FIELD OF INVENTION
The present invention relates to the field of agricultural herbicidal mixes. In particular, the present invention relates to a trimix herbicidal composition comprising Clodinafop propargyl, Metsulfuron methyl, and Carfentrazone ethyl.
BACKGROUND OF THE INVENTION 5
Weed control is an important practice for crops growth. The losses caused by weeds in agricultural production environments include reduced crop quality, increased irrigation costs, increased harvesting costs, reduced land value, injury to livestock and crop damage from insects and pests harbored by the weeds. Further, weeds may compete with crop plants for the essential nutrients and may produce toxic or irritant chemicals that cause 10 human or animal health problems. Some of the weed varieties also produce immense quantities of seed or vegetative reproductive parts or both that contaminate agricultural products and perpetuate the species in agricultural land.
Hence there is an ever growing need to develop herbicidal compositions that not only provide satisfactory control of weeds in the agricultural fields but also are non-phytotoxic 15 to the treated crops. It must however be appreciated that the process of combining the individual AIs or formulating one or more herbicides in a single composition poses many challenges to the formulator. Major challenges being stability of the co- formulation, decomposition of an active compound, or antagonism of the active compounds, phytotoxicity in the treated crops. Therefore, the process of co-formulating the active 20 ingredients requires rigorous experimentation.
Clodinafop-propargyl, chemical name: (prop-2-ynyl (2R)-2-[4-(5-chloro-3-fluoropyridin-2-20 yl) oxyphenoxy] propanoate) is a member of the aryloxyphenoxy propionate chemical family. It acts as a systemic herbicide that acts on post-emergent weeds such as selected grasses. It does not act on broad leaved weeds. It is applied to the 25 foliar parts of the weeds and is absorbed through the leaves. This foliar acting grass weed killer is translocated to the meristematic growing points of the plant where it interferes with the production of 25 fatty acids required for plant growth. Grass weeds controlled
3
include wild oats, rough meadow-grass, green foxtail, barnyard grass, Persian darnel, and volunteer canary seed.
Metsulfuron-methyl (methyl 2-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl) benzoate is a sulfonylurea herbicide used to control broadleaf weeds and some annual grasses. It is a systemic herbicide with foliar and soil activity and 5 works rapidly after it is taken up by the plant. It acts by inhibiting cell division in the shoots and roots of the plant, and it is biologically active at low use rates. The most common uses of metsulfuron-methyl include on crops like wheat, barley, rye, and pastures. Because it has residual activity in soils, it is necessary to allow ample time for the chemical to break down before planting certain crops. 10 Carfentrazone-ethyl (ethyl 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluorophenyl]propanoate) is a contact herbicide used to control broadleaf and sedge weeds in cereals. The mode of action of carfentrazone-ethyl is the disruption of membranes by inhibiting the action of protoporphyrinogen oxidase, causing cell death. Carfentrazone is non-selective, and can be used for complete vegetation 15 control, as well as in the form of a desiccant and a defoliant in some crops.
Although the three active ingredients above are individually known herbicides, it has been surprisingly found that applying the herbicidal composition comprising Clodinafop propargyl, Metsulfuron methyl, and Carfentrazone ethyl at specific weight range results in unexpected broad-spectrum control in wheat crop without any noticeable 20 phytotoxicity.
Some composition formulations are also known in the prior art, however these do not offer the multiple advantages as offered by the presently claimed herbicidal composition. For instance, CN106614622A provides a weeding composition, wherein the effective components comprise carfentrazone-ethyl, mesotrione, and atrazine. 25
Therefore, the present herbicidal composition has been developed to provide a superior control of weeds with no crop injury and no carryover problems and additionally minimize the total amount of herbicide being applied to cropland.
4
OBJECT OF THE INVENTION
It is an object of the present invention to provide a novel, synergistic, broad spectrum herbicidal composition of Clodinafop propargyl, Metsulfuron methyl, and Carfentrazone ethyl for effective control of broad-leaved weeds and narrow leaved weeds in various 5 agricultural crops, particularly wheat crop (Triticum aestivum).
