FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10)
"A NOVEL AND IMPROVED SYNERGISTIC COMPOSITION"
We, UNITED PHOSPHORUS LIMITED,
a company incorporated under the Companies Act,
1956 and having its registered office at 3-11, GIDC,
Vapi-396 195,
State of Gujarat, India,
INDIAN.
The following specification particularly describes the nature of this invention and the manner in which it is to be performed :


Field of the Invention
The present invention relates to an improvement in the fungicidal composition disclosed and claimed in Patent Application No.570/MUM/2000 granted as Patent No. IN- 204165.
The invention claimed in Patent No.-IN 204165 relates to an invention of synergistic "fungicidal composition" for controlling fungal infection in crops. The combination comprises active compounds (A) and (B), wherein (A) is Mancozeb and (B) is Carbendazim. The Mancozeb content in the fungicidal composition is 63 % and the Carbendazim content in the fungicidal combination is 12 % by weight of the composition. This composition is claimed to have superior bioefficacy.
It has been disclosed in the patent 204165 that the two well known fungicides Carbendazim and Mancozeb belonging to different groups, exhibits an extremely enhanced fungicidal activity, along with stabilizing dye (SXB), when employed in admixture. Surprisingly the inventors of this invention have found that addition of Urea to the synergistic combination of Carbendazim and Mancozeb with urea gives a superadditive effect by enhancing the bioefficacy than that of the synergistic combination of Carbendazim and Mancozeb combination.
So, more particularly, the present invention relates to a novel improved synergistic composition comprising the fungicidal components and Urea "invention relates to synergistic herbicide combinations for controlling fungal infection along with the fulfillment of nutritional requirements. This novel improved synergistic composition finally provides a healthy crop with the increased biomass of the plant, which finally improves the yield of the crops. The novel improves synergistic composition combinations comprise of fungicidal composition as active compounds (C) and urea as (D), where (C) is a fungicidal composition having optically active arninotriazines having a partial structure of the formula (I), or salts thereof, 63% (by weight of the fungicidal composition), this aminotriazines is Mancozeb 63 % and 12% (by weight of the fungicidal composition) as Carbendazim; and additionally (D) which is urea. This novel improved synergistic fungicidal composition is having superior bioefficacy and finally contributes to increase in biomass and yield over the fungicidal composition of Patent No. IN 204165.


The present invention relates generally to a novel composition comprising carbendazim, mancozeb and a fertilizer selected from the group comprising carbamide, nitrogen, phospharic and potash and organic manures, composting fertilizers, etc. More particularly, the present invention relates to a composition of Carbendazim and Mancozeb with carbamide fertilizer such as urea that enables not only a simultaneous reduction of fungal diseases in the crop plant, grain, fruits and vegetable field and but also increasing the biomass resulting in the enhanced crop yield.
Background of the Invention
Fungicides are chemical compounds used to prevent, control or eradicate the spread of fungi on crop or plants in the gardens or in nursery, ornamental plants, etc. This can cause serious damage resulting in the loss of yield and thus quality as well as profit from the crop plants. Fungicides are also used to fight fungal infections. Fungicides can either be contact or systemic fungicides. A contact fungicide kills fungi when sprayed on the infected its surface; and a systemic fungicide has to be absorbed by the plant.
The word fungicide has originated from two Latin words; viz., fungus and caedo. The word caedo means "to kill. Thus literally speaking a fungicide would be any agency which has the ability to kill fungus. According to this meaning, physical agencies like heat and ultraviolet light should also be called fungicides. By common usage, the word is restricted to chemicals .Hence the word fungicide should mean a chemical capable of killing, controlling or eradicating fungi.
This patent is basically for the novel improved synergistic combination product of carbendazim, mancozeb with urea.
A chemically stable fungicidal composition, being the combination of two fungicides Carbendazim and Mancozeb which displays a synergistically enhanced activity against fungus is disclosed in Patent No. IN 204165.
Patent No. IN 204165 discloses an enhanced synergistic fungicidal composition of'Crop Protection Application' which is characterised by the fact that it includes active agents:-


CARBENDAZIM chemically known as methyl benzimidazol-2-ylcarbamate with molecular formula as C9H9N302 Structure:

CH3-
Carbendazim is a systemic benzimidazole fungicide that plays a very important role in plant disease control. It was first reported in 1973 and was developed by BASF, Hoeschst (now part of Bayer) and Dupont. Pure carbendazim is a colourless, white crystaline, odourless solid which decomposes on melting at approximately 250°C. Technical grade is >98% pure (FAO specification). Carbendazim is not corrosive. Carbendazim is used to control a broad range of diseases on arable crops (cereals, oilseed rape), fruits, vegetables and ornamentals. It is also used in post-harvest food storage, and as a seed pre-planting treatment.
MANCOZEB chemically known as [[2-(dithiocarboxy)arnino]ethyl] carbamodithioato]]
(2-)-KS,KS']manganese mixture with [[2-
[(dithiocarboxy)ammo]ethyl]carbamodithioato]](2-)-KS,KS']zinc with molecular formula as :

and specially selected adjuvants, dispersing agents, wetting agents, thickeners, sticker, stabilizing dye and fillers.
They affect the nervous system through their main metabolite, carbon disulfide. They are effective in controlling the soil born diseases by entering in soil pores.
It has been observed that the most common problem that farmers are facing is of saprophyte in the field. "Saprophyte" is an older term that is now considered obsolete. The suffix -phyte means "plant". However, there are no truly saprophytic organisms that are embryophytes, and fungi and bacteria are no longer placed in the Plant Kingdom. Plants that were once considered saprophytes, such as non-photosynthetic orchids and monotropes, are now known to be parasites on other plants. They are termed myco-


