M (or mefenoxam), pefurazoate, valifenalate;
oxazolidinones is oxadixyl and butyrolactone is ofurace; hydroxy-(2-amino-) pyrimidines is selected from bupirimate, dimethirimol, and ethirimol; isoxazole is isothiazolone and carboxylic acid is oxolinic acid.

9. The synergistic fungicidal composition as claimed in claim 1, wherein the agrochemically acceptable excipients are selected from the group comprising of dispersing agent, wetting agent, anti-caking agent, thickener, preservative, diluent, stabilizer, defoamer, anti-freezing agent, and anti-penetrating agent or a mixture thereof.

10. The synergistic fungicidal composition as claimed in claim 1, wherein said composition is formulated as a solid or liquid formulation selected from the group comprising of wettable powders, water dispersible granule, granules, dusts, soluble (liquid) concentrates, suspension concentrates, oil in water emulsion, water in oil emulsion, emulsifiable concentrates, capsule suspensions, ZC formulations, oil dispersions.

11. Method for controlling fungi comprising the steps of applying the synergistic fungicidal composition according to claim 1 to the fungi and/or their habitat.

12. Use of the synergistic fungicidal composition claimed in any of the preceding claims for controlling fungi.