SUMMARY OF THE INVENTION
In an aspect of the present invention, there is provided a herbicidal composition comprising 1) Clodinafop propargyl 2) Metsulfuron methyl, and 3) Carfentrazone ethyl.
10
DETAILED DESCRIPTION OF THE INVENTION
Those skilled in the art will be aware that the invention described herein is subject to variations and modifications other than those specifically described. It is to be understood that the invention described herein includes all such variations and modifications. The invention also includes all such steps, features, compositions, and compounds referred to 15 or indicated in this specification, individually or collectively, and all compositions of any two or more of said steps or features.
Unless otherwise specified, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skill in the art to which the invention belongs. For further guidance, term definitions may 20 be included to better appreciate the teaching of the present invention.
As used herein, the term “plant” refers to any plant or part thereof including serial and subterranean parts of the plant. It is contemplated that the parts of the plant may be, for example, flowers, fruits or vegetables, shoots, leaves, needles, stalks, stems, fruiting bodies, seeds, also roots and that parts of the plants may or may not be attached to the 25 remainder of the plant.
As used herein, the term “weed” refers to the unwanted plant which competes for resources with the crop or plant of interest.
5
As used herein, the term “herbicide” refers to a substance which adversely affects the existence and growth of the target weed.
As used herein the term “herbicidally effective amount” is that quantity of the herbicide active ingredient, applied in an amount which will provide the required control of weed on commercial crops. The amount is dependent upon many factors including, for 5 example, type of formulations, the crop, weed sought to be controlled and environmental conditions.
As used herein, the term “agriculturally acceptable excipient” refers to an ingredient, additive, component or supplement, liquid or solid, suitable for incorporation in agricultural compositions. 10
As used herein, the terms “comprise”, “comprises”, “comprising”, “include”, “includes”, and “including” are meant to be non-limiting ie. other steps and other ingredients which do not affect the end of result can be added. The above terms encompass the terms “consisting of” and “consisting essentially of”.
The terms “weight percent”, “wt-%”, “percent by weight”, “% by weight” and variations 15 thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent “, “%” and the like are intended to be synonymous with “weight percent”, “wt. %”, etc.
The present invention provides a herbicidal composition comprising comprising 1) 20 Clodinafop propargyl; 2) Metsulfuron methyl; and 3) Carfentrazone ethyl along with at least one agriculturally acceptable excipient.
In an embodiment, the herbicidal composition comprises Clodinafop propargyl in amount ranging from 15-40% w/w; Metsulfuron methyl in an amount ranging from 1-5% w/w; and Carfentrazone ethyl in an amount ranging from 2-10%w/w. 25
In a particular embodiment, the herbicidal composition comprises 24%w/w of Clodinafop propargyl, 1.6% w/w of Metsulfuron methyl, and 4% w/w of Carfentrazone ethyl.
6
In a particular embodiment, the herbicidal composition comprises 20%w/w of Clodinafop propargyl, 1.2% w/w of Metsulfuron methyl, and 2% w/w of Carfentrazone ethyl.
In a particular embodiment, the herbicidal composition comprises 28%w/w of Clodinafop propargyl, 2% w/w of Metsulfuron methyl, and 4% w/w of Carfentrazone ethyl.
In an embodiment, the herbicidal composition actives exhibit synergistic effect in control 5 of narrow leaved weeds, broad leaved weeds and sedges in agricultural crops, particularly in wheat.
In an embodiment, the herbicidal composition further comprises at least one agriculturally acceptable excipient. In an embodiment, the at least one excipient is selected from the group consisting of at least a wetting agent, at least a dispersing agent, at least a binder, 10 at least a rheology modifier, at least a filler, and combinations thereof.
In an embodiment, the dispersing agent is selected from the group consisting of sodium lignosulphonates, sodium naphthalene sulphonate- formaldehyde condensates, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylates and esters, ethylene oxide/propylene oxide block copolymers. In an embodiment, said dispersing agent is present in an amount 15 ranging from 8-14% w/w.