heterotrophs because a mycorrhizal fungus connects the parasitic plant with its host plant. It has been observed that parasitic fungi are blocking the nutrition to the plants by blocking the nitrogen supply. It has been surprisingly found that application of 'Carbendazim, Mancozeb and Urea' in the form of a single composition due to the fungicidal property of combination product of carbendazim and mancozeb, the saprophytic fungi are controlled and due to the plant's undiseased state the nutritional requirement is fulfilled and the biomass of the plants is increased.
However, there exists a continuous need in the art for improved compositions that not only helps in controlling the fungal growth but also enhances bioefficacy, having reduced phytotoxicity and an improved stability characteristics and economic significance. Such composition should also have a property to control the diseases and saprophytic fungi. There is also a need in the prior art to have a composition with a super-additive complementation of fungal control with increased crop production over the application of individual active ingredients separately
Urea, a white crystalline solid containing 46% nitrogen, is widely used in the agricultural as a fertilizer. Commercially, fertilizer urea is available as prills or as a granulated material. In the past, it was usually produced by dropping liquid urea from a "prilling tower" while drying the product. The Prills formed a smaller and softer substance than other materials commonly used in fertilizer blends. Today, though, considerable urea is manufactured as granules. Granules are larger, harder, and more resistant to moisture. As a result, granulated urea has become a more suitable material for fertilizer blends.
Nitrogen from urea can be lost to the atmosphere if fertilizer urea remains on the soil surface for extended periods of time during warm weather. The key to the most efficient use of urea is to incorporate it into the soil during a tillage operation. It may also be blended into the soil with irrigation water. A rainfall of as little as 0.25 inches is sufficient to blend ureainto the soil to a depth at which ammonia losses will not occur.
Urea breakdown begins as soon as it is applied to the soil. If the soil is totally dry, no reaction happens. But with the enzyme urease, plus any small amount of soil moisture, urea normally hydrolyzes and converts to ammonium and carbon dioxide. The volatility of urea depends to a great extent on soil temperature and soil pH. Warm temperature and high pH causes more loss of urea and thus less availability to plants. If properly applied,


urea and fertilizers containing urea are excellent sources of nitrogen for crop production. After application to the soil, urea undergoes chemical changes and ammonium (NH44) ions form. Soil moisture determines how rapidly this conversion takes place. When a urea particle dissolves, the area around it becomes a zone of high pH and ammonia concentration. This zone can be quite toxic for a few hours. Seed and seedling roots within this zone can be killed by the free ammonia that has formed. Fortunately, this toxic zone becomes neutralized in most soils as the ammonia converts to ammonium. Usually it's just a few days before plants can effectively use the nitrogen. Although urea imparts an alkaline reaction when first applied to the soil, the net effect is to produce an acid reaction.
Due to extensive hydrogen bonding with water (up to six hydrogen bonds may form - two from the oxygen atom and one from each hydrogen), it is very soluble, and, thus, is also a good fertilizer. The urea molecule is planar and retains its full molecular point symmetry, due to conjugation of one of each nitrogen's P orbital to the carbonyl double bond. Each carbonyl oxygen atom accepts four N-H-0 hydrogen bonds, a very unusual feature for such a bond type. This dense (and energetically favourable) hydrogen bond network is probably established at the cost of efficient molecular packing: The structure is quite open, the ribbons forming tunnels with square cross-section. This structure accelerates the uptake of urea by the plants.
The ability of plants to uptake nitrogen through urea is enhanced by protecting the extraneous fungal elements. The rice plant in particular stands in water for almost all its life and is prone to gathering number of fungus including saprophytes. The presence of combination product of Carbendazim and Mancozeb ensures that these fungus are killed making the stem cells healthy and fit for effective transportation of the supply of nutrients released by urea. Because of the accumulation of saprophytic fungus the passage of the supply of nutrients is choked and thus the urea is not available to the plants. The present invention addresses this need in the art by controlling the fungus to stop or reduce choking clearing the choke and making the urea readily available to the plants.
It is known in the art that urea fertilizer can be coated with certain materials, such as sulfur, to reduce the rate at which the nitrogen becomes available to plants.


It has now been surprisingly found that the fungicidal composition of Patent No. IN 204165 that contains Carbendazim and Mancozeb having a further coating with urea or vice versa during the first broadcasting and/or second application greatly enhances bioefficacy. Thus, this novel improved synergistic composition of Carbendazim, Mancozeb and Urea not only imparts an improved bioefficacy and enhanced economic significance, but also acts without affecting the other advantages of the herbicidal fungicidal composition claimed in the Indian Patent number IN -204165.
The inventors of the invention disclosed herein have found that it is a difficult task to formulate a composition which is a combination of carbendazim and mancozeb with urea due to large difference in the doses of two actives and the differences in the density of the final product active ingredients. It is also a difficult task to alter the density of carbendazim and mancozeb by using various techniques of granulation which are known in the art and which is again a challenging job as carbendazim and mancozeb is available in the form of fine powder form, which is having the sticking and dusting property. So there exists a need to develop a composition having content uniformity when carbendazim and mancozeb and urea mixed together as a one product. The inventors of this invention have successfully formulated a novel improved synergistic composition having a content uniformity to the product. The product further has an ease of handling and applicability with or without further dilution.
One form of the said product is available in the form of carbendazim and mancozeb coated with urea.
The other form in which the product is available is in the form of Urea coated with carbendazim and mancozeb.
The product is also available in the form wherein carbendazim and mancozeb is granulated to match the density of urea granules.
A further embodiment of the improvement encompasses in adding Carbendazim and mancozeb to the binding liquidified gum solution during the process of urea granulation. The flowable 'Carbendazim and Mancozeb' when diluted with the gum solution provides the requisite impregnation on the urea granules thus effectively providing the final embodiment.


