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Synergistic Fungicidal Composition

Abstract: The present invention relates to a synergistic fungicidal composition. More particularly, the present invention relates to a synergistic fungicidal composition comprising a) Cyazofamid or its agrochemically acceptable salts; and b) Dimethomorph or its agrochemically acceptable salts and c) a triazole fungicide or its agrochemically acceptable salts. The present invention further relates to the said synergistic fungicidal composition comprising bio-based efficacy enhancing agents with one or more agrochemically acceptable excipients. The present invention also relates to a process for preparation of such synergistic fungicidal composition.

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Patent Information

Application #
Filing Date
17 November 2021
Publication Number
48/2021
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
drshilpaarora@gmail.com
Parent Application
Patent Number
Legal Status
Grant Date
2022-10-27
Renewal Date

Applicants

SEEDLINGS INDIA PRIVATE LIMITED
S-1A, first floor, Bhagwan Das Nagar, East Punjabi Bagh, New Delhi-110026

Inventors

1. Hardik Sabalpara
S-1A, first floor, Bhagwan Dass Nagar, East Punjabi Bagh, New Delhi -110026
2. Vimal Kumar
S-1A, first floor, Bhagwan Dass Nagar, East Punjabi Bagh, New Delhi -110026
3. Raajan Kumar Ailawadhi
S-1A, first floor, Bhagwan Dass Nagar, East Punjabi Bagh, New Delhi -110026

Specification

The present invention relates to a synergistic fungicidal composition. More particularly, the present invention relates to a synergistic fungicidal composition comprising a) Cyazofamid or its agrochemically acceptable salts; and b) Dimethomorph or its agrochemically acceptable salts and c) a triazole fungicide or its agrochemically acceptable salts. The present invention further relates to the said synergistic fungicidal composition comprising bio-based efficacy enhancing agents with one or more agrochemically acceptable excipients. The present invention also relates to a process for preparation of such synergistic fungicidal composition.
BACKGROUND OF THE INVENTION
Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi. Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides. Using fungicides allows a grower to increase the yield and the quality of the crop and consequently, increase the value of the crop. In most situations, the increase in value of the crop is worth at least three times the cost of the use of the fungicide.
Various compositions have been developed to control fungi. Practical agricultural experience has shown that the repeated and exclusive application of an individual active compound for the control of harmful fungi in many cases leads to rapid development of those strains which have developed natural or adapted resistance against the active compound in question. Effective control of these fungi with the active compound in question is very difficult in such cases. To reduce the risk of development of resistant strains, mixtures of different active compounds are nowadays conventionally employed for controlling harmful fungus or pests. It is possible to ensure successful control over a relatively long period of time by combining active compounds having different mechanisms of action.
Most crop and ornamental plants are subject to attack by several fungi. Damage due to plant diseases to ornamentals, vegetable, field, cereal and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Serious disorders in combination or singly has resulted in the need for broad-spectrum disease control. Although there
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are available numerous chemical compounds (fungicides), which aid in preventing diseases of plants, each of these have practical deficiencies, which restrict their use.
Combinations of fungicides are often used to facilitate disease control, to broaden spectrum of control and to retard resistance development. Accordingly, new advantageous combinations are needed to provide a variety of options to best satisfy particular plant disease control needs. Furthermore, certain rare combinations of fungicides demonstrate a greater-than-additive (i.e. synergistic) effect to provide commercially important levels of plant disease control.
When two or more substances in combination demonstrate unexpectedly high biological activity, for example fungicidal activity, the resultant phenomenon may be referred to as synergism.
Conventional fungicide compositions comprising Cyazofamid and/or Dimethomorph showing anti-fungal activity sometimes do not show a practically sufficient control effect on plant diseases including preventive and curative activity against Ascomycetes (e.g. powdery mildew), Basidomycetes (e.g. rusts & smuts) and Deuteromycetes (e.g. blights & downy mildew), since it has an insufficient effect on particular plant diseases or its residual effectiveness lasts for a relatively short period. Thus, there is limited spectrum of fungal diseases and fungi which may be controlled and treated by such fungicides and which fail to have a preventive action apart from curative action. Further, the risk of resistance development with use of specific type of fungicide is pronounced when used for a long period of time.
In order to achieve the high crop productivity, it is important to control the plant from damages which can be caused by plant pathogenic (disease-causing) organisms including various types of plant fungal infections. However, there exists a continuous need in the art for improved compositions that not only helps in controlling the fungal growth but also enhances bio-efficacy including increase in plant yield, having reduced phytotoxicity and an improved stability characteristics and economic significance including ease of manufacture with higher benefit: cost ratio i.e. higher return on investment. Therefore, there is a long felt need to develop novel and effective synergistic fungicidal composition comprising combination of Cyazofamid and/or Dimethomorph for controlling the harmful pests, fungi in plants and demonstrating a high efficacy and high selectivity and which is environmentally safe and can be advantageously formulated using reduced dosages of individual fungicides/technicals in the final composition.
Fungicidal combinations offer significant advantages over individual applications including improved and extended fungal control, reduced fungicide application rates and costs, shorter

contact times for improved results, less stringent use restrictions, improved selectivity, improved spectrum of fungi controlled, reduced cost and reduced residue problems. However, identifying appropriate fungicide application rates and ratio of the combinations is essential to achieve efficacious disease control. In view of the above, obtaining a fungicidal composition comprising a combination of fungicides which demonstrates no cross-resistance to the existing fungicidal agents, no toxicity problems, is stable, offers broad spectrum control of fungal diseases, reduces pest resistance development and has little negative impact on the environment is extremely difficult. Hitherto, there have been no studies to determine the most-efficacious and synergistic ratios at which such broad spectrum fungicides synergistically complement each other's fungicidal properties not seen at other ratios. Thus, there exists a need in the art for a composition comprising fungicides which show superior and effective control of fungal infections.
The present inventors have surprisingly developed an effective synergistic fungicidal composition which ameliorates the aforesaid shortcomings of the prior art.
Over the years there are various prior arts which have offered various fungicidal compositions useful for protecting the plant from damage by harmful pests such as Downy mildew, Crown rot, Late blight, etc.
Reference may be made to CN103749466, wherein it discloses a sterilization composition containing Cyazofamid and a triazole compound comprising an active component A and an active component B with a weight ratio of 1-50%: 1-50%, wherein the active component A is Cyazofamid, and the active component B is one selected from tebuconazole, imibenconazole, bitertanol, ipconazole, metconazole, triticonazole, fenbuconazole and difenoconazole.
Reference may be made to CN101642111, wherein it discloses a novel pesticide sterilizing composition preparation, in particular to a suspending emulsion compounded from difenoconazole and dimethomorph and a preparing method thereof.
Reference may be made to CNl01690484, wherein it discloses a suspending agent compounded by dimethomorph and cyazofamid as well as a preparation method thereof.
Reference may be made to CNl04642329, wherein it discloses a bactericidal composition containing Prothioconazole and Cyazofamid, which is characterized in that, the weight ratio of prothioconazole to cyazofamid is (1-70): 1 to 50.

Accordingly, there exists a need for combining more than two fungicides belonging to different chemical classes and showing different mechanism of action and is useful against Foliar, Seed and soil borne diseases at all stages of life cycle of the pest/fungi. The present invention provides a synergistic composition of more than two fungicides. The composition of the present invention is synergistic, reduces amount of pesticide used, is environmentally friendly, easy to formulate and is safe to use.
Cyazofamid IUPAC name:4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-l-sulfonamide, CAS No. 120116-88-3. introduced by ISHfflARA SANGYO KAISHA, LTD and marketed under the tradename Ranman and having the following chemical structure:

Cyazofamid
Cyazofamid is a fungicide belonging to both the cyano-imidazole and sulphonamide classes of compounds. Cyazofamid is a Qi (quinone inside reducing site) inhibitor. Cyazofamid has a foliar and soil preventative action with some residual activity. Cyazofamid has very low water solubility; the mobility within the leaf is low and a short hydrolytic half-life. The biochemical mode of action is inhibition of all stages of fungal development. It is registered for control of and protection against Oomycete fungi. It has been shown to affect all stages in the life cycle of Phytophthora infestans (Late Blight of Potato) & Downy mildew of Grapes (Vitis vinifera). The product is particularly suited for use in preventive spray schedules. Numerous studies have found out that Cyazofamid degrades rapidly when exposed to natural light. Therefore, it is recommended that the application of cyazofamid be done at low temperature and weak light in the evening so as to get greater efficacy.

Dimethomorph was first disclosed in US 4933449 and US4923866.Dimethomorph is chemically known as (EZ)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine and having chemical structure as below:

Dimethomorph
Dimethomorph is a systemic morpholine fungicide. It has a low aqueous solubility and a low volatility. It may be moderately persistent in both soil and water systems. It is a cinnamic acid derivative and a member of the morpholine chemical family. It is a mixture of two isomers but only the Z isomer has fungicidal activity. Dimethomorph disrupts cell wall formation by interfering with the molecular arrangement of cell wall components. Its mode of action is the inhibition of sterol (ergosterol) synthesis. Morpholines are all systemic with curative and preventative qualities. Dimethomorph was developed for downy mildews, late blights, crown and root rots for grapes, potatoes, tomatoes, and other vegetables.
Triazole pesticide derivatives represent the most important category of fungicides that have excellent protective, curative and eradicant power towards a wide spectrum of crop infestations. The fungicide group, demethylation inhibitors (DMI), which contain the triazole fungicides, was introduced in the mid-1970s. These fungicides are highly effective against many different fungal diseases, especially powdery mildews, rusts, and many leaf-spotting fungi. Various triazole fungicides are known in the art. Chemical structure of some of such fungicides are provided below:


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Most of the triazole fungicides have excellent fungicidal action against Foliar, Seed and soil borne diseases. In particular, these fungicides are active as systemic & broad spectrum and effective against diseases caused by Ascomycetes, Basidiomycetes & Deuteromycetes.
Above mentioned fungicides can be formulated into a variety of different forms preferably into liquid and solid compositions.
Accordingly, it is desirable to develop compositions and processes comprising combinations of above-mentioned fungicides that can be used for treatment of various pests and plant fungal diseases such as late blight, scab, powdery mildew and downy mildews against Phytophthora species, Leptosphaerulina and Curvularia species.
The present invention thus provides a novel and effective fungicidal composition comprising synergistic and bio-effective amount of fungicidal composition comprising a) Cyazofamid or its agrochemically acceptable salts; and b) Dimethomorph or its agrochemically acceptable salts and c) a triazole fungicide or its agrochemically acceptable salts. The said synergistic fungicidal composition further comprises of bio-based efficacy enhancing agents with one or more agrochemically acceptable excipients.
The present invention further provides a novel method of preparing compositions comprising

Embodiments of the present invention may therefore ameliorate one or more of the above-mentioned problems.
OBJECTS AND ADVANTAGES OF THE INVENTION:
It is an object of the present invention to provide a novel and effective synergistic fungicidal composition demonstrating high efficacy and high selectivity.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition for controlling the harmful pests and fungi in plants and offer broad spectrum control of plant fungal diseases
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition that enhances the greening of crops to which it is administered.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition that delays senescence to the crop to which it is applied thereby resulting in an increased yield of the crop.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which is ideal for fungicide resistance management and enhanced disease control.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which can be easily formulated with high stability.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which uses lesser amounts of the actives as compared to the actives when used alone.
It is another object of the present invention to provide novel & effective synergistic fungicidal composition with high degree of rain fastness having longer residual action on pathogens, thereby reducing the number of foliar spray applications.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which is environmentally safe, possesses broad spectrum bio-efficacy, is less toxic in terms of phytotoxicity.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which is stable at various temperature ranges and variable environmental changes.

It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which increases crop yield.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which provides maximum benefit with reduced cost thus providing higher benefit:cost ratio.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which gives longer and excellent residual control.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which has both preventive and curative action and is active against all life stages of major fungi.
Another object of the present invention is to provide a novel and effective synergistic fungicidal composition which is more stable and has enhanced shelf life.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which uses green surfactants including silicone ethoxylated oils and suitable bio-based efficacy enhancing agents including blend of polyterpene resin.
It is another object of the present invention to provide a novel and effective synergistic fungicidal composition which has enhanced efficacy and penetration capacity.
Yet another object of the present invention is to provide a method of controlling fungi using fungicidal composition comprising synergistic and bio-effective amount of fungicidal composition comprising a) Cyazofamid or its agrochemically acceptable salts; and b) Dimethomorph or its agrochemically acceptable salts; and c) a triazole fungicide or its agrochemically acceptable salts; and d) one or more agrochemically acceptable excipients.
The synergistic fungicidal composition of the present invention is found to be useful in protecting a wide range of crops like fruits, vegetables, cereals, flowers etc. against major diseases. The composition achieves improved biological efficacy by enhancing overall control of fungus over a shorter period of time. Additional benefits of using the fungicidal composition of the present invention includes reduced risk of occupational hazard, lower cost of application, better benefit: cost ratio to the end user, reduced fuel and labour cost. Saving in applicator's time and reduced wear of equipment and loss caused by mechanical damage to the crop and soil.