In an embodiment, the wetting agent is selected from the group consisting of blend of alkyl naphthalene sulfonate, sodium salt, Sodium lauryl sulphate, dioctylsulfosuccinate, alkyl phenol ethylene oxide derivatives, and combinations thereof. In an embodiment, 20 said at least a wetting agent is present in an amount ranging from 4-7% w/w.
In an embodiment, the at least a binder is selected from the group consisting of Starch paste, Carboxymethyl cellulose (CMC), Hydroxypropyl methyl cellulose (HPMC), Polyvinyl Pyrrolidone (PVP), Lactose monohydrate, xanthan gum, modified guar gum 25 and combinations thereof. In an embodiment, said at least a binder is present in an amount ranging from 11-20% w/w.
In an embodiment, the at least theology modifier is selected from the group consisting of polysaccharides, including xanthan gum, guar gum, and hydroxyethyl cellulose, Clays, 30
7
including montmorillonite, bentonite, sepeolite, attapulgite, laponite, hectorite, colloidal and previously precipitated silica. In an embodiment, precipitated silica can be clays, including montmorillonite, bentonite, sepeolite, attapulgite, laponite, hectorite, montmorillonite clays, bentonite clays and colloidal silicon dioxide. In a preferred embodiment, the rheology modifier is precipitated silica. In a preferred embodiment, said 5 at least a rheology modifier is present in an amount ranging from 5-9% w/w.
In an embodiment, the at least a filler is selected from the group consisting of dextrose, lactose, soluble starch, galactose, amylodextrin, ammonium sulfate, maltose, mannitol, sucrose, sorbitol, china clay, and combinations thereof. In a preferred embodiment, said at least a filler is present in an amount ranging from 20-33% w/w. 10
The herbicidal composition of the present invention may be applied to a variety of agricultural crops, particularly wheat for control of narrow leaved and broad leaved weeds.
In an embodiment, the present herbicidal composition is effective in controlling broad leaved weeds in various agricultural crops including but not limited to Chenopodium, 15 Rumex spp., Malwa spp., Fumaria spp., and Solanum nigrum
In an embodiment, the present herbicidal composition is effective in controlling narrow leaved weeds in various agricultural crops including but not limited to Avena fatua, Phalaris minor, etc.
In an embodiment, the herbicidal composition is formulated as one of water-soluble 20 concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macrogranules (GG), dry flowables (DF), aqueous 25 Suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG). In a preferred embodiment, the herbicidal composition is formulated as dry flowables (DF).
Wettable powders (WP) , water dispersible granule (WDG) and dry flowables (DF) are solid formulations which are usually applied as spray by mixing them with water. Water-
8
dispersible Granules (WDG) or Dry Flowables (DF) possess some of the same characteristics as wettable powders except they are formulated into granular-sized particles, so are easier to handle with little inhalation hazard. DF formulations readily pour out of their containers and are easier to measure and cleaner to handle than WPs.
EXAMPLES 5
The examples below are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Example 1: Preparation of herbicidal composition as Dry flowable (DF)
Table 1 below provides the composition of the present herbicidal composition as a dry 10 flowable formulation:
Table 1: Herbicidal composition (CH2414 DF)
Ingredient
Tentative percentage w/w
Clodinafop propargyl technical (96%)
15-40%
Metsulfuron methyl technical (96%)
1-5%
Carfentrazone technical (90%)
2-10%
Dispersing agent (polyisobutylene succinic anhydride-polyethylene glycol)
8-14%
Wetting agent (Sodium lauryl sulphate)
4-7%
Binder
11-20%
Rheology modifier
5-9%
Filler
20-33%
Preparation method of DF formulation is described below
All the raw materials such as wetting agent, dispersing agent, filler and technical were 15 mixed in the given proportion. This mass was mixed in the blender and grinding was carried out in jet mill, until a mean particle size of below 10 micron was obtained. The mixture was then homogenized by blender after which a dough was prepared by dough
9
mixer. Granules were then prepared through an extruder. The granules obtained were dried by hot air or in oven and were finally checked for quality parameters.