Objects of the Invention:
Accordingly, it is an object of the present invention to provide an improvement in the fungicidal composition claimed in Patent No. IN 204165.
Another object of the present invention is to provide an improvement in the bioefficacy after adding urea to the combination product of 'Carbendazim and Mancozeb' and the resultant product in turn is with enhanced bioefficacy and imparts economic significance to the fungicidal composition of Patent No. IN 204165. Most important is that the resultant product is synergistic in nature.
It is also an object of the present invention to provide an improvement over the fungicidal composition of Patent No. IN204165 without reducing or differing its other advantages such as chemical stability, physico-chemical compatibility, synergism, and the like.
It is also a further aspect of the invention to have a triple combination product of carbendazim, mancozeb and urea in a single pack container.
Another object of the present invention is to provide a synergistic composition that not only controls the fungal growth, but also helps in enhancing the biomass and in turn enhances the productivity and crop yield.
Another object of the present invention is to provide synergistic composition which demonstrates a superadditive complementation of fungal control with increased crop production, by increasing root length over the application of individual active ingredients separately.
Another object of the present invention is to provide synergistic composition which demonstrates a superadditive complementation of fungal control by having clear roots without fungal spots.
Yet another object of the invention is to provide a synergistic composition which demonstrates a superadditive complementation of having increased in the tillers and resulted in the increase in the final crop yield.


Yet another object of the invention is to provide a synergistic composition which demonstrates a superadditive complementation in the form of Carbendazim and Mancozeb having a further coating with urea or vice versa.
It was found in further aspect of the invention is a composition comprising carbendazim, mancozeb and urea; the latter active ingredient is a used in the concentration ranging from 10 kgs to 25 kgs of urea with 500 Gms of combination product of 'Carbendazim and Mancozeb.'
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided an improvement in the bioefficacy fungicidal composition claimed in Patent No.IN204165, said improved composition comprising Carbendazim, Mancozeb and Urea as actives. The content of the active ingredients is 500 gms of 'Carbendazim and Mancozeb' (Carbendazim (12%) + Mancozeb (63%) i.e. in the gravimetric (weight) ratio of Carbendazim to Mancozeb is 12:63) with urea. Carbendazim, Mancozeb and urea in the form of a stable composition which is also highly bioefficient is prepared with specially selected adjuvants, dispersing agents, wetting agents, thickeners, sticker, stabilizing dye and fillers.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the first aspect of the present invention, there is provided an improvement in the fungicidal composition claimed in Patent No. IN 204165 having Carbendazim, Mancozeb and Urea.
The fungicidal composition of Patent No. IN 204165 that contains 'Carbendazim and Mancozeb' on addition of Urea during the first broadcasting and/or second application shows the enhances bioefficacy. Thus, this synergistic combination of Carbendazim, mancozeb and urea is not only imparted an improved bioefficacy and enhanced economic significance, but act without affecting the other advantages of the herbicidal fungicidal composition claimed in the Indian patent number IN 204165.


Yet another object of the invention is to provide a synergistic composition which demonstrates a superadditive complementation in the form of Carbendazim and Mancozeb having a further coating with Urea or vice versa.
The inventors of this invention have also tried granulating the powder mixture of Carbendazim and Mancozeb to match the density to that of the urea granules, so that the mixing of these two components will give the content uniformity to the final product.
One embodiment of the invention is in the form of Carbendazim and Mancozeb coated with urea. The invented product granules having a desired size are produced in a fluid bed processor by feeding the Carbendazim+Mancozeb solid seed granules into the bowl. A spraying liquid is prepared by mixing urea into water andVsolvent(s) in the required strength. Thereafter atomizing/spraying the spraying liquid onto the Carbendazim + Mancozeb seed granules through spraying means. Simultaneously providing a hot air having a temperature of 35 to 110 °C. The liquid droplets adhere to the seed granules and get dried and solidified to have a product having carbendazim+ Mancozeb coated with Urea.
The other form in which the product is available is in the form of Urea coated with Carbendazim and Mancozeb. Half of the required quantity of Urea is charged into a mixing tank (like Nauto mixer, booth mixer, blender, etc.). A required quantity of Carbendazim + Mancozeb technical/formulation is added in the mixing tank for the required rate of application. Mixing is continued and the remainder quantity of the Urea is added to the mixing tank. Mixing is continued for another 5 to 30 minutes. The ready to use product (where Urea is coated with Carbendazim+Mancozeb) is available. This product can be diluted or applied as such by broadcasting at the required rates.
The product is also available in the form wherein Carbendazim and Mancozeb is granulated to match the density of urea granules. This is done by processing a powder blend of Carbendazim + Mancozeb with or without Urea. The product obtained is made to have a density equal to that of urea granules by using the selected inerts. These inert(s) may or may not include Urea. In such case the urea needs to be micronized into the powder form and later used as a part or whole in place of inert. Later the blended mixture, if needed to be grinded, is granulated in the form of dry, free- flowable granules.