Some or all these and other objects of the invention can be achieved by way of the invention described hereinafter.
SUMMARY OF THE INVENTION
Accordingly, the present invention relates to novel and effective fungicidal composition comprising synergistic and bio-effective amount of a) Cyazofamid or its agrochemically acceptable salts; and b) Dimethomorph or its agrochemically acceptable salts and c) a triazole fungicide or its agrochemically acceptable salts.
In one embodiment of the present invention, the fungicidal composition comprises:
a) Cyazofamid or its agrochemically acceptable salts; and
b) Dimethomorph or its agrochemically acceptable salts; and
c) at least one triazole fungicide selected from Hexaconazole, Cyproconazole, Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole, Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its agrochemically acceptable salts; and
d) One or more agrochemically acceptable excipients.
In another embodiment of the present invention, the fungicidal composition comprises:
a) Cyazofamid or its agrochemically acceptable salts in the range of 2-30% by weight of the formulation; and
b) Dimethomorph or its agrochemically acceptable salts in the range of 10-70% by weight of the formulation; and
c) at least one triazole fungicide selected from Hexaconazole, Cyproconazole, Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole, Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its agrochemically acceptable salts in the range of 2-40% by weight; and
d) One or more of agrochemically acceptable excipients.
In another embodiment of the present invention, the fungicidal composition comprises:
a) Cyazofamid or its agrochemically acceptable salts in the range of 2-30% by weight of the formulation; and
b) Dimethomorph or its agrochemically acceptable salts in the range of 10-70% by weight of the formulation; and
c) at least one triazole fungicide selected from Hexaconazole, Cyproconazole, Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole,

Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its agrochemically acceptable salts in the range of 2-40% by weight; and
d) bio based efficacy enhancing agents including blend of polyterpene resin.
e) One or more of agrochemically acceptable adjuvants
In another embodiment of the present invention, it is provided a process for preparation of the synergistic fungicidal composition comprising:
a) Cyazofamid or its agrochemically acceptable salts; and
b) Dimethomorph or its agrochemically acceptable salts; and
c) at least one triazole fungicide selected from Hexaconazole, Cyproconazole, Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole, Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its agrochemically acceptable salts; and
d) One or more agrochemically acceptable excipients.
In another embodiment of the present invention, the invention provides a method for effective control of various fungi in crops and plants.
In another embodiment of the present invention, the fungicidal composition of the present invention further comprises agrochemically acceptable excipients selected from the group comprising of anti-freezing agent, dispersing agents, wetting agents, antifoaming agents, biocides, thickeners, surfactants, preservatives, colorants, pigments, buffers, solvents, and the like. Additional components may also be included, e.g., protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active materials can be combined with any solid or liquid additive, formulation aids which complies with usual formulation techniques.
The remainder of the aqueous formulation is preferably wholly water but may comprise other materials, such as inorganic salts. The formulation is preferably, completely free from organic solvents.
In another embodiment of the present invention, the fungicidal composition of the present invention further comprises organosilicone surfactants/adjuvant as spreading and sticking agents and bio based efficacy enhancing agents.
In another embodiment of the present invention, the fungicidal composition of the present invention further comprises trisiloxane ethoxylate as organosilicone surfactant/adjuvant.

In another embodiment of the present invention, the fungicidal composition of the present invention further comprises blend of polyterpene resin (natural oils) as bio based efficacy enhancing agents.
In another embodiment, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pathogenic damage or pest damage by applying to the plant propagation material a composition of the present invention.
In one aspect/ another embodiment of the present invention, the present fungicidal composition can be applied to a plant/crop by spraying, rubbing, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, pouring, mist blowing, soil mixing, foaming, painting, spreading-on, drenching, dipping or drip irrigation. Etc.
In another embodiment of the present invention the present fungicidal composition controls various pests in field crops, vegetables, oil seed and pulses, horticulture & forestry, Veterinary, etc.
In yet another embodiment of the present invention, the present fungicidal composition can be applied as a foliar spray to cotton, wheat, soyabean, pulses and vegetables including but not limited to okra, tomato, sugar beet, egg-plants, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as potato, sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium, etc.
In yet another embodiment of the present invention, the fungicidal composition is formulated as but not limited to Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed

treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE) and a mixed formulation of CS and EW (ZW).
In yet another embodiment of the present invention, the invention further provides the process for preparation of the said formulation wherein, the said formulation can be one or more of Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE) and a mixed formulation of CS and EW (ZW).
DETAILED DESCRIPTION OF THE INVENTION
Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods. The illustrative examples are described in this section in connection with the embodiments and methods provided. The invention according to its various aspects is particularly pointed out and distinctly claimed in the appended claims read in view of this specification and appropriate equivalents.
All technical and scientific terms used herein have the same meanings as commonly understood by someone ordinarily skilled in the art to which the present subject matter belongs.
It is to be noted that, as used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" includes a mixture of two or more compounds. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.
The expression of various quantities in terms of "% w/w" or "%" means the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified.

The term "control" as used in the present disclosure and claims, means to prevent the appearance of undesired vegetation or to reduce its growth or vigor.
The term "active ingredient" (a.i.) or "active agent" used herein refers to that component of the composition responsible for control and killing of pest/fungi.
The term "formulation" and "composition" as used herein conveys the same meaning and can be used interchangeably.
The terms "plants" and "vegetation" include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, and established vegetation.
The term "Rainfastness" as used herein, refers to the ability of a compound to resist removal or wash-off due to rain and other environmental effects.
The term "crop" shall include a multitude of desired crop plants or an individual crop plant growing at a locus.
The term "synergistic", as used herein, refers to the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.
"Bioactive amounts" as mentioned herein means that amount which, when applied for treatment of crops, is sufficient to give effect in such treatment.
The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as, but not limited to, seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting.
The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health; yield, plant vigour, quality and tolerance to abiotic or biotic stress is increased. It is noteworthy that the health of a plant when applying the composition according to the present invention, is increased independently of the pesticidal properties of the active ingredients used; because the increase in health is not based upon the reduced pest pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defence system. As a result, the health of a plant is increased even in the absence of pest pressure. Accordingly, in an especially preferred embodiment of the method according to the invention, the health of a plant is increased both in the presence and absence of biotic or abiotic stress factors. The above identified indicators for the health condition

of a plant may be interdependent or they may result from each other. An increase in plant vigor may for example result in an increased yield and/or tolerance to abiotic or biotic stress.
One indicator for the condition of the plant is the yield. "Yield" is to be understood as any plant product of economic value that is produced by the plant such as grains, fruits, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants) or even flowers (e.g. in the case of gardening plants, ornamentals). The plant products may in addition be further utilized and/or processed after harvesting.
In an especially preferred embodiment of the invention, the yield of the treated plant is increased.
In another preferred embodiment of the invention, the yield of the plants treated according to the method of the invention, is increased synergistically.
According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the mixture according to the invention.
Increased yield can be characterized, among others, by the following improved properties of the plant: increased plant weight, increased plant height, increased biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves, increased shoot growth, increased protein content, increased oil content, increased starch content, increased pigment content, increased leaf index. According to the present invention, the yield is increased by at least 4 %, preferable by 5 to 10 %, more preferable by 10 to 20 %, or even 20 to 30 % compared to the untreated control plants or plants treated with 10 pesticides in a way different from the method according to the present invention. In general, the yield increase may even be higher.
The term "benefit: cost" as mentioned herein is a ratio used in a cost-benefit analysis to summarize the overall relationship between the relative costs and benefits of a proposed composition. If a treatment has a benefit-cost ratio greater than 1.0, the treatment is expected to deliver a positive and better outcome.
A further indicator for the condition of the plant is the plant vigour. The plant vigour manifests in several aspects such as the general visual appearance. Improved plant vigour can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant, improved plant growth, improved plant development, improved visual appearance, improved plant

stand (less plant verse/lodging), improved emergence, enhanced root growth and/or more developed root system, enhanced nodulation, in particular rhizobial nodulation, bigger leaf blade, bigger size, increased plant weight, increased plant height, increased tiller number, increased number of side shoots, increased number of flowers per plant, increased shoot growth, increased root growth (extensive root system), increased yield when grown on poor soils or unfavourable climate, enhanced photosynthetic activity (e.g. based on increased stomatal conductance and/or increased C02 assimilation rate), increased stomatal conductance, increased C02 assimilation rate, enhanced pigment content (e.g. chlorophyll content), earlier flowering, earlier fruiting, earlier and improved germination, earlier grain maturity, improved self-defence mechanisms, improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, insects, heat stress, cold stress, drought stress, UV stress and/or salt stress, less non-productive tillers, less dead basal leaves, less input needed(such as fertilizers or water), greener leaves, complete maturation under shortened vegetation periods, less fertilizers needed, less seeds needed, easier harvesting, faster and more uniform ripening, longer shelf-life, longer panicles, delay of senescence, stronger and/or more productive tillers, better extractability of ingredients, improved quality of seeds (for being seeded in the following seasons for seed production), better nitrogen uptake, improved reproduction, reduced production of ethylene and/or the inhibition of its reception by the plant.
In another especially preferred embodiment of the invention, the plant vigour of the treated plant is increased. In another preferred embodiment of the invention, the plant vigour of the plants treated according to the method of the invention is increased synergistically.
The improvement of the plant vigour according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved.
Another indicator for the condition of the plant is the "quality" of a plant and/or its products.
In an especially preferred embodiment of the invention, the quality of the treated plant is increased.
In another preferred embodiment of the invention, the quality of the plants treated according to the method of the invention, is increased synergistically.
According to the present invention, enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions. Enhanced quality can be characterized, among others, by following improved properties of the plant or its

product: increased nutrient content, increased protein content, increased content of fatty acids, increased metabolite content, increased carotenoid content, increased sugar content, increased amount of essential amino acids, improved nutrient composition, improved protein composition, improved composition of fatty acids, improved metabolite composition, improved carotenoid composition, improved sugar composition, improved amino acids composition, improved or optimal fruit colour, improved leaf colour, higher storage capacity, higher processability of the harvested products.
Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors. Biotic and abiotic stress, especially over longer terms, can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "enhanced tolerance or resistance to biotic and/or abiotic stress factors" means (1) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with the composition of the present invention and (2) that the negative effects are not diminished by a direct action of the mixture according to the invention on the stress factors, e.g. by its fungicidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors.
In accordance with an embodiment of the invention, there is provided a synergistic fungicidal composition comprising active ingredients present in the weight ratios as given below; and one or more customary formulation adjuvants.