The desired quantity of the active ingredients and excipients were weighed and mixed in a blender. The mixture was then subjected to grinding through a jet mill and grinding was carried out until a mean particle size of below 10 micron was obtained. After grinding, 5 the homogenous mix was again put in a blender and a dough was prepared by dough mixer. After this step, granules were prepared by carrying the dough through an extruder. The granules thus prepared were then dried by using hot air or and oven. The dried granules were then checked for quality parameters.
The DF formulation as described above in Table 1 was tested for the below mentioned 10 quality parameters as listed in Table 2.
Table 2: Quality parameters of DF formulation
S.no.
Parameter
Desired quality
1.
Description
Dry, free flowing granules shall wet on mixing with water providing solution suitable for spray.
The material shall be free from visible extraneous matter.
2.
A.I. Content
Clodinafop propargyl :24% m/m
Metsulfuron methyl :1.6% m/m
Carfentrazone: 4.0% m/m
3.
Persistent foaming
not more than 60 ml after 1 min
4.
Wettability
max 120 sec
5.
Suspensibility
60% min.
6.
Acidity as H2SO4
0.5% max
Example 2: Field evaluation of the bioefficacy of the present herbicidal composition
Location/season/crop: 15
The presently disclosed herbicidal trimix i.e., CH2414 DF was tested for its bioefficacy against narrow leaved weeds and broad- leaved weeds in wheat crop. The trial was
10
conducted during the Rabi season 2021 at Rudrapur, Uttarakhand on PBW-343 variety of wheat.
Trial layout:
The plants were aligned in a plot size of 50 sqm., with the spacing of 10 cm between individual crop plants and the same spacing of 10 cm between the rows. The trial was laid 5 out in a random block design consisting of a total of 16 treatments in three replications.
Climatic conditions: The trial was conducted at a temp. of 22℃ under 85% relative humidity with no winds.
Application: The application of the herbicidal trimix was carried out at post emergence stage 35 days after sowing and at 2-4 leaves stage of weed. 10
Measured quantity of the chemical was added to required volume of water @ 375 lit. /ha for spray. The spray tank was filled with ½ the quantity of clean required volume of water and then the measured chemical (according to the dose) was added followed by the rest half quantity of water. The solution was stirred well before application. Knapsack sprayer fitted with boom along with flood jet nozzle was used to apply the herbicidal composition. 15
Table 3 below provides the treatment details
S.No.
Treatments
a.i./Ha
Dose/Ha
1
Untreated
2
CH 2414 DF
54 + 3.6 + 9
225
3
CH 2414 DF
60 + 4 +10
250
4
CH 2414 DF
66 + 4.4 +11
275
5
CH 2012 DF
45 + 2.7 + 4.5
225
6
CH 2012 DF
50 + 3 +5
250
7
CH 2012 DF
55 + 3.3+5.5
275
8
CH-2824 DF
63 + 4.5 + 9
225
9
CH-2824 DF
70 + 5 + 10
250
10
CH-2824 DF
77 + 5.5 + 11
275
11
Clodinafop Propargyl 15% WP
60
400
12
Metsulfuron methyl 20% WP
4
20
13
Carfentrazone ethyl 40% DF
20
50
Note
Sample-1
Clodinafop 24% + Metsulfuron 1.6% + Carfentrazone 4% DF
CH-2414 DF
Sample-2
Clodinafop 20% + Metsulfuron 1.2% + Carfentrazone 2% DF
CH-2012 DF
Sample-3
Clodinafop 28% + Metsulfuron 2.0 % + Carfentrazone 4% DF
CH-2824 DF
11
Example 2: Evaluation of bio-efficacy in Wheat crop
The weed control efficacy was calculated as percent weed control as follows:
Weed count: A quadrate (0.5m × 0.5m) was placed at 3 randomly selected places in all the plots of the experimental field and the number of weed flora were counted uniformly at 14 and 28 days after application. 5
Weed control: The weed control was calculated based on no. of live weed flora at 14 and 28 days after application.