The composition or formulation is prepared by known or recognised methods for example by homogeneously mixing and grinding the active components with extenders, e.g. solid carriers, surface active components, dispersants, wetting agents, thickners, stickers, stabilizing - dye, and the like. The solid carriers used are normally natural mineral filler(s) such as precipitated silica, china clay and kaolin. Fillers are selected but are not limited to precipitated silica, china clay and kaolin and other such agents known in the art.
The inert filler may be selected from precipitated silica, kaolin, bentonite, dolomite, Attapulgite, ammonium sulphate and the like or a mixture thereof. In a preferred embodiment, the inert filler is ammonium sulphate and / or a mixture of Attapulgite (30-40%) and precipitated silica (60-70%).
The stabilizer optionally present in the composition in a preferred embodiment is hexamethylene tetramine.
The defoamer is selected from silicone defoamers and the like. In a preferred embodiment, the defoamer is tallow soap, Rhodorsil 426R and / or a mixture thereof.
The wetting agent is selected from sodium dialkyl naphthalene sulphonates, alkyl ethoxylates, ether sulphates , salts of alkyl aryl sulfonate and other such agents known in the art.
The dispersing and /or suspending agent is selected from sodium naphthalene sulphonate, alkyl naphthyl sulfonate ,sodium lignosulphonate, polycarboxylates and other such agents known in the art.
The stabilizing dye is selected from Stabmet XE Blue (SXB) which is a stabilized copper phthalocynanine pigment and which is also conducive to reduce the generation of ethylene thiourea on long term storage. Stabilizing dye can also selected from other such agents known in the art.
The combination product of "Carbendazim, Mancozeb and Urea" is found effective in controlling the fungal diseases in paddy, wheat, black gram, chilli, and tomato, while combination of "Carbendazim and Mancozeb" was effective only on paddy and


Groundnut. The commonly observed fungal diseases in these crops are sheath blight, sheath rot, brown spot of rice, blast of rice, root rot, leaf rust, stem rust, alternarial leaf blight, cercospora leaf spot, powdery mildew, corynespora leaf spot, rust, anthracnose, cercospora leaf spot, alternaria leaf spot, die back of chilli, anthracnose, powdery mildew, septoria leaf blight, anthracnose, early blight, late blight, fusarium wilt which are successfully controlled by the combination product of "Carbendazim, Mancozeb and Urea". The invention disclosed in this specification is not limited to these crops and diseases but can also extended to the crops diseases known to the person skilled in the art.
The invention will be illustrated with reference to the following examples.
Example -1
The product of the invention can be prepared by feeding the urea solid granules into the blender. Thereafter atomizing and spraying a liquid containing a fungicidal composition onto the urea granules through the spraying means. Passing the hot air stream (30 -110 degree C) whereby the atomizing liquid droplets adhere to the urea granules. Drying or solidification done in Fluid bed dryer. Discharging the resultant granules. Sieving, if required, to get the product as per this invention.
Example-2
The product of this invention can be prepared by charging half of the required quantity of Urea granules into the blender. Then adding slowly the requisite quantity of fungicidal composition onto the Urea granules. Blending/mixing for sufficient time. Adding the balance quantity of Urea granules into the blender. Mixing for another 5 -30 minutes to have a homogenous granulated urea coated with fungicidal composition ready to use by direct broadcasting.
Example - 3
The product of this invention can also be prepared by grinding urea, ganules/fine or recyclable product obtained during the urea manufacture, into powder form using a suitable grinder. Charging the required quantity of urea powder into the blender. Starting the blender. Adding the requisite quantity of fungicidal composition into the blender. Blending the mixture to have a homogenous powder. Granulating the homogenous powder. If necessary, drying the granulated product of previous step. Sieving the dried product to have a granulated product of this invention.


Example-4
The product of this invention can be prepared by charging the seed particles (fungicidal composition) in the fluid bed processor. Preparing a sprayable slurry using urea. Spraying the slurry on the seed particles. Simultaneously drying the product by maintaining an inlet temperature >60 Degree C and outlet. 35 Degree C. Sieving the granules to have required size range of granules.
Example-5
The product of this invention can be prepared by charging the seed particles (urea) in the fluid bed processor. Preparing sprayable slurry using the other component (fungicidal composition). Spraying the slurry on the seed particles. Simultaneously drying the product by maintaining an inlet temperature >60 Degree C and outlet .35 Degree C. Sieving the granules to have required size range of granules.
Example-6
The slurry or solution added to the powder or seed granules can be prepared to have a urea concentration of 30 -70 % by weight. The slurry or solution may or may not include the binders which help to stick the spraying material to the seed granules.
Example-7
The product as required for application for direct broadcasting can also be prepared without urea. This product needs to match the density and granule range of the urea, with which it will be diluted as per the requirement prior to use. This can also be used directly.
Example 7A.
A general composition for the granules of fungicidal composition is as follows:
The following composition was used to produce Mancozeb 44.1% + Carbendazim 8.4%
(52.50% WG) granules. The ratio of the active ingredients Mancozeb : Carbendazim is
63:12.