Triazole Fungicide
Hexaconazole
Cyproconazole
Diclobutrazol
Difenoconazole
Diniconazole
Cyazofamid Dimethomorph Epoxiconazole
Etaconazole
Fenbuconazole
Propiconazole
Tebuconazole
Tetraconazole
Triticonazole
2% to 30% 10% to 70% 2% to 40%

Surprisingly it has been found that by combining the fungicides of the present synergistic fungicidal composition, the dose per hectare (ha) is reduced and benefit-cost ratio is increased; there is longer duration of pest control with enhanced fungicidal control effect and reduced phytotoxicity with enhanced shelf life/stability. Further, the present synergistic fungicidal composition also exhibits enhanced greening, increased crop yield and better pest control during wet season due to its effective rainfastness property.
In preferred embodiment of the present invention, Cyazofamid is present in the range of 2-30% weight of the total composition.
In another preferred embodiment of the present invention, Cyazofamid is present in an amount of 5% weight of the total composition.
In preferred embodiment of the present invention, Dimethomorph is present in the range of 10-70% weight of the total composition.
In another preferred embodiment of the present invention, Dimethomorph is present in an amount of 32%) weight of the total composition.
In another preferred embodiment of the present invention, triazole fungicide is Difenoconazole and is present in the range of 2-40% weight of the total composition.
In yet another preferred embodiment of the present invention, Difenoconazole is present in an amount of 8%> weight of the total composition.
In another embodiment of the present invention, the invention further provides the process for preparation of the said formulation wherein, the said formulation can be one or more of Capsule suspension (CS), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion for foliar spray (ES), Emulsion, oil in water (EW), Flowable suspension/concentrate for foliar spray (FS), Granule/ soil applied (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (flowable concentrate) (SC), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP), Water dispersible granule (WG or WDG), Wettable powder (WP), Water dispersible powder for slurry treatment (WS), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

In yet another embodiment of the present invention, the agrochemically acceptable excipients of the formulation are selected from the group consisting of anti-freezing agent, dispersing agents, wetting agents, antifoaming agents, biocides, thickening agent, adjuvants and solvents. One or more inactive excipient is selected from 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"), spreading agents, buffering agent, binders, adjuvants, fillers, emulsifiers, colouring pigments, dyes, preservatives and mixtures thereof.
An adjuvant used in the present invention is any material that is added to an agrochemical formulation to enhance or modify the performance of the formulation. An adjuvant used in the present invention to make it safer to ecological environmental, having low toxicity and having no phytotoxicity effects on any part of the plant.
Extender or sticker/sticking agent keeps pesticides active on a target for an extended period or on waxy foliage. Sticker allows pesticides to stay on a treated surface longer. Some stickers help to hold solid particles to a treated surface. This reduces the amount that washes off due to rain or irrigation. Others reduce evaporation and/or slow breakdown by sunlight.
Spreader allows a pesticide to form a uniform layer over a treated surface. Spreaders such as Silicone Ethoxylated Oil lowers the surface tension of spray solutions beyond that which is achievable with conventional non-ionic surfactants. In fact, it has the potential to provide adequate coverage in many low volume spray applications at rates between 0.025% and 0.1%. It decreases the surface tension of spray solutions to much lower values, in comparison to conventional adjuvants. This results in significantly enhanced spreading of spray solutions over the treated plant surfaces which carries tank mix products to morphologically complex and thus difficult-to- to-reach parts of the plant.
Advantages of organosilicone adjuvants (OSSA):
• Quick spreading and wetting
• Uniform droplet distribution
• Absorption on leaf and stem surfaces
• Known benefits: Increases pesticide efficacy

In yet another embodiment of the present invention, the agrochemically acceptable adjuvants-Silicone Ethoxylated Oil, Polyvinyl Pyrrolidone, Polyvinyl Alcohol, Blend of poly terpene resin, are present in the range of 0.1-10% of the total composition.
In another embodiment of the present invention, the fungicidal composition of the present invention further comprises organosilicone surfactants/adjuvant as spreading and sticking agents and bio based efficacy enhancing agents.
In another embodiment of the present invention, the fungicidal composition of the present invention further comprises trisiloxane ethoxylate as organosilicone surfactant/adjuvant.
In another embodiment of the present invention, the fungicidal composition of the present invention further comprises blend of polyterpene resin (natural oils) as bio based efficacy enhancing agents.
AltaHance 3S is a distilled tall oil based green adjuvant. It is a biobased sticker adjuvant that enhances the effectiveness of agrochemicals by increasing their rainfastness—even under challenging conditions, such as cold temperatures and hard water. AltaHance provides the ability to tune rainfastness based on your formulation needs, providing flexibility, ease of handling and formulation robustness for customers.
Altastick HG (a blend of polyterpene resin and emulsifier) is commonly used as a sticker adjuvant to improve rainfastness and retention of the particles on foliage. Altastik HG is a blend of terpene resin and surfactant. Altastick HG is ready to use and can be applied in combination with penetrants to improve efficacy of pesticides. Altastick HG is free of nonylphenol ethoxylate (NPE).
Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures both the types. 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. Examples of dispersants used herein include but not limited to sodium lignosulphonates, calcium ligno sulphate, sodium naphthalene sulphonate formaldehyde condensates, Polyphenyl ether phosphate, thoxylated fatty alcohol, Tristyrylphenol Ethoxylate Amine salt of phosphate, tristyryl phenol ethyoxylate, Acrylic Copolymer, Ethoxylated Tristryl phenol Sulphate, Naphthalene sulfonic acid, sodium salt condensate with formaldehyde,

Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol ether, EO-PO block copolymers, and graft copolymers or mixtures thereof
In one embodiment of the present invention, surfactants/dispersing agents are present in the range 0.5-10% of the total composition.
Emulsifiers are added to buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
Emulsifier are further added to Oil Dispersion formulations for uniform emulsions and are selected from Castor oil ethoxylates, Calcium alkyl benzene sulfonate or mixtures thereof, in the range from 0.1-10% of the total composition.
Anti-freezing agent as used herein can be selected from the group consisting of glycols, monoethylene glycol, diethylene glycol, propylene glycol, polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.
In one embodiment of the present invention, anti-freezing agents are present in the range of 0.1-10%) of the total composition.
Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency of foaming; anti-foaming agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foaming agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the nonsilicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.
A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in

wettable powder, suspension concentrate, and water-dispersible granule formulations include but not are limited to Tristyrylphenol ethoxylate non-ionic emulsifier, mixture of non-ionic surfactants & Alkoxylated Alcohol/Block copolymer, sodium lauryl sulphate, sodium dioctylsulphosuccinate, alkyl phenol ethoxylates and aliphatic alcohol ethoxylates and the salts thereof.
In one embodiment of the present invention, wetting agents are present in the range of 0.5-10% of the total composition.
Fillers/ 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).
The anti-bacterial agents are used to eliminate or reduce the effect of microorganisms. Examples of such agents include, but are not limited to propionic acid and its sodium salt, sorbic acid and its sodium or potassium salts, sodium o-phenyl phenate, benzoic acid and its sodium salt, 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, Benzisothiazolin-3-one, formaldehydes or mixtures thereof.
In one embodiment of the present invention, antimicrobial/anti-bacterial agents are present in the range of 0.01-1% of the total composition.
Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspo-emulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, bentonite, magnesium aluminium silicate, and attapulgite. Water soluble polysaccharides most commonly used as thickening-gelling agents are natural extracts of seaweeds, synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum, carrageenan, xanthan gum, alginates, methyl cellulose,

carboxymethyl cellulose (CMC), 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.
In one embodiment of the present invention, thickeners or gelling agents are present in the range of 0.01-3% of the total composition.
Defoamer/Antifoaming agent are used in agro-chemical formulations to prevent foaming during mixing and spraying stage and generally added to the composition as foam formation prevents the efficient filling of a container. Antifoaming agent are selected form the group consisting of silicon emulsion based anti-foam agents, Siloxane polyalkyleneoxide, trisiloxane ethoxylates and mixtures thereof
In one embodiment of the present invention, antifoaming agents are present in the range of 0.01-1% of the total composition.
Filler is added to the composition to improve the handling and storage characteristics of the composition. Fillers also add mass and/or volume to the active ingredient in order to facilitate precise measurement of the doses. Suitable fillers that may be used in the composition of the present invention include, but not limited to, Silicon Dioxide, bentonite clay, china clay, silica, kaolin, talc, starch, diatomaceous earth and mixtures thereof.
In one embodiment of the present invention, fillers are present in the range of 0.1-5% of the total composition.
Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
The 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 copolymers and 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(styrenecomaleic 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 ester aliphatic polyester blends, modified corn starch, polycaprolactone, poly(n-amylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.
The solvent for the formulation of the present invention may include water, 1-octanol, water soluble alcohols. 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, 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, di ethylene 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.
In one embodiment of the present invention, the solvent is present in the range of 10-30% of the total composition.
Spray colourants/ dyes are used as crop protectants as it helps in identification of areas where product has previously been applied, and for health & safety precaution & awareness.

In yet another embodiment of the present invention, the adjuvants are bio based performance enhancing agents which promote sticking and spreading of the pesticidal composition and also improve rainfastness of the pesticide composition.
In yet another embodiment the adjuvants further consist of castor oil ethoxylates, polyterpene resin and emulsifier blend.
In a specific embodiment, the fungicidal composition of the present invention may be applied in an amount of about 1250g/ha.
In one embodiment, the compositions according to the present invention acts synergistically to control fungi in various crops. In an especially preferred embodiment of the invention, the yield of the treated plant and crop is increased.
In another preferred embodiment of the invention, the yield of the plants treated according to the method of the invention, is increased synergistically. According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the mixture according to the invention.
Increase in yield of treated plants (cereals, pulses, oilseeds, fibre crop, sugar crops, leafy vegetables, tuber crops, fruit crops, flowers, ornamentals etc.). Increase in yield means increased plant weight, increased plant height, increased biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves, increased shoot growth, increased protein content, increased oil content, increased starch content, increased pigment content, Increase in yield due to protection against Insect-pest damage and fungal diseases, Increase in yield due to plant growth regulation, check vegetative growth and increase in reproductive parts of plant, Increase in yield due to more number of tillers, more branches and sub branches, more number of fruits, flowers, and grains size, Increase plant vigor, Increase tolerance to insect-pests and fungal damage, Increase tolerance to the weather stress, moisture stress and heat stress, Prevents lodging in susceptible plants (lodging due to biotic and abiotic factors, like heavy rains, winds, insects and diseases damage.
The compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes.

They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops.
These pathogens include:
Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamoni, Phytophthora capsici; Pythium diseases such as Pythium aphani dermatum; and diseases in the Peronosporaceae family, Such as Plasmopara viticola, Peronospora sp. (including Peronospora tabacina and Peronospora parasitica), Pseudop eronospora sp. (including Pseudoperonospora cubensis), and Bremia lactucae;
Ascomycetes, including Alternaria diseases such as Alternaria Solani and Alternaria brasicae, Guignardia diseases such as Guignardia bidwel. Venturia diseases such as Venturia inaequalis, Septoria diseases such as Septoria nodorum and Septoria tritici; powdery mildew diseases such as Erysiphe sp.(including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca filigena, and Podosphaera leucotricha, Pseudocercosporellaherpotrichoides, Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viti cola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora teres; anthracnose diseases such as Glomerella or Colletotrichum sp. (Such as Colletotrichum graminicola); and Gaeumannomyces graminis;
Basidiomycetes, including rust diseases caused by Puccinia sp. (such as Puccinia recondita, Puccinia striformis, Puccinia hordei, Puccinia graminis, and Puccinia arachidis); Hemileia vastatrix; and Phakopsora pachyrhizi;
Other pathogens including Rhizoctonia spp (such as Rhizoctonia solani); Fusarium diseases such as Fusarium roseum, Fusarium graminearum, Fusarium oxysporum, Verticilium dahliae, Sclerotium rolfsi. Rynchosporium secalis, Cercosporidium personatum, Cercospora arachidicola and Cercospora beticola, and other genera and species closely related to these pathogens.
The composition of the present invention also provides control of diseases caused by a broad spectrum of fungal plant pathogens preventatively or curatively by applying an effective amount of the composition either pre-or post-infection.
Plant disease control is ordinarily accomplished by applying an effective amount of a synergistic composition of the present invention either pre-or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The composition can also be applied to the

seed to protect the seed and seedling. Typically, the composition is applied in the form of a composition comprising at least one additional component selected from the group consisting of Surfactants, Solid diluents and liquid diluents.
The synergistic fungicidal composition of the present invention is very helpful to the farmers to protect crops from following fungal diseases: late blight, scab, powdery mildew and downy mildews, Phytophthora, Leptosphaerulina and Curvularia species infections.
The synergistic fungicidal composition of the present invention is very helpful to the farmers to protect crop/plants selected from but not limited to cotton, wheat, soyabean, pulses and vegetables including but not limited to okra, tomato, sugar beet, egg-plants, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as potato, sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium, etc.
Thus, before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified systems or process parameters that may of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only and is not intended to limit the scope of the invention in any manner. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification. Unless otherwise defined, 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 pertains. In the case of conflict, the present document, including definitions will control.
In order that the present invention may be more readily understood, reference will now be made, by way of example, to the following description. It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art. Other embodiments can be practiced that are also within the scope of the present invention. The following illustrations of examples are intended to illustrate a stable synergistic fungicidal composition, but in no way limit the scope of the present invention.
Examples

A stable Suspension Concentrate (SC) formulation of Dimethomorph, Cyazofamid and Difenoconazole according to the present invention was prepared as follows:

SC (Suspension Concentrate)
Sr.
No. Component Composition


1 2 3 4 5
1 Dimethomorph Technical 32 32 32 32 32
2 Cyazofamid Technical 5 5 5 5 5
3 Difenoconazole Technical 8 8 8 8 8
4 Acrylic graft Copolymer 3.00 3.00 3.00 3.00 3.00
5 Naphthalene sulfonic acid, sodium salt condensate with formaldehyde 4.00 4.00 4.00 4.00 4.00
6 Blend of Poly terpene Resin 0.00 0.50 1.00 2.50 5.00
7 Silicone Antifoam 0.50 0.50 0.50 0.50 0.50
8 Benzisothiazoline 0.10 0.10 0.10 0.10 0.10
9 Glycol 5.00 5.00 5.00 5.00 5.00
10 Polysaccharides 0.10 0.10 0.10 0.10 0.10
11 DM water QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100
Example 1:

SC (Suspension Concentrate)
Sr. No. Recipe % w/w
1 Dimethomorph Technical 10-70%
2 Cyazofamid Technical 2-30%
3 Difenoconazole Technical 2-40%
4 Dispersing Agent- Polyarylphenyl ether phosphate, tristyryl phenol ethylated /Acrylic Copolymer/ Ethoxylated Tristryl phenol Sulphate, Naphthalene sulfonic acid, sodium salt condensate with formaldehyde, Ethoxylated oleyl cetyl alcohol, Polyalkylene glycol ether, Ethoxylated Fatty alcohol 0.5-10%
5 Wetting Agent- Tristyryl phenol ethoxylate
nonionic
emulsifier/ Mixture of non-ionic surfactants
& Alkoxylated Alcohol/Block copolymer, 0.5-10%
6 Antifoaming Agent-Siloxane polyalkyleneoxide 0.01-1%
7 Antifreezing Agent- Glycol, Propylene Glycol, Mono ethylene glycol, Glycerin, Diethylene glycol 0.1-10%
8 Adjuvants-Silicone Ethoxylated Oil, Polyvinyl Pyrrolidon,Poly vinyl Alcohol, Blend of poly terpene resin 0.1-10%

9 Filler- Silicon Dioxide/China -Clay/Kaolin/T ale/starch 0.1-5%
10 Anti-bacterial - Benzisothiazolin-3-one / Formaldehyde/Sodium benzoate/Sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one 0.01-1%
11 Polysaccharides/carboxymethyl cellulose/Bentonite Clay/Aluminium Magnesium Silicate 0.01-3%
12 DM water Q.sto
make
100
Total 100
Example 2:

SC (Suspension Concentrate)
Sr. No. Recipe % w/w
1 Dimethomorph Technical 20.00%
2 Cyazofamid Technical 10.00%
3 Difenoconazole Technical 10.00%
4 Dispersing Agent- Tristyrylphenol Ethoxylate Amine salt of phosphate 3%
5 Wetting Agent- Block copolymer, 2%
6 Antifoaming Agent-Siloxane polyalkyleneoxide 0.20%
7 Antifreezing Agent- Propylene Glycol 5%
8 Adjuvants-Blend of poly terpene resin 1%
9 Filler- China -Clay 1%
10 Anti-bacterial - Benzisothiazolin-3-one 0.10%
11 Polysaccharides 0.10%
12 DM water Q.sto make 100
Total 100
Process: Required quantity of water, biocide, and defoamer followed by addition of gum powder are homogenized with stirring to obtain a gum solution (Gum Solution should be made 12-18 hour prior to use). Required quantity of DM water, wetting agent, dispersing agent & suspending agents, colourant/dye was added into the charged vessel followed by homogenization for a period of ranging between 45 - 60 minutes using high shear homogeniser to obtain a homogenized slurry. Technical and other remaining adjuvants excluding 'antifreeze & thickeners' were added into the homogenized slurry to obtain a uniform slurry. Half of the quantity of required antifoam

agent was added into the slurry. The uniform slurry mixture was then passed through appropriate particle size reduction equipment (Dyno-Mill) until the granule material of the desired particle size was achieved. Remaining half of the quantity of required antifoam agent along with the antifreeze agent was added to the granule material as obtained. Gum solution as obtained in the first step was then added to obtain the Suspension Concentrate formulation.
A stable Water Dispersible Granule (WG) formulation of Dimethomorph, Cyazofamid and Difenoconazole according to the present invention was prepared as follows:

WG (Water Dispersible Granule)
Sr. No. Component Composition


1 2 3 4 5
1 Dimethomorph Technical 70 10 15 20 30
2 Cyazofamid Technical 2 30 15 25 20
3 Difenoconazole Technical 2 2 40 5 10
4 Sodium Polycarboxylate 8.00 11.00 10.00 1.00 10.00
5 Sodium Lauryl Sulphate 6.00 7.00 4.00 5.00 4.00
6 Sodium ligno sulfonate 2.00 1.00 1.00 1.00 1.00
7 Sodium alkylnaphthalenesulfonate, formaldehyde condensate 0.50 0.50 0.50 0.50 0.50
8 Silicone based antifoam 0.10 0.10 0.10 0.10 0.10
9 Blend of poly terpene resin 0.10 0.10 0.10 0.10 0.10
10 Precipitated Silica 0.10 0.10 0.10 0.10 0.10
11 China Clay QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100
Example 3:

WG (Water Dispersible Granule)
Sr. No. Recipe % w/w
1 Dimethomorph Technical 50.00%
2 Cyazofamid Technical 15.00%
3 Difenoconazole Technical 10.00%
5 Dispersing Agent-Sodium Polycarboxylate 3.00
6 Wetting Agent-Sodium Lauryl Sulphate 4.00
7 Dispersing agent: Sodium alkyl naphthalene sulfonate blend 1.00
8 Adjuvants-Poly vinyl pyrrolidone 0.10
9 Antifoam-Polydimethyl Siloxane 0.10

10 Filler-China Clay QS to Make 100
Process: Required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical was mixed in a premixing blender for homogenization for a period of 30 minutes to obtain a pre-blended material. The pre-blended material as obtained in the first step was blended through Jet mill/ air classifier mills followed by blending in post blender for a period of ~1.5 hour to obtain a homogeneous mixture. Required quantity of water (qs) was then added to make a dough. The dough was then passed through the extruder to obtain granules of required size. Wet granules as obtained were passed through the fluidised bed drier followed by grading using vibrating screens to obtain the wettable granules.
A stable Wettable Powder (WP) of Dimethomorph, Cyazofamid and Difenoconazole according to the present invention was prepared as follows:

WP (Wettable Powder)
Sr. No. Component Composition


1 2 3 4 5
1 Dimethomorph Technical 70 10 15 20 30
2 Cyazofamid Technical 2 30 15 25 20
3 Difenoconazole Technical 2 2 40 5 10
4 Sodium Polycarboxylate 8.00 8.00 8.00 8.00 8.00
5 Sodium Lauryl Sulphate 5.00 5.00 5.00 5.00 5.00
6 Blend of poly terpene resin 1.00 1.00 1.00 1.00 1.00
7 Sodium alkylnaphthalenesulfonate, formaldehyde condensate 0.50 0.50 0.50 0.50 0.50
8 Silicone based antifoam 0.10 0.10 0.10 0.10 0.10
9 Starch 5.00 5.00 5.00 5.00 5.00
10 Precipitated Silica 0.10 0.10 0.10 0.10 0.10
11 China Clay QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100
Example 4:

WP (Wettable Powder)
Sr. No. Recipe % w/w
1 Dimethomorph Technical 50.00%
2 Cyazofamid Technical 30.00%
3 Difenoconazole Technical 5.00%

5 Dispersing Agent-Sodium ligno sulfonate 3.00
6 Wetting Agent-Sodium Lauryl Sulphate 4.00
7 Dispersing Sodium alkyl naphthalene sulfonate blend 1.00
8 Adjuvants-Poly vinyl pyrrolidone 1.00
9 Antifoam-Polydimethyl Siloxane 0.10
10 Filler-China Clay QSto
Make
100
Process: Required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical were charged in premixing blender for homogenization for a period of 30 minutes to obtain a pre-blended material. The pre-blended material was grinded through Jet mill/ air classifier mills followed by blending in post blender for a period of -1.5 hr to obtain a homogeneous material. The homogenous material as obtained was unloaded and analysed.
A stable Flowable concentrate for seed treatment (FS) of Dimethomorph, Cyazofamid and Difenoconazole according to the present invention was prepared as follows:

FS (Flowable Slurry)
Sr. No. Component Composition


1 2 3 4 5
1 Dimethomorph Technical 10 30 10 12 14
2 Cyazofamid Technical 2 10 30 5 20
3 Difenoconazole Technical 2 5 3 30 6
4 Acrylic Copolymer 3.00 3.00 3.00 3.00 3.00
5 Naphthalene sulfonic acid, sodium salt condensate with formaldehyde 4.00 4.00 4.00 4.00 4.00
6 Blend of poly terpene resin 1.00 1.00 1.00 1.00 1.00
7 Silicone Antifoam 0.50 0.50 0.50 0.50 0.50
8 Benzisothiazoline 0.10 0.10 0.10 0.10 0.10
9 Glycol 5.00 5.00 5.00 5.00 5.00
10 Polysaccharides 0.10 0.10 0.10 0.10 0.10
11 DM water QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100
Example 5:

Flowable Slurry (FS)
Sr. No. Recipe % w/w
1 Dimethomorph Technical 15.00%
2 Cyazofamid Technical 10.00%
3 Difenoconazole Technical 20.00%

4 Dispersing Agent- Tristyrylphenol Ethoxylate Amine salt of phosphate 3%
5 Wetting Agent- Block copolymer, 2%
6 Antifoaming Agent-Siloxane polyalkyleneoxide 0.20%
7 Antifreezing Agent- Propylene Glycol 5%
8 Filler- China -Clay 1%
9 Anti-bacterial - Benzisothiazolin-3-one 0.10%
10 Adjuvants-Blend of poly terpene resin 1%
11 Polysaccharides 0.10%
12 DM water Q.s to make 100
Total 100
Process: Required quantity of water, biocide, and defoamer followed by addition of gum powder are homogenized with stirring to obtain a gum solution (Gum Solution should be made 12-18 hour prior to use). Required quantity of DM water, wetting agent, dispersing agent & suspending agents, colourant/dye was added into the charged vessel followed by homogenization for a period of ranging between 45 - 60 minutes using high shear homogeniser to obtain a homogenized slurry. Technical and other remaining adjuvants excluding 'antifreeze & thickeners' were added into the homogenized slurry to obtain a uniform slurry. Half of the quantity of required antifoam agent was added into the slurry. The uniform slurry mixture was then passed through appropriate particle size reduction equipment (Dyno-Mill) until the granule material of the desired particle size was achieved. Remaining half of the quantity of required antifoam agent along with the antifreeze agent was added to the granule material as obtained. Gum solution as obtained in the first step was then added to obtain the Flowable concentrate for seed treatment (FS).
A stable Granule (GR) formulation Dimethomorph, Cyazofamid and Difenoconazole
according to the present invention was prepared as follows:

GR (Granule)
Sr. No. Component Composition


1 2 3 4 5
1 Dimethomorph Technical 10 11 12 15 10
2 Cyazofamid Technical 3 5 5 5 5
3 Difenoconazole Technical 2 5 6 3 7
4 Sodium Polycarboxylate 3.00 3.00 3.00 3.00 3.00
5 Sodium Lauryl Sulphate 4.00 4.00 4.00 4.00 4.00
6 Pigment blue 0.10 0.10 0.10 0.10 0.10
7 Blend of poly terpene resin 0.50 0.50 0.50 0.50 0.50
9 China Clay 5.00 5.00 5.00 5.00 5.00

10 DM water 1.00 2.00 1.00 2.00 1.00
11 Sand QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100
Example 6:

Granule (GR)
Sr. No. Recipe % w/w
1 Dimethomorph Technical 10.00%
2 Cyazofamid Technical 2.00%
3 Difenoconazole Technical 2.00%
4 Dispersing Agent- Calcium Ligno sulphate 3%
5 Pigment Blue 0.20%
6 Filler- China -Clay 5%
7 Adjuvants-Poly vinyl pyrrolidone 0.10%
8 DM water 1%
9 Sand Q.sto make 100
Total 100
Process: Required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical was mixed in a premixing blender for homogenization for a period of 30 minutes to obtain a pre-blended material. The pre-blended material as obtained in the first step was blended through Jet mill/ air classifier mills followed by blending in post blender for a period of ~1.5 hour to obtain a homogeneous mixture. Then required quantity of sand was charged in the granulator, later DM water sticking agent and remaining material was added till it became homogeneous. The finely grinded material was then completely coated on sand and the resulting formulation was blended for 30 minutes to obtain the granule formulation.
A stable Suspo-emulsion (SE) of Dimethomorph, Cyazofamid and Difenoconazole according to the present invention was prepared as follows:

SE (Suspo Emulsion)
Sr.
No. Component Composition


1 2 3 4 5
1 Dimethomorph Technical 32 32 32 32 32
2 Cyazofamid Technical 5 5 5 5 5
3 Difenoconazole Technical 8 8 8 8 8
4 Acrylic graft Copolymer 3.00 3.00 3.00 3.00 3.00
5 Naphthalene sulfonic acid, sodium salt condensate with formaldehyde 4.00 4.00 4.00 4.00 4.00

6 Blend of Poly terpene Resin 0.00 0.50 1.00 2.50 5.00
7 Silicone Antifoam 0.50 0.50 0.50 0.50 0.50
8 Benzisothiazoline 0.10 0.10 0.10 0.10 0.10
9 Glycol 5.00 5.00 5.00 5.00 5.00
10 1-Octanol 30.00 25.00 20.00 30.00 15.00
11 Polysaccharides 0.10 0.10 0.10 0.10 0.10
12 DM water QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100 QSto
Make
100
Example 7:

Suspo-Emulsion (SE)
Sr. No. Raw Materials details % w/w
1 Dimethomorph Technical 12.00%
2 Cyazofamid Technical 15.00%
3 Difenoconazole Technical 10.00%
4 Dispersing Agent- Tristyrylphenol Ethoxylate Amine salt of phosphate 3%
5 Wetting Agent- Block copolymer, 2%
6 Antifoaming Agent-Siloxane polyalkyleneoxide 0.20%
7 Antifreezing Agent- Propylene Glycol 5%
8 1-octanol 10%
9 Anti-bacterial - Benzisothiazolin-3-one 0.10%
10 Adjuvants-Blend of poly terpene resin 1%
11 Polysaccharides 0.10%
12 DM water Q.s to make 100
Total 100
Process: Required quantity of water, biocide, and defoamer followed by addition of gum powder are homogenized with stirring to obtain a gum solution (Gum Solution should be made 12-18 hour prior to use). Required quantity of DM water is charged, wetting agent, dispersing agent & suspending agents, colorant/dye was added into the charged vessel followed by homogenization for a period of ranging between 45 - 60 minutes using high shear homogeniser to obtain a homogenized slurry. Technical and other remaining adjuvants excluding 'antifreeze & thickeners' were added into the homogenized slurry to obtain a uniform slurry. Half of the quantity of required antifoam agent was added into the slurry. The uniform slurry mixture was then passed through appropriate particle size reduction equipment (Dyno-Mill) until the granule material of the desired particle size was achieved. Remaining half of the quantity of required antifoam agent along with

the antifreeze agent was added to the granule material as obtained. Gum solution as obtained in the first step was then added to obtain the suspo-emulsion.
Storage stability and shelf-life study
Accelerated Heat Stability (AHS) Study:
According to the FAO/ WHO manual, accelerated stability study is conducted at 54 ± 2 °C for 14 days as default parameters. A study was conducted at accelerated conditions for upto 42 days and it was found that the active ingredients were storage stable at normal and accelerated conditions without any degradation.
Table 1

imeters Specification (In House) Initial Cold
storage
stability
at 0 + 2
°C for 14
days Heat stability study at
54 + 2
°C for 14
days Heat stability study at
54 + 2
°C for 21
days Heat stability study at
54 + 2
°C for 28
days Heat stability study at
54 + 2
°C for 35
days Heat stability study at
54 + 2
°C for 42
days
ription Off white to
light brown
Colour Complies Complies Complies Complies Complies Complies Complies
sthomorph ent 25(+5%,-5%) 25.9 25.8 25.7 25.7 25.6 25.4 25.2
sthomorph ensibility Min 60% 96.5 96.4 95.6 95.4 95.1 94.5 94.3
:ofamid ent 3.5(+10%,-
5%) 3.66 3.65 3.63 3.61 3.58 3.56 3.54
:ofamid ensibility Min 60% 98.7 98.5 98.2 97.9 97.8 97.8 97.5
noconazole ent 6(+10%,-5%) 6.27 6.27 6.23 6.22 6.21 6.19 6.15
noconazole ensibility Min. 60 96.7 96.4 96.3 95.9 95.4 95.2 95.1
1% ous tion) 4 to 9 6.5 6.5 6.5 6.5 6.5 6.5 6.5
osity, Cps 300-700 456 460 458 459 462 463 465
Sieve
ses through
icron) Min 98.0% 99.5 99.4 99.4 99.2 99.1 99 98.9
Density 1.0-1.20 1.1 1.1 1.1 1.1 1.1 1.1 1.1
ability ue Max 5.0% 2.8 2.8 2.9 3.1 3.1 3.1 3.2
Room temperature storage data

Table 2

Specification Study Duration
rameters In House 1 month 6 months 12 months 24 months 30 months 36 months 42 months
ription Off white to
light brown
Color Complies Complies Complies Complies Complies Complies Complies
sthomorph ent 25 (+5%, -5%) 25.9 25.8 25.7 25.6 25.5 25.4 25.1
sthomorph ensibility Min 60% 96.5 96.4 95.6 95.4 95.1 94.5 94.3
:ofamid ent 3.5(+10%,-5%) 3.66 3.64 3.62 3.61 3.57 3.56 3.52
:ofamid ensibility Min 60% 98.7 98.6 98.4 97.9 97.5 97.4 97.1
noconazole ent 6(+10%,-5%) 6.263 6.25 6.23 6.21 6.21 6.19 6.14
noconazole ensibility Min. 60 96.5 96.4 96.2 95.7 95.5 95.3 95.1
1% ous tion) 4 to 9 6.5 6.5 6.5 6.5 6.5 6.5 6.5
osity, Cps 300-700 456 459 460 461 462 463 465
Sieve
ses through
icron) Min 98.0% 99.5 99.5 99.4 99.2 99.1 99 98.7
Density 1.0-1.20 1.1 1.1 1.1 1.1 1.1 1.1 1.1
ability ue Max 5.0% 2.8 2.9 3.1 3.2 3.3 3.4 3.5
The shelf life of commercially available formulations comprising Cyazofamid or Dimethomorph or Difenoconazole fungicides is 2 years. However, the composition of the present invention is found to be stable for at least 42 months.
Biological Examples: Bio-efficacy studies
Bio-efficacy of the fungicidal composition of the present invention:
Field trials were conducted on Tomato crop infested with Late Blight (Phytopthora infestans) and the effect of the present invention was studied to understand the selective and effective control of Phytopthora infestans, phytotoxicity, crop yield and increase in rainfastness.
A synergistic effect exists wherever the action of a combination 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 fungicidal activity than the sum of the fungicidal activities of the individual components.
The presence of a synergistic effect between three active ingredients is established with the aid of the Colby equation (se S. R. Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations', Weeds, 1967,15,20-22). The action expected for a given combination of two active components can be calculated as follows:
p = A + B + c _ {d£lf£±g£} + {JE£.}
r L 100 y L10000 J
Using the method of Colby, the presence of a synergistic interaction between three active ingredients is established by first calculating the predicted activity, p, of the mixture based on activities of the three components applied alone. If'p' is lower than the experimentally established efficacy, Synergism has occurred. In the equation above, A is the fungicidal activity in percentage control of one component applied alone at rate x. The B is the fungicidal activity in percentage control of the second component applied at rate y & similarly C is the corresponding value for the third component applied at rate z. The equation estimates p, the fungicidal activity of the mixture of A at rate X with B at rate y & C at rate z if their effects are strictly additive and no interaction has occurred.
Table 3

Details of Experiment
Experiment design: Randomized Block Design (RBD)
Replication: Three
Treatments: 35 including control plot
Plot size: 5MX5M
Plant Spacing: Row to Row 75 cm, Plant to plant 45 cm
Crop & Variety Tomato (Variety - Pusa Hybrid-1)
Time & no. of Sprays: Two sprays at 10 days interval
Spray volume: 500 1/ha
Method of application: Knap sack spray fitted with flat fan nozzle

The Tomato crop was raised in the field as per the standard agronomic practices, fertilization @ N: P205: K20 : 75:40:25 kg/ha was given at the required stages. The fungicidal sprayings were done as preventive spray and second spray at 10 days after first spray. The observations on cumulative disease severity and incidence of late blight were recorded at 10 days after second application.
Late blight disease:
Total number of healthy and infected leaves from a sample of 100 leaves in a plot area was recorded. Later the % of disease incidence was calculated by using the formula given below:

% Disease incidence on leaves

No. of leaves infected X 100 No. of leaves observed

The disease severity score can be interpreted as per the table given below:
The Disease severity was recorded by using the following scale prescribed by Mayee & Datar, 1986.
Table 4

Score Disease symptoms of Early blight
0 Disease free leaves of test plants
1 Sparingly small irregular brown spots covering maximum of 1% of leaf surface area
3 Small irregular, brown spots with concentric rings covering of 1% - 10% of leaf surface area
5 Enlarging of lesions, irregular, brown in colour with concentric rings, covering 11-25% of leaf surface area.
7 Lesions coalesce to form irregular, dark brown patches with concentric rings covering 26-50% of the leaf surface area, Lesions also appear on stems and petioles of affected plants.
9 Lesions coalesce to form irregular, dark brown patches with concentric rings covering >51% of the leaf surface area, Lesions also appear on stems and petioles of affected plants.

Blight oPD! (Severity %)

Sum of numerical disease rating X 100 Total No. of samples X Maximum of disease rating scale

Bio-Efficacy Experiments
Test Suspensions comprising a single active ingredient is sprayed to demonstrate the control efficacy of the active ingredient individually. To demonstrate the control efficacy of a combination, the active ingredients can be combined in the appropriate amounts in a single test Suspension, stock solutions of individual active ingredients can be prepared and then combined in the appropriate ratio, and diluted to the final desired concentration to form a test Suspension or test Suspensions comprising single active ingredients can be sprayed sequentially in the desired ratio.

Target disease: Late blight of Tomato Phytophthora infestans
Results of Bio-efficacy tests comprising of Experiments are given in Table. 7 & 8, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to control). Columns labelled Avg. Observed % disease control indicates average of three replications. Columns labelled Expected indicate the expected value for each treatment mixture using the Colby equation.
TEST COMPOSITIONS PREPARATION:
Test compositions were first mixed with purified water.
The resulting test Suspensions were then used in the following tests.
Test Suspensions were sprayed to the point of run-of on the test plants at the equivalent rates as
mentioned in the Table. 5. as g/ha of the active ingredient.
The tests were replicated three times and the results reported are the mean average of the three
replicates.