Percent weed control = WC – WT
…………. × 100
WC 10
Where WC= No. of weed in control plot
WT= No. of weed in treated plot
Table 4: Effect of herbicidal treatment on weed density of narrow leaved weeds at 15 15 DAA & 30 DAA
Table 4(a): Phalaris minor population (0.25 sqm) at 15 & 30 days after application
Treatments
a.i./Ha
Dose/Ha
15 DAA
% Control
30 DAA
% Control
Untreated
50
60
CH 2414 DF
54 + 3.6 + 9
225
10
80
12
80.00
CH 2414 DF
60 + 4 +10
250
3
94
2
96.67
CH 2414 DF
66 + 4.4 +11
275
2.5
95
1.8
97.00
CH 2012 DF
45 + 2.7 + 4.5
225
14
72
17
71.67
CH 2012 DF
50 + 3 +5
250
12
76
13
78.33
CH 2012 DF
55 + 3.3+5.5
275
10
80
11
81.67
CH-2824 DF
63 + 4.5 + 9
225
2
96
3
95.00
CH-2824 DF
70 + 5 + 10
250
2
96
2
96.67
CH-2824 DF
77 + 5.5 + 11
275
1.8
96.4
2
96.67
Clodinafop Propargyl 15% WP
60
400
27
46
32
46.67
12
Metsulfuron methyl 20% WP
4
20
44
12
48
20.00
Carfentrazone ethyl 40% DF
20
50
41
18
49
18.33
Table 4.(b): Effect of herbicidal treatment on weed density of Broad leaves weeds at 15 & 30 days after application
Solanum nigrum population (0.25 sqm) @ 15 & 30 DAA
Treatments
a.i./Ha
Dose/Ha
15 DAA
% Control
30 DAA
% Control
Untreated
30
34
CH 2414 DF
54 + 3.6 + 9
225
6
80.00
7
79.41
CH 2414 DF
60 + 4 +10
250
4
86.67
4.4
87.06
CH 2414 DF
66 + 4.4 +11
275
3.5
88.33
4
88.24
CH 2012 DF
45 + 2.7 + 4.5
225
15
50.00
17
50.00
CH 2012 DF
50 + 3 +5
250
13
56.67
15
55.88
CH 2012 DF
55 + 3.3+5.5
275
12
60.00
14
58.82
CH-2824 DF
63 + 4.5 + 9
225
7
76.67
8
76.47
CH-2824 DF
70 + 5 + 10
250
6
80.00
7
79.41
CH-2824 DF
77 + 5.5 + 11
275
6
80.00
6
82.35
Clodinafop Propargyl 15% WP
60
400
24
20
26
23.53
Metsulfuron methyl 20% WP
4
20
12
60
14
58.82
Carfentrazone ethyl 40% DF
20
50
14
53.33
17
50
5
Table 4.c: Effect of herbicidal treatment on weed density of Broad- leaved weeds at 15 & 30 days after application.
Chenopodium album population (0.25 sqm) @ 15 & 30 DAA
Treatments
a.i./Ha
Dose/Ha
15 DAA
% Control
30 DAA
% Control
Untreated
17
21
CH 2414 DF
54 + 3.6 + 9
225
5
70.59
7
66.67
CH 2414 DF
60 + 4 +10
250
0
100.00
0
100.00
CH 2414 DF
66 + 4.4 +11
275
0
100.00
0
100.00
CH 2012 DF
45 + 2.7 + 4.5
225
6
64.71
9
57.14
CH 2012 DF
50 + 3 +5
250
3
82.35
4
80.95
CH 2012 DF
55 + 3.3+5.5
275
3
82.35
3
85.71
CH-2824 DF
63 + 4.5 + 9
225
5
70.59
4
80.95
CH-2824 DF
70 + 5 + 10
250
4
76.47
3
85.71
CH-2824 DF
77 + 5.5 + 11
275
4
76.47
3
85.71
Clodinafop Propargyl 15% WP
60
400
15
11.76
17.00
19.05
13
Metsulfuron methyl 20% WP
4
20
4
76.47
3.00
85.71
Carfentrazone ethyl 40% DF
20
50
6
64.71
5.00
76.19
Example 3: Evaluation of Phytotoxicity
A) Visual observations
Visual observations were recorded at 3, 7 and 10 days after application (DAA) of testing 5 products. The parameters were observed leaf injury on tip/surface, necrosis, vein clearing, epinasty, hyponasty and wilting. The score scale (1-10) followed for leaf injury on tips/surface is given.