Sr. No. Ingredients Base of formulation (%) Weight % by mass
1 Mancozeb technical purity 80% 44.1 55.125


Sr. No. Ingredients Base of formulation (%) Weight % by mass
2 Carbendazim technical purity 98% 8.4 8.572
3 Ammonium lignosulfonate 8.000
4 Sodium lauryl sulphate 3.000
5 Geropon T 77 4.000
6 Dye 1.000
7 Precipitated silica 6.000
8 Soap stone 14.303
Total 100.00%
Above all ingredients were weighed and mixed in a pre-blender. Thereafter the ingredients were micronized by using air jet mill. The micronised product was post blended in the post blender and then granulated on Pan granulator, using water as a granulating liquid. The granules obtained were dried and sieved through 8/36 BSS. The granules obtained were of bluish green coloured free flowing granules . The shape of the granules is almost spherical having a bulk density of 0.728 g/ml which is same as of urea granules 0.731 g/ml. The oversize and fines were recycled. The overall yield was found to be 90.50% of the powder charged. Rest of the material 9.5% was recycled in the next batch of same composition. The granules were found to have a gravimetric. Suspensibility of 68.4%. The column shows a persistent foam of more than 40 ml. So this composition requires modification for persistence foam.
Example 7 B.
A general composition for the granules of fungicidal composition is as follows: The following composition was used to produce Mancozeb 44.1% + Carbendazim 8.4% (52.50% WG) granules having less than 5 ml of persistent foaming. The ratio of the active ingredients Mancozeb : Carbendazim is 63:12.

S.No. Ingredients Base of formulation (%) Weight % by mass
1 Mancozeb technical purity 80% 44.1 55.125
2 Carbendazim technical purity 98% 8.4 8.572
3 Ammonium lignosulfonate 10.000
4 Sodium lauryl sulphate 5.000
5 Dye 1.000


S.No. Ingredients Base of formulation (%) Weight % by mass
6 Precipitated silica 4.000
7 Soap stone 16.303
Total 100.00%
Above all ingredients wee weighed and mixed in a pre-blender. Thereafter the ingredients were micronized by using air jet mill. The micronised product was post blended in the post blender and then granulated on Pan granulator, using water as a granulating liquid. The granules obtained were dried and sieved through 8/36 BSS. The granules obtained were of bluish green coloured free flowing granules . The shape of the granules is almost spherical having a bulk density of 0.729 g/ml which is same as of urea granules 0.731 g/ml. The oversize and fines were recycled. The overall yield was found to be 93.75 % of the powder charged. Rest of the material 6.25% was recycled in the next batch of same composition. The granules were found to have a gravimetric Suspensibility of 78.8%. The column shows a persistent foam of less than 5 ml. So this composition gives a good product.
Example 7C.
A general composition for the granules of fungicidal composition is as follows:
The following composition was used to produce Mancozeb 3.15 % + Carbendazim 0.6 %
(3.75 % G) granules. These granules can be used direct broadcasting. These granules can
also be prepared without urea. This product obtained matches in the density and granule
size of the urea. This can be diluted as per the requirement prior to use and as well as
directly. The ratio of the active ingredients Mancozeb : Carbendazim is 63:12.
.A general composition for Granules of fungicidal composition is as follows:

Sr. No. Ingredients Base of formulation (%) Weight (g)
1 Mancozeb technical purity 80% 3.5 4.375
2 Carbendazim technical purity 98% 0.7 0.715
3 Ammonium lignosulfonate 2.000
4 Sodium iignosulphate 2.000
5 Dye (Rhodamine) 1.810
6 Kaoline 32.000
7 Precipitated silica 12.000


Sr. No. Ingredients Base of formulation (%) Weight (g)
8 Soap stone 45.100
Total 100.00 g
The ingredients weighed and charged in mixer cum grinder pot and processed for 3 minutes at highest speed. The powder obtained was looking like golden colour powder. This powder was taken for granulation in Pan and only water was sprayed. The product obtained had lumps and granules. The required size product of 8/36 BSS sieved and collected . The obtained granules were dried in oven and tested for performance. The lumps obtained were extruded manually through 22 BSS sieve and dried. The extrudates were dried and sieved. The granules by pan and extrusion are found to be good in dispersion but pink in colour and low binding property. The binding needs to be improved so that the product can stand the force in storage, filling, transportation and use. The granules is almost having a bulk density of 0.697 to 0.710 g/ml which is same as of urea granules 0.731 g/ml.
Example 7D
A general composition for the granules of fungicidal composition is as follows:
The following composition was used to produce Mancozeb 3.15 % + Carbendazim 0.6 %
(3.75 % G) granules. These granules can be used direct broadcasting. These granules can
also be prepared without urea. This product obtained matches in the density and granule
size of the urea. This can be diluted as per the requirement prior to use and as well as
directly.
The ratio of the active ingredients Mancozeb: Carbendazim is 63:12. A general composition for Granules of fungicidal composition is as follows:

S.No. Ingredients Base (%) Weight (g)
1 Manozeb technical purity 80% 3.5 4.375
2 Carbendazim technical purity 98% 0.7 0.715
3 Morwet D-425 5.000
4 Sodium ligno sulfonate 5.000
5 Precipitated Silica 12.000
5 Dye (Brilliant blue+ Ocean blue) 3 : 2 1.000
6 Inert filler(s) Kaolin 71!910