Table 5

Second active Compound Dose Rate First active compound -Dimethomorph Third active Compound Dose Rate
g a.i./ha Dose Rate (g a.i./ha)
g a.i./ha
0 0 100 200 400 500 Cyazofamid 0
25 0 100 200 400 500
25
Difenoconazole 50 0 100 200 400 500
50
100 0 100 200 400 500
62.5
125 0 100 200 400 500
75
The treatments marked with * Asterix are pre-formulated compositions prepared as per the present invention. The % amount of active(s) in each of these treatments is as follows:
Table 6

Tl9*

Ready to use premix formulation of Dimethomorph 8% + Difenoconazole 8% + Cyazofamid 5% - SC/SE


T24*

Ready to use premix formulation of Dimethomorph 16% + Difenoconazole 8% + Cyazofamid 5% - SC/SE


T29*

Ready to use premix formulation of Dimethomorph 32% + Difenoconazole 8% + Cyazofamid 5% - SC/SE

Table 7
ic Fungicidal effect of the fungicidal composition comprising Dimethomorph + Difenoconazole + Cyazofamid against Late Blight (Phytopthora infestans) based on reduction of Disease incidence %

Dimethomorph
50% WP Difenoconazole 25% EC Cyazofamid 34.5% SC Application dose Observed Late Blight
Phytophthora
infestans @10 DAT
(2nd Spray) Expected Late Blight
Phytophthor a infestans @10 DAT (2nd Spray) Colby
Ratio =
Observed
/ Expected
%
infection
incidence
or PDA
g a.i./ha g or ml/ha Disease Incidence
% Disease control %over control Disease control % Disease control
%
100 0 0 200.00 62.00 30.85 - -
200 0 0 400.00 51.33 42.75 -
400 0 0 800.00 38.50 57.06 - -
500 0 0 1000.00 27.67 69.14 - -
0 25 0 100.00 59.66 33.46 -
0 50 0 200.00 47.00 47.58 - -
0 100 0 400.00 35.60 60.29 - -
0 125 0 500.00 29.33 67.29 - -
0 0 25 62.50 66.33 26.02 - -
0 0 50 125.00 49.00 45.35 - -
0 0 62.5 156.25 35.66 60.23 - -
0 0 75 187.50 25.50 71.56 - -
400 0 62.5 (800+0+ 156.25) 17.00 81.04 82.92 0.98
400 100 0 (800+400+0) 18.33 79.56 82.95 0.96
0 100 62.5 (0+400+ 156.25) 19.66 78.07 84.21 0.93
100 25 25 (200+100+ 62.5) 45.00 49.81 65.96 0.76
100 50 50 (200+200+ 125) 33.30 62.86 80.19 0.78
100 100 62.5 (200+400+ 156.25) 23.30 74.01 89.08 0.83
100 100 62.5 1250.00 15.66 82.53 89.08 0.93

T20 100 125 75 (200+500+ 187.5) 12.33 86.25 93.57 0.92
T2i 200 25 25 (400+100+ 62.5) 28.00 68.77 71.82 0.96
T22 200 50 50 (400+200+ 125) 19.50 78.25 83.60 0.94
T23 200 100 62.5 (400+400+ 156.25) 10.00 88.85 90.96 0.98
T24» 200 100 62.5 1250.00 8.00 91.08 90.96 1.00
T25 200 125 75 (400+500+ 187.5) 5.67 93.68 94.67 0.99
T26 400 25 25 (800+100+ 62.5) 22.67 74.72 78.86 0.95
T27 400 50 50 (800+200+ 125) 12.67 85.87 87.70 0.98
T28 400 100 62.5 (800+400+15 6.25) 6.87 92.34 93.22 0.99
T29* 400 100 62.5 1250.00 1.33 98.52 93.22 1.06
T30 400 125 75 (800+500+ 187.5) 0.00 100.00 96.01 1.04
T31 500 25 25 (1000+100+ 62.5) 8.67 90.33 84.81 1.07
T32 500 50 50 (1000+200+ 125) 5.33 94.06 91.16 1.03
T33 500 100 62.5 (1000+400+ 156.25) 0.00 100.00 95.13 1.05
T34 500 125 75 (1000+500+ 187.5) 0.00 100.00 97.13 1.03
T35 0 0 0 Control plot 89.66 0.00 - -
5 Treatments marked with * are pre-mix formulation as per the present invention
Table 8

Synergistic Fungicidal effect of the fungicidal composition comprising Dimethomorph + Difenoconazole + Cyazofamid against Late Blight {Phytophthora infestans) based on reduction in PDI
Treatments Dimethomorph
50% WP Difenoconazole 25% EC Cyazofamid 34.5% SC Application dose Observed Late Blight Phytopthora infestans
@10 DAT (2nd Spray) Expected
Late Blight
Phytopthora
infestans
@10 DAT (2nd Spray) Colby Ratio = Observed /Expected % Disease incidence or PDI

g a.i./ha g or ml/ha PDI
(Percent Disease Index) Reducti on in PDI over
control Reduction in PDI
Ti 100 0 0 200.00 60.30 34.69 - -

T2 200 0 0 400.00 45.67 50.54 -
T3 400 0 0 800.00 35.00 62.09 - -
T4 500 0 0 1000.00 25.00 72.92 - -
T5 0 25 0 100.00 62.00 32.85 -
T6 0 50 0 200.00 53.30 42.27 - -
T7 0 100 0 400.00 43.30 53.10 - -
T8 0 125 0 500.00 36.00 61.01 - -
T9 0 0 25 62.50 56.00 39.35 - -
Tio 0 0 50 125.00 49.00 46.93 - -
Tn 0 0 62.5 156.25 33.00 64.26 - -
T12 0 0 75 187.50 26.00 71.84 - -
T13 400 0 62.5 (800+0+ 156.25) 16.00 82.67 86.45 0.96
T14 400 100 0 (800+400+ 0) 19.00 79.42 82.22 0.97
Ti5 0 100 62.5 (0+400+ 156.25) 18.00 80.50 83.24 0.97
Tl6 100 25 25 (200+100+ 62.5) 45.00 51.26 73.40 0.70
T17 100 50 50 (200+200+ 125) 37.00 59.93 79.99 0.75
Tig 100 100 62.5 (200+400+ 156.25) 29.67 67.87 89.05 0.76
Tl9» 100 100 62.5 1250.00 24.66 73.29 89.05 0.82
T20 100 125 75 (200+500+ 187.5) 20.00 78.34 92.83 0.84
T21 200 25 25 (400+100+ 62.5) 31.00 66.42 79.85 0.83
T22 200 50 50 (400+200+ 125) 26.67 71.11 84.85 0.84
T23 200 100 62.5 (400+400+ 156.25) 21.00 77.26 91.71 0.84
T24» 200 100 62.5 1250.00 17.33 81.23 91.71 0.89
T25 200 125 75 (400+500+ 187.5) 16.33 82.31 94.57 0.87
T26 400 25 25 (800+100+ 62.5) 19.67 78.70 84.56 0.93
T27 400 50 50 (800+200+ 125) 12.00 87.00 88.39 0.98
T28 400 100 62.5 (800+400+ 156.25) 7.00 92.42 93.65 0.99
T29» 400 100 62.5 1250.00 3.33 96.39 93.65 1.03

T30 400 125 75 (800+500+ 187.5) 0.00 100.00 95.84 1.04
T3i 500 25 25 (1000+100 +62.5) 7.00 92.42 88.97 1.04
T32 500 50 50 (1000+200 +125) 0.00 100.00 91.70 1.09
T33 500 100 62.5 (1000+400 +156.25) 0.00 100.00 95.46 1.05
T34 500 125 75 (1000+500 +187.5) 0.00 100.00 97.03 1.03
T35 0 0 0 Control plot 92.33 0.00 - -
5 Treatments marked with * are pre-mix formulation as per the present invention
It can be observed from table 7 and table 8 that the compositions of the present invention showed synergistic effect and increased disease control as compared to binary and solo treatments. Further, it can also be observed that the composition of the present invention comprising bio-based efficacy enhancer such as blend of poly terpene resin showed better disease control as
10 compared to the tank-mix composition of same concentration of a.i/ hectare. For instance, Ti8 is
a tank mix of Dimethomorph lOOg + Difenoconazole lOOg + Cyazofamid 62.5G a.i./ha and T19 is a composition as claimed by the present invention with same % actives applied per hectare, However, T19 shows less disease incidence as compared to Tis. Similarly, T23 (tank-mix) and T24 (preformulated composition as per the present invention); T28 (tank-mix) and T29 (preformulated
15 composition as per the present invention) can be compared on the same lines, wherein, T24 and
T29 show better disease control over T23 and T28 respectively.
Table 9

Effect on Tomato yield of various Fungicidal composition comprising Dimethomorph + Difenoconazole + Cyazofamid
(mean average of 4 pickings)
Treatments Dimethomorj 50% WP Difenoconazole 25% EC Cyazofamid 34.5% SC Application dose of
formulated products Weighted average of Tomato yield after 3 pickings MT/ha Colby Ratio = Observ
ed /Expect
ed yield

g a.i./ha g or ml/ha Mean of
two
seasons
Yield
MT/ha % Yield
increased
over the
control
(observed
) % Yield
increase
(expected
)by
Colby
equation
Ti 100 0 0 200.00 7.80 23.81 - -

T2 200 0 0 400.00 8.33 32.22 -
T3 400 0 0 800.00 9.50 50.79 - -
T4 500 0 0 1000.00 10.00 58.73 - -
T5 0 25 0 100.00 6.50 3.17 -
T6 0 50 0 200.00 7.67 21.75 - -
T7 0 100 0 400.00 8.33 32.22 - -
T8 0 125 0 500.00 9.00 42.86 - -
T9 0 0 25 62.50 8.87 40.79 - -
Tio 0 0 50 125.00 9.00 42.86 - -
Tn 0 0 62.5 156.25 10.33 63.97 - -
T12 0 0 75 187.50 11.33 79.84 - -
T13 400 0 62.5 (800+0+15 6.25) 18.67 196.35 18.85 0.99
T14 400 100 0 (800+400+ 0) 16.33 159.21 17.04 0.96
Ti5 0 100 62.5 (0+400+15 6.25) 16.00 153.97 17.80 0.90
Tl6 100 25 25 (200+100+ 62.5) 12.33 95.71 21.44 0.58
T17 100 50 50 (200+200+ 125) 14.50 130.16 22.53 0.64
Tig 100 100 62.5 (200+400+ 156.25) 16.33 159.21 24.21 0.67
Tl9» 100 100 62.5 1250.00 17.50 177.78 24.21 0.72
T20 100 125 75 (200+500+ 187.5) 17.67 180.48 25.60 0.69
T21 200 25 25 (400+100+ 62.5) 14.00 122.22 21.89 0.64
T22 200 50 50 (400+200+ 125) 15.67 148.73 22.98 0.68
T23 200 100 62.5 (400+400+ 156.25) 17.00 169.84 24.65 0.69
T24» 200 100 62.5 1250.00 18.50 193.65 24.65 0.75
T25 200 125 75 (400+500+ 187.5) 18.33 190.95 26.03 0.70
T26 400 25 25 (800+100+ 62.5) 16.33 159.21 22.89 0.71
T27 400 50 50 (800+200+ 125) 21.33 238.57 23.96 0.89
T28 400 100 62.5 (800+400+ 156.25) 23.67 275.71 25.61 0.92
T29* 400 100 62.5 1250.00 27.00 328.57 25.61 1.05

T30 400 125 75 (800+500+ 187.5) 27.33 333.81 26.98 1.01
T3i 500 25 25 (1000+100 + 62.5) 22.67 259.84 23.31 0.97
T32 500 50 50 (1000+200 +125) 25.33 302.06 24.38 1.04
T33 500 100 62.5 (1000+400 + 156.25) 27.00 328.57 26.02 1.04
T34 500 125 75 (1000+ 500+ 187.5) 28.00 344.44 27.38 1.02
T35 0 0 0 Control plot 6.30 0.00 - -
5 Treatments marked with * are pre-mix formulation as per the present invention
Highest yield was recorded with the compositions of the present invention which is optimum and at par with the yield observed at higher doses in treatments from T30-T34.
Moreover, there is an increase in yield with T29 as compared to T28, wherein T28 is a tank-mix of
the claimed composition.
10 Further, there is an improved yield with the composition of the present invention comprising
specific bio-based efficacy enhancers such as blend of poly terpene resin.
Effect of Blend of Poly terpene resin with respect to Rainfastness:
A study was conducted in order to check the effectiveness of blend of poly terpene resin added
as an adjuvant in the composition of the present invention.
15 Material & Method:
Pots with grown up tomato plants at 40 days after transplanting were taken. 20 such pots with
plants of uniform height and growth were taken for the study. 10 different treatments were carried
out on 2 plants each.
The effect of following different compositions were studied at two different intervals on each
20 plant.
1. Dimethomorph 800 ppm of 7 different compositions with varying amount of blend of
poly terpene resin added as an adjuvant in 0.00, 0.50, 1.00, 2.50, 5.00, 7.5 and 10 weight
% of the total formulation.
2. Cyazofamid 125 ppm of 7 different compositions with varying amount of blend of poly
25 terpene resin added as an adjuvant in 0.00, 0.50, 1.00, 2.50, 5.00, 7.5 and 10 weight % of
the total formulation.