Table 6: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface
10
15
(B) Phytotoxicity studies
Table-6. Evaluation of phytotoxic effect of various treatments on wheat crop at 3 DAA 20
Treatments
Treatment details
Dose a.i./hectare
3 DAA
L
N
V
E
H
W
T-1
Untreated
-
-
-
-
-
-
T-2
CH 2414 DF
54 + 3.6 + 9
0
0
0
0
0
0
T-3
CH 2414 DF
60 + 4 +10
0
0
0
0
0
0
T-4
CH 2414 DF
66 + 4.4 +11
0
0
0
0
0
0
T-5
CH 2012 DF
45 + 2.7 + 4.5
0
0
0
0
0
0
T-6
CH 2012 DF
50 + 3 +5
0
0
0
0
0
0
Leaf injury on tips/surface
Rating
0-10%
1
11-20%
2
21-30%
3
31-40%
4
41-50%
5
51-60%
6
61-70%
7
71-80%
8
81-90%
9
91-100%
10
14
Treatments
Treatment details
Dose a.i./hectare
3 DAA
L
N
V
E
H
W
T-7
CH 2012 DF
55 + 3.3+5.5
0
0
0
0
0
0
T-8
CH-2824 DF
63 + 4.5 + 9
0
0
0
0
0
0
T-10
CH-2824 DF
70 + 5 + 10
0
0
0
0
0
0
T-11
CH-2824 DF
77 + 5.5 + 11
1
3
0
1
0
0
T-12
Clodinafop Propargyl 15% WP
60
0
0
0
0
0
0
T-13
Metsulfuron methyl 20% WP
4
0
0
0
0
0
0
T-14
Carfentrazone ethyl 40% DF
20
1
3
0
1
0
0
DAA – Days after application,
L- Leaf injury on tips/surface, N-Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting
Table-6. b Evaluation of phytotoxic effect of various treatments on wheat crop after 7 DAA 5
Treatments
Treatment details
Dose a.i./hectare
7 DAA
L
N
V
E
H
W
T-1
Untreated
-
-
-
-
-
-
T-2
CH 2414 DF
54 + 3.6 + 9
0
0
0
0
0
0
T-3
CH 2414 DF
60 + 4 +10
0
0
0
0
0
0
T-4
CH 2414 DF
66 + 4.4 +11
0
0
0
0
0
0
T-5
CH 2012 DF
45 + 2.7 + 4.5
0
0
0
0
0
0
T-6
CH 2012 DF
50 + 3 +5
0
0
0
0
0
0
T-7
CH 2012 DF
55 + 3.3+5.5
0
0
0
0
0
0
T-8
CH-2824 DF
63 + 4.5 + 9
0
0
0
0
0
0
T-10
CH-2824 DF
70 + 5 + 10
0
0
0
0
0
0
T-11
CH-2824 DF
77 + 5.5 + 11
1
3
0
1
0
0
T-12
Clodinafop Propargyl 15% WP
60
0
0
0
0
0
0
T-13
Metsulfuron methyl 20% WP
4
0
0
0
0
0
0
T-14
Carfentrazone ethyl 40% DF
20
1
3
0
1
0
0
DAA – Days after application,
L- Leaf injury on tips/surface, N-Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting
Table-6.c Evaluation of phytotoxic effect of various treatments on wheat crop at 10 DAA 10
Treatments
Treatment details
Dose a.i./hectare
10 DAA
L
N
V
E
H
W
T-1
Untreated
-
-
-
-
-
-
T-2
CH 2414 DF
54 + 3.6 + 9
0
0
0
0
0
0
T-3
CH 2414 DF
60 + 4 +10
0
0
0
0
0
0
15
Treatments
Treatment details
Dose a.i./hectare
10 DAA
L
N
V
E
H
W
T-4
CH 2414 DF
66 + 4.4 +11
0
0
0
0
0
0
T-5
CH 2012 DF
45 + 2.7 + 4.5
0
0
0
0
0
0
T-6
CH 2012 DF
50 + 3 +5
0
0
0
0
0
0
T-7
CH 2012 DF
55 + 3.3+5.5
0
0
0
0
0
0
T-8
CH-2824 DF
63 + 4.5 + 9
0
0
0
0
0
0
T-10
CH-2824 DF
70 + 5 + 10
0
0
0
0
0
0
T-11
CH-2824 DF
77 + 5.5 + 11
1
3
0
1
0
0
T-11
Clodinafop Propargyl 15% WP
60
0
0
0
0
0
0
T-13
Metsulfuron methyl 20% WP
4
0
0
0
0
0
0
T-14
Carfentrazone ethyl 40% DF
20
1
3
0
1
0
0
DAA – Days after application,
L- Leaf injury on tips/surface, N-Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting
Results and conclusions 5
The prominent narrow leaved weed species in the weedy plot at the time of application were Phalaris minor while among the broad leaves weeds the major weed flora was of Solanum nigrum and Chenopodium album