S.No. Ingredients Base (%) Weight (g)
Total 100.00 g
The ingredients weighed and charged in blender and processed to have a homogenous mixture. The powder obtained was then micronize using air jet mill and the same after milling was post blended. This powder was taken for dough preparation in PSM (Plough Shear Mixer) to have a wet consistent dough suitable to be processed through UPL axial extruder. The product obtained is in the form of extrudates. The extrudates were semi dried and processed for sizing to have the required size product of 8/36 BSS. The product then sieved and collected . The obtained granules were dried in fluid bed drier and tested for performance. The granules were found to be good in dispersion and the bulk density was 0.73 g/ml. The binding of the granules was good and do not produce dust during packing, storage, transport and use. These granules were being of the same density as of the urea granules can be easily mixed with them can be combined and applied with the urea granules. The distribution was found to be uniform throughout. The binding was perfect. The shape of the granules is cylindrical to almost spherical having a bulk density of 0.73 g/ml which is same as of urea granules 0.731 g/ml.
A general composition for Granules of fungicidal composition is as follows:

S.No. Ingredients Purity(%) Weight % by mass
1 Mancozeb technical 80% 3.9375
2 Carbendazim technical 99% 0.661
3 Wetting agent - 5.00
4 Dispersing agent - 10.00
5 Dye - 1.00
6 Inert filler(s) - Q.S.
Total 100.00%
Example-8
The following composition is used for the preparation of granules which can be used with or without further dilution with required quantity of urea. A best example and the process for its preparation is as follows: Composition:


Sr.No. Ingredients Weight % by mass Quantity (Kg)
1 Manozeb technical purity 80% (base 3.15%) 3.9375 39.375
2 Carbendazim technical purity 99% base 0.60%) 0.6061 6.0610
3 Wetting agent (Morwet D 425) 5.0000 50.000
4 Dispersing agent (SLS) 10.0000 100.0000
5 Dye(s) 1.0000 10.0000
6 Inert filler(s)
a) Precipitated silica 10.0000 100.0000
b) Kaolin/Clay/Soapstone 69.4564 694.5640
Total 1000.000
The above ingredients were charged into the blender for premixing. This premix was then micronised through Air classifying mill/Air Jet Mill and then charged into the post-blender to have a homogenous powder. Thereafter this post mixed powder was charged into the plough shear mixer to form the dough of uniform consistency using water (15-40%). This dough is then extruded into the extrudates which later dried, sized and sieved to have the product.
Example 9.
A general composition for the granules of fungicidal composition is as follows: The following composition was used to produce "SAAF" Mancozeb 3.15 % + Carbendazim 0.6 % (3.75 % G) granules. These granules can be used direct broadcasting. These granules can also be prepared without urea. This product obtained matches in the density and granule size of the urea. This can be diluted as per the requirement prior to use and as well as directly.
The ratio of the active ingredients Mancozeb : Carbendazim is 63:12. A general composition for Granules of fungicidal composition is as follows:

S.No. Ingredients Base of formulation (%) Weight (g)
1 Mancozeb technical purity 80% 3.5 4.375
2 Carbendazim technical purity 98% 0.7 0.715
3 Ammonium lignosulfonate 2.000
18

S.No. Ingredients Base of formulation (%) Weight (g)
4 Sodium lignosulphate 2.000
5 Dye (Rhodamine) 1.810
6 Kaoline 42.000
7 Precipitated silica 2.000
8 Urea powder 45.100
Total 100.00 g
The ingredients weighed and charged in mixer cum grinder pot and processed for 3 minutes at highest speed. This powder was taken for granulation in Roto granulator and only water was sprayed. The product obtained was semi dried and sieved. The required size product of 8/36 BSS sieved and collected . The obtained granules were dried in FBD and tested for performance. The oversize and fines obtained were recycled. The granules are found to be good in dispersion. The granules is almost having a bulk density of 0.731 g/ml which is same as of urea granules 0.731 g/ml.
Table-1
The below table shows the synergestic effect of combination product of effect of carbendazim and mancozeb and urea when tried on paddy .the samples tested are (a)"carbendazim and mancozeb",
(b) only urea, and
(c) "Carbendazim and mancozeb and urea "effect on paddy.
The below table is the trial conducted in Zone 1 Zone 1

Crop Dose/Acre waiting Period root length (Cm) Tillering
(No) Diseases managed Yield/ Acre
Car ben dazim
+
Manco zeb (g) Urea (Kg)

PADDY 0 0 50 Days Very poor Growth with Fungal Attack (10) Very Less No of tillers (10) No control Below Average (15-17Qt/Acre)
PADDY 0 25 50 Days Average Growth with Fungal Infection (13-14) Average No. of tillers (10-12) No control Poor Yield
(20
Qt/Acre)
500 0 20 Days Average Average No. of Sheath Avg. 0.5 Qt


after Growth tillers (10-12) Blight, higher than
Application without fungal Blast and controlled
PADDY Infection (13-14) Root Rot and Sheath Rot (20-22Qt/Acre)
Sheath Avg 1.5 to
20 Days
after
Application 6-8 cm more 3-4 tillers more Blight, 2.0 Qt
500 25
than the than the Blast and higher than
PADDY


controlled controlled Root Rot controlled

Plot (16-18) (15-17) & Sheath (23-25
Rot Qt/Acre)
Table-2
The below table shows the synergestic effect of triple combination product of effect of carbendazim and mancozeb and urea when tried on paddy .the samples tested are (a)"carbendazim + mancozeb",
(b) only urea, and
(c) "Carbendazim and mancozeb and urea "effect on paddy.
The below table is the trial conducted in Zone 2
Zone 2

Crop DOSE/Acre WAITING Period ROOT LENGTH
(Cm) Tillering
(No) DISEAS ES
MANAG ED YIELD/Ac re
Carbe
ndazi
m +
Mane
ozeb
(E) UREA
(Kg)