3. Difenoconazole 200 ppm of 7 different compositions with varying amount of blend of poly terpene resin added as an adjuvant in 0.00, 0.50, 1.00, 2.50, 5.00, 7.5 and 10 weight % of the total formulation.
4. SC formulation of 7 different compositions comprising a synergistic combination of Dimethomorph 800 ppm, Cyazofamid 125 ppm and Difenoconazole 200 ppm with varying amount of blend of poly terpene resin added as an adjuvant in 0.00, 0.50, 1.00, 2.50, 5.00, 7.5 and 10 weight % of the total formulation.
5. SE formulation of 7 different compositions comprising a synergistic combination of Dimethomorph 800 ppm, Cyazofamid 125 ppm and Difenoconazole 200 ppm with varying amount of blend of poly terpene resin added as an adjuvant in 0.00, 0.50, 1.00, 2.50, 5.00, 7.5 and 10 weight % of the total formulation.
Step 1: Each of the composition was sprayed on 2 crops each till the point of run-off Later an
average of 2 readings were recorded in the table represented as table 9.
After spraying of the above compositions, 2 hours post treatment, 5 leaves were plucked from
the plant for sampling. The leaves of the treated plants were washed separately in Acetone taken
as a solvent. After gently brushing off for any residual active on the leaves, the acetone solution
as obtained was run in HPLC developed in a suitable mobile phase. The amount of absorbance
at the fixed wavelength and retention time was noted for each of the acetone sample.
Step 2: The sprayed plants were washed under an artificial rain shower staged to discharge 250ml
of water per minute for 5 minutes. 2 hours after the shower, 5 leaves were again plucked from
the plants for sampling and same procedure with HPLC was repeated as above. Absorbance in
milli-Absorbance Units (mAU) was noted as an indicator of the amount of active(s) retained
before and after showering the plants. The same experiment was repeated for all the different
compositions comprising varying amount of blend of poly terpene resin.
A reading was also taken with 0% poly terpene resin to differentiate in the change in amount of
active(s) retained with and without its presence.
Table 10:

Concentration of a.i sprayed Total amount
of a.i sprayed in ppm Sampling Time % Amount of Blend of Poly terpene Resin



0.00 0.50 1.00 2.50 5.00 7.5 10
Dimethomorph
32% 800 ppm Amount of active retained in ppm (2 hours after spraying, 345 374 427 478 533 565 572
48

before washing under artificial rain shower)
2.

Amount of active retained in ppm (2 hours after washing under artificial rain shower) 111 153 235 291 384 429 446
% Retention after exposure to artificial rainfall 32.00 % 41.00
% 55.00 % 61.00
% 72.00 % 76.00 % 78.00 %
3. Cyazofamid
5% 125 ppm Amount of active retained in ppm (2 hours after spraying, before washing under artificial rain shower) 45 52 59 70 84 88 90
4.

Amount of active retained in ppm (2 hours after washing under artificial rain shower) 5 12 26 37 57 63 67
% Retention after exposure to artificial rainfall 11.11
% 23.08 % 44.07 % 52.86 % 67.86
% 71.59
% 74.44 %
5. Difenoconazole
8% 200 ppm Amount of active retained in ppm (2 hours after spraying, before washing under artificial rain shower) 46 60 88 108 135 136 151
6.

Amount of active retained in ppm (2 hours after washing under artificial rain shower) 14 27 40 54 84 96 101
% Retention after exposure to artificial rainfall 30.43 % 45.00 % 45.45 % 50.00 % 62.22 % 70.59 % 66.89
%
7. Dimethomorph 32% +
Difenoconazole 8% +
Cyazofamid 5% SC (800 +
125 +
200) ppm Amount of active retained in ppm (2 hours after spraying, before washing under artificial rain shower) 444 502 597 686 795 811 823
8.

Amount of active retained in ppm (2 hours after washing under artificial rain shower) 126 202 323 405 553 601 623
49

% Retention after exposure to artificial rainfall 28.38 % 40.24 % 54.10
% 59.04 % 69.56
% 74.11
% 75.70 %
9. Dimethomorph 32% +
Difenoconazole 8% +
Cyazofamid 5% SE (800 +
125 +
200) ppm Amount of active retained in ppm (2 hours after spraying, before washing under artificial rain shower) 453 512 624 701 825 834 836
10.

Amount of active retained in ppm (2 hours after washing under artificial rain shower) 133 222 343 439 589 609 620
% Retention after exposure to artificial rainfall 29.36 % 43.36 % 54.97 % 62.62 % 71.39 % 73.02 % 74.16
%
5 From the table above, it can be observed that the amount of Dimethomorph, Cyazofamid and
Difenoconazole retained on the leaves in each of the compositions solo as well as SC and SE
formulations increases with the increase in the percentage amount of blend of poly terpene resin.
Further, % retention (with increase in % amount of blend of poly terpene resin) of actives is more
in the SC and SE compositions of the present invention as compared to solo compositions. Thus,
10 it can be concluded that optimum amount of blend of poly terpene resin acts as bio-based efficacy
enhancer by preventing the washing off of the active(s) (increased % retention of a.i) from the surface of the leaves by increasing the rainfastness of the composition of the present invention thereby providing improved penetration and efficacy.
Table 11:
15

Phytotoxicity effect of Fungicidal composition comprising Dimethomorph + Difenoconazole + Cyazofamid on
Tomato crop
Treatments Dimethomorj 50% WP Difenoconazole 25% EC Cyazofamid 34.5% SC Application dose Phytotoxicity % after 14
days of spray (mean of 2
sprays)

g a.i./ha g or ml/ha On leaves On flowers
and
Flower
drops Fruits and fruit
drops
Ti 100 0 0 200.00 NP NP NP
50

T2 200 0 0 400.00 NP NP NP
T3 400 0 0 800.00 NP NP NP
T4 500 0 0 1000.00 NP NP NP
T5 0 25 0 100.00 NP NP NP
T6 0 50 0 200.00 NP NP NP
T7 0 100 0 400.00 NP NP NP
T8 0 125 0 500.00 NP NP NP
T9 0 0 25 62.50 NP NP NP
Tio 0 0 50 125.00 NP NP NP
Tn 0 0 62.5 156.25 NP NP NP
T12 0 0 75 187.50 NP NP NP
T13 400 0 62.5 (800+0+ 156.25) NP NP NP
T14 400 100 0 (800+400+0) NP NP NP
Ti5 0 100 62.5 (0+400+ 156.25) NP NP NP
Tl6 100 25 25 (200+100+ 62.5) NP NP NP
T17 100 50 50 (200+200+ 125) NP NP NP
Tig 100 100 62.5 (200+400+ 156.25) NP NP NP
Tl9» 100 100 62.5 1250.00 NP NP NP
T20 100 125 75 (200+500+ 187.5) NP NP NP
T21 200 25 25 (400+100+ 62.5) NP NP NP
T22 200 50 50 (400+200+ 125) NP NP NP
T23 200 100 62.5 (400+400+ 156.25) NP NP NP
T24» 200 100 62.5 1250.00 NP NP NP
T25 200 125 75 (400+500+ 187.5) NP NP NP
T26 400 25 25 (800+100+ 62.5) NP NP NP
T27 400 50 50 (800+200+ 125) NP NP NP
T28 400 100 62.5 (800+400+15 6.25) NP NP NP
T29* 400 100 62.5 1250.00 NP NP NP
T30 400 125 75 (800+500+ 187.5) NP NP NP
51

T3i 500 25 25 (1000+100+ 62.5) NP NP NP
T32 500 50 50 (1000+200+ 125) NP NP NP
T33 500 100 62.5 (1000+400+ 156.25) NP NP NP
T34 500 125 75 (1000+500+ 187.5) NP NP NP
T35 0 0 0 Control plot NP NP NP
5 Treatments marked with * are pre-mix formulation as per the present invention
No signs of phytotoxicity or any incidence of flower/fruit drop was observed on tomato crops even at the higher doses of the ternary combination of the present invention.
Table 12:

tment; Dimethomoi 50% WP Difenoconazole 25% EC Cyazofamid 34.5% SC Application dose of
formulated products Weighted average of
Tomato yield after 3 pickings
MT/ha Cost
of Two
Fungicidal
sprays
including
spraying
operation/
ha. (Rs) Total
produce
income
Rs/ha
based
on Increased income
over control Benefit:
Cost
Ratio
g a.i./ha g or ml/ha Mean of
two
seasons
Yield
MT/ha
Tomato whole
sale price ofRs 9.5/kg Rs/ha

100 0 0 200.00 7.80 4360.00 74100 14250.00 3.27
200 0 0 400.00 8.33 6720.00 79135 19285.00 2.87
400 0 0 800.00 9.50 11440.00 90250 30400.00 2.66
500 0 0 1000.00 10.00 13800.00 95000 35150.00 2.55
0 25 0 100.00 6.50 2448.40 61750 1900.00 0.78
0 50 0 200.00 7.67 2896.80 72865 13015.00 4.49
0 100 0 400.00 8.33 3793.60 79135 19285.00 5.08
0 125 0 500.00 9.00 4242.00 85500 25650.00 6.05
0 0 25 62.50 8.87 4603.38 84265 24415.00 5.30
0 0 50 125.00 9.00 7206.75 85500 25650.00 3.56
0 0 62.5 156.25 10.33 8508.44 98135 38285.00 4.50
0 0 75 187.50 11.33 9810.13 107635 47785.00 4.87
400 0 62.5 (800+0+ 18.67 17948.44 177365 117515.00 6.55
52

156.25)
TM 400 100 0 (800+400+0) 16.33 13233.60 155135 95285.00 7.20
T15 0 100 62.5 (0+400+ 156.25) 16.00 10302.04 152000 92150.00 8.94
Tlfi 100 25 25 (200+100+ 62.5) 12.33 7411.78 117135 57285.00 7.73
T17 100 50 50 (200+200+ 125) 14.50 10463.55 137750 77900.00 7.44
Tig 100 100 62.5 (200+400+ 156.25) 16.33 12662.04 155135 95285.00 7.53
Tl9» 100 100 62.5 1250.00 17.50 12000.00 166250 106400.00 8.87
T20 100 125 75 (200+500+ 187.5) 17.67 14412.13 167865 108015.00 7.49
T21 200 25 25 (400+100+ 62.5) 14.00 9771.78 133000 73150.00 7.49
T22 200 50 50 (400+200+ 125) 15.67 12823.55 148865 89015.00 6.94
T23 200 100 62.5 (400+400+ 156.25) 17.00 15022.04 161500 101650.00 6.77
T24* 200 100 62.5 1250.00 18.50 13250.00 175750 115900.00 8.75
T25 200 125 75 (400+500+ 187.5) 18.33 16772.13 174135 114285.00 6.81
T26 400 25 25 (800+100+ 62.5) 16.33 14491.78 155135 95285.00 6.58
T27 400 50 50 (800+200+ 125) 21.33 17543.55 202635 142785.00 8.14
T28 400 100 62.5 (800+400+ 156.25) 23.67 19742.04 224865 165015.00 8.36
T29* 400 100 62.5 1250.00 27.00 14500.00 256500 196650.00 13.56
T30 400 125 75 (800+500+ 187.5) 27.33 21492.13 259635 199785.00 9.30
T31 500 25 25 (1000+100+ 62.5) 22.67 16851.78 215365 155515.00 9.23
T32 500 50 50 (1000+200+ 125) 25.33 19903.55 240635 180785.00 9.08
T33 500 100 62.5 (1000+400+ 27.00 22102.04 256500 196650.00 8.90
53

156.25)
T34 500 125 75 (1000+500+ 187.5) 28.00 23852.13 266000 206150.00 8.64
T35 0 0 0 Control plot 6.30 0 59850 0.00 -
5 Treatments marked with * are pre-mix formulation as per the present invention
From the above table, it can be observed that the Mean yield of two seasons increases with T19,
T24, T29 i.e. compositions of the present invention as compared to Ti8, T23 and T28 respectively
(tank mixtures) and any other binary or solo treatments. The composition of the present invention
provides significantly high yield at reduced doses of the a.i, thus, reducing the cost of a.i/ha.
10 Moreover, there is a significant increase in the income per/ha. Hence, the benefit: cost ratio is
high with the composition of the present invention.
The cost of a.i per kg/It is shown in the table below:
15 Table 13:

Spraying cost Rs/ha (per spray) 1000
Cost of Dimethomorph 50 WP Rs/kg 5900
Cost of Difenoconazole 25EC Rs/Lt 2242
Cost of Cyazofamid 34.4% EC Rs/Lt 20827
Cost of Dimethomorph 32%+ Difenoconazole 8% + Cyazofamid 5%-SE Rs/1 5000
Cost of Dimethomorph 16%+ Difenoconazole 8% + Cyazofamid 5%-SE Rs/1 4500
Cost of Dimethomorph 8%+ Difenoconazole 8% + Cyazofamid 5%-SE Rs/1 4000
From the foregoing it will be observed that numerous modifications and variations can be
effectuated without departing from the true spirit and scope of the novel concepts of the present
invention. It is to be understood that no limitations with respect to the specific embodiments
20 illustrated is intended or should be inferred. It should be understood that all such modifications
and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.