PADDY 0 0 50 Days Very poor Growth with Fungal Attack (10) Very Less No of tillers (H) No control Below Average (14-17Qt/Acre)
PADDY 0 25 50 Days Good
Growth
with
Fungal
Infection
(12-14) Average No. of tillers (12-13) No control Poor Yield
(18-20
Qt/Acre)
PADDY 500 0 20 Days
after
Application Average
Growth
without
fungal
Infection
(12-14) Average No. of tillers (12-13) Sheath Blight, Blast and Root Rot & Sheath Rot Avg. 0.5 Qt higher than controlled (20-22Qt/Acre)


PADDY 500 25 20 Days
after
Application 2-4 Cm
more than
the
controlled
Plot
(14-16) 3-4 tillers more than the
controlled (15-16) Sheath Blight, Blast and Root Rot & Sheath Rot Avgl.Oto 1.5 Qt higher than controlled (22-23 Qt/Acre)
Table-3
The below table shows the synergestic effect of triple combination product of effect of carbendazim and mancozeb and urea when tried on paddy .the samples tested are (a)"carbendazim + mancozeb",
(b) only urea, and
(c) "Carbendazim and mancozeb and urea "effect on paddy.
The below table is the trial conducted in Zone 3
Zone 3

CROP DOSE/Acre WAITING Period ROOT LENGTH
(Cm) Tillering(No) DISEAS ES
MANAG ED YIELD/Ac re
Carbe
ndazi
m +
Mane
ozeb
(E) UREA
(Kg)
PADDY 0 0 50 Days Very poor Growth with Fungal Attack (10) Very Less No of tillers (10) No control Below Average (15-17Qt/Acre)
PADDY 0 25 50 Days Good
Growth
with
Fungal
Infection
(12-15) Average No. of tillers (10-12) No control Poor Yield
(20
Qt/Acre)
PADDY 500 0 20 Days after Application Average Growth without fungal Average No. of tillers (10-12) Sheath Blight, Blast and Root Rot Avg. 0.5 Qt higher than controlled (20-


Infection(l 3-14) & Sheath Rot 22Qt/Acre)
PADDY 500 25 20 Days after Application 4-5 Cm more than the
controlled Plot (16-18) 3-4 tillers more than the controlled (14) Sheath Blight, Blast and Root Rot & Sheath Rot Avg 1.5 to 2.0 Qt higher than controlled (24-25 Qt/Acre)
Table-4
The below table shows the synergestic effect of triple combination product of effect of carbendazim and mancozeb and urea when tried on paddy .the samples tested are (a)"carbendazim + mancozeb",
(b) only urea, and
(c) "Carbendazim and mancozeb and urea "effect on paddy.
The below table is the trial conducted in Zone 4
Zone 4

CROP DOSE/Acre WAITING Period ROOT LENGTH
(Cm) Tillering (No) DISEASES MANAGED YIELD/Acre
Carbe ndazi m + Mane ozeb
te) UREA
(Kg)

PADDY 0 0 50 Days Very poor Growth with Fungal Attack (10) Very Less No of tillers (10-11) No control Below Average
(14-
180t/Acre)
PADDY 0 ' 25 50 Days Good
Growth
with
Fungal
Infection
(13-14) Average No. of tillers (10-12) No control Poor Yield (18-20 Qt/Acre)
PADDY 500 0 20 Days after Application Average
Growth
without
fungal
Infection(l Average No., of tillers (10-12) Sheath Blight, Blast and Root Rot Avg. 0.5 Qt higher than controlled (20-21Qt/Acre)


3-14)
PADDY 500 25 20 Days after Application 2-3 Cm more than the
controlled Plot(15-16) 3-4 tillers more than the
controlled (15 -16) Sheath Blight, Blast and Root Rot Avgl.0tol.5 Qt higher than controlled (22-24 Qt/Acre)
Table-5
Apart from paddy, the combination product of "carbendazim, mancozeb and urea" are also found effective in controlling the fungal diseases as mentioned in the table below .they are found effective on wheat, black gram, chilli and tomatoes.

CROP MAJOR DISEASES DISEASES
CONTROLLED BY
THE COMBINATION
PRODUCT OF
"CARBENDAZIM AND
MANCOZEB AND
UREA" 1st Top Dressing 2nd Top Dressing 3rd Top Dressing
PADDY Sheath blight, sheath rot, brown spot of rice, blast of rice,root rot, bacterial leaf blight, false smut Sheath blight, sheath rot, brown spot of rice, blast of rice,root rot 25-35 20-30 20-30
WHEAT Leaf rust,stem rust, alternarial leaf blight, karnal bunt, loose smut of wheat, barley yellow dwarf Leaf rust,stem rust, alternarial leaf blight 25-35 25-30 25-30
BLACK GRAM Cercospora leaf spot, powdery mildew, corynespora leaf spot, rust, anthracnose, powdery mildew, root rot and leaf blight, seed and seedling rot, stem Cercospora leaf spot, powdery mildew, corynespora leaf spot, rust, anthracnose, 20-25 Kg/ Acre If
Required
-10-15
Kg -


canker
CHILLI Cercospora leaf spot, alternaria leaf spot, die backofcilli, anthracnose, powdery mildew, damping off, fusarium, leaf curl, mosaic Cercospora leaf spot, alternaria leaf spot, die backofcilli,, anthracnose, powdery mildew, 30-40 30-40 30-40
TOMATO Septoria leaf blight, anthracnose, early blight, late blight, fusarium wilt, bacterial spots, bacterial wilt, collar rot, damping off, leaf curl, mosaic, powdery mildew, spotted wilt. Septoria leaf blight, anthracnose, early blight, late blight, fusarium wilt 20-25 20-25 -
Example -10
Control of fungus by using novel improved synergistic composition shows control of Fungus at commercial levels by using Urea with Mancozeb and Carbendazim at various rates. The results shown in table -2 were obtained by applying Mancozeb technical/formulation, Carbendazim technical/formulation, Carbendazim+ Mancozeb technical/formulation and urea mixture to 5 fields infected with various fungal diseases (indicated in table-2).
Fungus control was obtained in 21 days after treatment (DAT) at a braodcast volume of 25 Kg/ha at different rates. No fungus control was observed in control and where urea was applied alone. Additional supporting bioefficacy was independently observed on fungus such as Sheath Blight, Blast and Root Rot, etc. The result demonstrates the utility of the Urea in preparing broadcastable and bioactive mixture of Carbendazim and/or Mancozeb for controlling the fungus. The urea tested in this example contained about 46.64% Nitrogen, 20% Carbon, 6.71% Hydrogen, 26.64% Oxygen.
Wherein the aforegoing reference has been made to components having known equivalents, then such equivalents are herein incorporated as if individually set forth. Accordingly, it will be appreciated that changes may be made to the above described aspects and embodiments of the invention without departing from the principles taught


herein. Additional advantages of the present invention will become apparent for those skilled in the art after considering the principles in particular form as discussed and illustrated. Thus, it will be understood that the invention is not limited to the particular embodiments described or illustrated, but is intended to cover all alterations or modifications which are within the scope of the appended claims.




We claim:
1. An improvement in and relating to a more bioefficatious synergistic fungicidal composition for crop protection claimed in Patent No. IN 204165 which comprises as active ingredients consisting of Carbendazim of the formula:

/ CH3—O
and Mancozeb of the formula:
[-Mn-SCSNHCH2CH2NHCSSMn-] x Zn Y
wherein x & y are natural numbers (positive integers) viz: 1, 2, 3, and urea wherein said Carbendazim and Mancozeb are present in a gravimetric weight ratio of 12:63 to 12:63: and the balance if any, comprising of one or more optional ingredients selected from adjuvants, dispersing agents, wetting agents, stabilizing dye and filler(s).
2. An improved composition as claimed in claim 1 wherein said dispersing agent is an alkyl naphthyl sulfonate derivative.
3. An improved composition as claimed in claim 1 wherein said wetting agent comprises salts of alkyl aryl sulfonate.
4. An improved composition as claimed in any preceding claim wherein said stabilizing dye comprises Stabmet XE Blue (SXB) which is a stabilized copper phthalocynanine pigment.
5. A composition as claimed in any preceding claim wherein said fillers are selected from one or more of precipitated silica, china clay and kaolin.
6. An improvement in and relating to a more bioefficacious synergistic fungicidal composition prepared by the process comprising,


a) urea solid granules are loaded into the blender,
b) an aqueous slurry of Carbendazim and Mancozeb is sprayed onto the urea granules,
c) pass the hot air stream whereby the atomizing liquid droplets adhere to the urea granules,
d) drying or solidification is done in fluid bed dryer,
e) the resultant granules are collected.
7. An improvement in and relating to a more bioefficacious synergistic fungicidal composition prepared by the process comprising,
a) Carbendazim and Mancozeb is added in the mixing tank,
b) a required amount of urea is added to the mixing tank and mixing continued and remainder amount of Urea is added to the mixing tank,
c) homogeneous synergistic composition is obtained.

8. An improvement in and relating to a more bioefficacious synergistic fungicidal composition prepared by the process comprising,
a) the urea is grinded into powder form using a suitable grinder and charged into a blender,
b) requisite quantity of Carbendazim and Mancozeb is added into the blender and continue mixing to have a homogenous powder,
c) granulating the homogenous powder,
d) drying the granulated product and sieving the dried product to have a granulated product.

9. An improvement in and relating to a more bioefficacious synergistic fungicidalcomposition prepared by the process comprising,
a) seed particles of urea are charged in the fluid bed processor,
b) preparing a aqueous sprayable slurry using the Carbendazim and Mancozeb,
c) spraying the slurry on the seed particles,
d) simultaneously drying the product by maintaining an inlet temperature >60°C and outlet 35°C,
e) sieving the granules to have required size range of granules.


10. An improvement in and relating to a more bioefficacious synergistic fungicidal
composition prepared by the process comprising,
a) seed particles of Carbendazim and Mancozeb are charged in the fluid bed processor,
b) preparing a aqueous sprayable slurry using urea,
c) spraying the slurry on the seed particles,
d) simultaneously drying the product by maintaining an inlet temperature >60°C and outlet 35°C,
e) sieving the granules to have required size range of granules

11. An improvement in and relating to a more bioefficacious synergistic fungicidal composition prepared by the process as substantially described herein.
12. An enhanced fungicidal composition for crop protection substantially as hereinbefore described with reference to the foregoing examples.






Abstract:
An improvement in the bioefficacy of a fungicidal composition claimed in Patent No. IN 204165, said improved composition comprising Carbendazim, Mancozeb and Urea as actives. Carbendazim, Mancozeb and urea are in the form of a stable composition which is prepared with selected adjuvants, dispersing agents, wetting agents, thickeners, sticker, stabilizing dye and fillers. Also described is a process for the preparation of the improved compositions.