WE CLAIM:
[CLAIM 1]. A synergistic fungicidal composition comprising:
a. Cyazofamid or its agrochemically acceptable salts; and
b. Dimethomorph or its agrochemically acceptable salts; and
c. at least one triazole fungicide selected from Hexaconazole, Cyproconazole,
Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole,
Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its
agrochemically acceptable salts; and
d. One or more agrochemically acceptable excipients.
5
[CLAIM 2]. A synergistic fungicidal composition as claimed in claim 1 comprising:
a. Cyazofamid or its agrochemically acceptable salts in the range of 2-30% by weight of
the formulation; and
b. Dimethomorph or its agrochemically acceptable salts in the range of 10-70% by weight
of the formulation; and
c. at least one triazole fungicide selected from Hexaconazole, Cyproconazole,
Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole,
Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its
agrochemically acceptable salts in the range of 2-40% by weight; and
d. One or more of agrochemically acceptable excipients.
[CLAFM 3]. A synergistic fungicidal composition comprising:
a. Cyazofamid or its agrochemically acceptable salts in the range of 2-30% by weight of
the formulation; and
b. Dimethomorph or its agrochemically acceptable salts in the range of 10-70% by weight
of the formulation; and
c. at least one triazole fungicide selected from Hexaconazole, Cyproconazole,
Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole,
Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its
agrochemically acceptable salts in the range of 2-40% by weight; and
d. bio based efficacy enhancing agents;
e. One or more of agrochemically acceptable adjuvants; and
57

f One or more of agrochemically acceptable excipients.
[CLAIM 4]. The fungicidal composition as claimed in claim 1 to 3, wherein triazole fungicide is Difenoconazole.
[CLAIM 5]. The fungicidal composition as claimed in claim 1 to 3, wherein the agrochemically acceptable excipients are surfactant/dispersing agent, anti-freezing agent, anti-foaming agent, wetting agent, suspension aid, antimicrobial/anti-bacterial agent, thickening agent, quick coating agent or sticking agents/sticker, spreader, binders, adjuvants, fillers, emulsifiers, colouring pigments, dyes, preservatives, buffering agent and solvent thereof.
[CLAIM 6]. The fungicidal composition as claimed in claim 3, wherein the agrochemically acceptable adjuvants are selected from Silicone Ethoxylated Oil, Polyvinyl Pyrrolidone, Polyvinyl Alcohol or mixtures thereof and present in the range of 0.1-10% weight of the total composition.
[CLAIM 7]. The fungicidal composition as claimed in claim 3, wherein bio based efficacy enhancing agent is blend of polyterpene resin (natural oils) and present in the range of 0.1-10% weight of the total composition.
[CLAIM 8]. The fungicidal composition as claimed in claim 5, wherein wetting agent is selected form the group consisting of sodium lauryl sulphate, sodium dioctylsulphosuccinate, Tristyrylphenol ethoxylate non-ionic emulsifier/ mixture of non-ionic surfactants & Alkoxylated Alcohol/Block copolymer, alkyl phenol ethoxylates, and aliphatic alcohol ethoxylates, their salts and mixtures thereof and is present in the range of 0.5-10%) weight of the total composition.
[CLAIM 9]. The fungicidal composition as claimed in claim 5, wherein surfactants/dispersing agent is selected form the group consisting of sodium polycarboxylate, sodium lignosulphonates, calcium ligno sulphate, Polyphenyl ether phosphate, Tristyrylphenol Ethoxylate Amine salt of phosphate, tristyryl phenol ethylate, Acrylic Copolymer, Ethoxylated Tristryl phenol Sulphate, Naphthalene sulfonic acid, sodium salt condensate with formaldehyde, Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol, naphthalene sulphonate formaldehyde condensates, tristyrylphenolethoxylate phosphate, ethoxylated fatty alcohol, alky ethoxylates, EO-PO block copolymers, and
58

graft copolymers or mixtures thereof and present in the range of 0.5-10% weight of the total composition.
[CLAIM 10]. The fungicidal composition as claimed in claim 5, wherein antifoaming agent is selected form the group consisting of silicon emulsion based anti-foam agents, Siloxane polyalkyleneoxide, trisiloxane ethoxylates and mixtures thereof and present in the range of 0.01-1% weight of the total composition.
[CLAIM 11]. The fungicidal composition as claimed in claim 5, wherein anti-freezing agent is selected from the group consisting of glycols, monoethylene gycol, diethylene glycol, polyethylene glycols, methoxypolyethylene glycols, propylene glycol, polypropylene glycols, polybutylene glycols, glycerine, ethylene glycol and mixtures thereof and present in the range of 0.1-20% weight of the total composition.
[CLAIM 12]. The fungicidal composition as claimed in claim 5, wherein emulsifiers are selected from Castor oil ethoxylates, Calcium alkyl benzene sulfonate or mixtures thereof and present in the range of 0.1-10%) weight of the total composition.
[CLAIM 13]. The fungicidal composition as claimed in claim 5, wherein thickening agent is selected from the group consisting of montmorillonite, bentonite clay, magnesium aluminum silicate, attapulgite, natural extracts of seeds and seaweeds, guar gum, locust bean gum, carrageenam, xanthan gum, alginates, polysaccharides, methyl cellulose, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), bentonite clay, modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures thereof and present in the range of 0.01-3%> weight of the total composition
[CLAIM 14]. The fungicidal composition as claimed in claim 5, wherein antimicrobial/anti-bacterial agent is selected from the group consisting of propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt, hydroxy benzoic acid sodium salt, methyl p-hydroxy benzoate, and biocide such as sodium benzoate, sodium o-phenyl phenate, l,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates, Benzisothiazolin-3-one, Formaldehyde or mixtures thereof and present in the range of 0.01-1%) weight of the total formulation.
[CLAIM 15]. The fungicidal composition as claimed in claim 5, wherein filler is selected from the group consisting of Silicon Dioxide, bentonite clay, china clay, silica, kaolin, talc,
59

starch and diatomaceous earth and mixtures thereof and present in the range of 0.1-5% weight of the total composition.
[CLAIM 16]. The fungicidal composition as claimed in claim 5, wherein solvent is selected from glucitol, sorbitol, methanol, ethanol, n-propanol, dihydroxy alcohol alkyl ether, dihydroxy alcohol aryl ethers, 1-octanol and the like and present in the range of 10-30% weight of the total composition.
[CLAIM 17]. The fungicidal composition as claimed in claim 1 to 3, wherein the composition is in the form of Capsule suspension (CS), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion for foliar spray (ES), Emulsion, oil in water (EW), Flowable suspension/concentrate for foliar spray (FS), Granule/ soil applied (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (flowable concentrate) (SC), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP), Water dispersible granule (WG or WDG), Wettable powder (WP), Water dispersible powder for slurry treatment (WS), A mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), mixed formulation of CS and EW (ZW) or combination thereof.
[CLAFM 18]. The fungicidal composition as claimed in claim 1 to 3, wherein the composition is applied to a plant/crop by spraying, rubbing, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, pouring, mist blowing, soil mixing, foaming, painting, spreading-on, drenching, dipping or drip irrigation.
[CLAFM 19]. A kit-of-parts comprising a plurality of components, wherein said plurality of components comprises:
a. Cyazofamid or its agrochemically acceptable salts; and
b. Dimethomorph or its agrochemically acceptable salts; and
c. at least one triazole fungicide selected from Hexaconazole, Cyproconazole,
Diclobutrazol, Difenoconazole, Diniconazole, Epoxiconazole, Etaconazole,
Fenbuconazole, Propiconazole, Tebuconazole, Tetraconazole and Triticonazole or its
agrochemically acceptable salts; and
60

d. One or more agrochemically acceptable excipients

Documents

Application Documents

# Name Date
1 202111052842-RELEVANT DOCUMENTS [14-04-2023(online)].pdf 2023-04-14
1 202111052842-STATEMENT OF UNDERTAKING (FORM 3) [17-11-2021(online)].pdf 2021-11-17
2 202111052842-REQUEST FOR EARLY PUBLICATION(FORM-9) [17-11-2021(online)].pdf 2021-11-17
2 202111052842-IntimationOfGrant27-10-2022.pdf 2022-10-27
3 202111052842-PROOF OF RIGHT [17-11-2021(online)].pdf 2021-11-17
3 202111052842-PatentCertificate27-10-2022.pdf 2022-10-27
4 202111052842-Response to office action [27-10-2022(online)].pdf 2022-10-27
4 202111052842-POWER OF AUTHORITY [17-11-2021(online)].pdf 2021-11-17
5 202111052842-FORM-9 [17-11-2021(online)].pdf 2021-11-17
5 202111052842-CLAIMS [13-08-2022(online)].pdf 2022-08-13
6 202111052842-FORM FOR SMALL ENTITY(FORM-28) [17-11-2021(online)].pdf 2021-11-17
6 202111052842-FER_SER_REPLY [13-08-2022(online)].pdf 2022-08-13
7 202111052842-FORM FOR SMALL ENTITY [17-11-2021(online)].pdf 2021-11-17
7 202111052842-FER.pdf 2022-02-14
8 202111052842-FORM 18A [13-12-2021(online)].pdf 2021-12-13
8 202111052842-FORM 1 [17-11-2021(online)].pdf 2021-11-17
9 202111052842-FORM28 [13-12-2021(online)].pdf 2021-12-13
9 202111052842-EVIDENCE FOR REGISTRATION UNDER SSI(FORM-28) [17-11-2021(online)].pdf 2021-11-17
10 202111052842-EVIDENCE FOR REGISTRATION UNDER SSI [17-11-2021(online)].pdf 2021-11-17
10 202111052842-MSME CERTIFICATE [13-12-2021(online)].pdf 2021-12-13
11 202111052842-COMPLETE SPECIFICATION [17-11-2021(online)].pdf 2021-11-17
11 202111052842-DECLARATION OF INVENTORSHIP (FORM 5) [17-11-2021(online)].pdf 2021-11-17
12 202111052842-COMPLETE SPECIFICATION [17-11-2021(online)].pdf 2021-11-17
12 202111052842-DECLARATION OF INVENTORSHIP (FORM 5) [17-11-2021(online)].pdf 2021-11-17
13 202111052842-EVIDENCE FOR REGISTRATION UNDER SSI [17-11-2021(online)].pdf 2021-11-17
13 202111052842-MSME CERTIFICATE [13-12-2021(online)].pdf 2021-12-13
14 202111052842-EVIDENCE FOR REGISTRATION UNDER SSI(FORM-28) [17-11-2021(online)].pdf 2021-11-17
14 202111052842-FORM28 [13-12-2021(online)].pdf 2021-12-13
15 202111052842-FORM 1 [17-11-2021(online)].pdf 2021-11-17
15 202111052842-FORM 18A [13-12-2021(online)].pdf 2021-12-13
16 202111052842-FER.pdf 2022-02-14
16 202111052842-FORM FOR SMALL ENTITY [17-11-2021(online)].pdf 2021-11-17
17 202111052842-FER_SER_REPLY [13-08-2022(online)].pdf 2022-08-13
17 202111052842-FORM FOR SMALL ENTITY(FORM-28) [17-11-2021(online)].pdf 2021-11-17
18 202111052842-CLAIMS [13-08-2022(online)].pdf 2022-08-13
18 202111052842-FORM-9 [17-11-2021(online)].pdf 2021-11-17
19 202111052842-Response to office action [27-10-2022(online)].pdf 2022-10-27
19 202111052842-POWER OF AUTHORITY [17-11-2021(online)].pdf 2021-11-17
20 202111052842-PROOF OF RIGHT [17-11-2021(online)].pdf 2021-11-17
20 202111052842-PatentCertificate27-10-2022.pdf 2022-10-27
21 202111052842-REQUEST FOR EARLY PUBLICATION(FORM-9) [17-11-2021(online)].pdf 2021-11-17
21 202111052842-IntimationOfGrant27-10-2022.pdf 2022-10-27
22 202111052842-STATEMENT OF UNDERTAKING (FORM 3) [17-11-2021(online)].pdf 2021-11-17
22 202111052842-RELEVANT DOCUMENTS [14-04-2023(online)].pdf 2023-04-14

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