As seen from Table 4(a), Clodinafop treatment alone at 60g a.i./ha shows about 45% 10 control by day 15 and day 30 post application. Metsulfuron treatment alone at 4g a.i./ha shows 12% and 20% control by day 15 and day 30 respectively. Carfentrazone treatment alone at 20g a.i./ha shows about 18% control by day 15 and day 30 post application. A person skilled in the art, would reasonably expect to apply Clodinafop, Metsulfuron, and Carfentrazone together at their recommended dosages (total concentration of 84g a.i./ha) 15 to get the desired effect. However, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2414 DF, where Clodinafop concentration is 54g a.i./ha, Metsulfuron concentration is 3.6g a.i./ha, and Carfentrazone concentration is 9g a.i./ha, where total dosage concentration is 66.6g a.i./ha, shows 80% control at day 15 and day 30 post application. This higher efficacy is achieved at 20% less total concentration of the 3 20 herbicides, and further, the concentration of each active is also less than the individual concentrations. This is completely unexpected and surprising.
16
Still further, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2414 DF, where Clodinafop concentration is 60g a.i./ha, Metsulfuron concentration is 4g a.i./ha, and Carfentrazone concentration is 10g a.i./ha, where total dosage concentration is 74g a.i./ha, shows 94% control at day 15 and about 97% control at day 30 post application. This higher efficacy is achieved at about 12% less total concentration of the 5 3 herbicides, and further, the concentration of Carfentrazone is 50% less than the recommended concentration. This is completely unexpected and surprising.
Still further, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2012 DF, where Clodinafop concentration is 45g a.i./ha, Metsulfuron concentration is 2.7g a.i./ha, and Carfentrazone concentration is 4.5g a.i./ha, where total dosage 10 concentration is 52.2g a.i./ha, shows 72% control at day 15 and at day 30 post application. This higher efficacy is achieved at about 38% less total concentration of the 3 herbicides when combined at their recommended concentration. This is completely unexpected and surprising.
Still further, unexpectedly and surprisingly, it was found that in the trimix coded as CH 15 2012 DF, where Clodinafop concentration is 50g a.i./ha, Metsulfuron concentration is 3g a.i./ha, and Carfentrazone concentration is 5g a.i./ha, where total dosage concentration is 58g a.i./ha, shows 76% control at day 15 and 78% control at day 30 post application. This higher efficacy is achieved at about 31% less total concentration of the 3 herbicides when combined at their recommended concentration. This is completely unexpected and 20 surprising.
Still further, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2012 DF, where Clodinafop concentration is 55g a.i./ha, Metsulfuron concentration is 3.3g a.i./ha, and Carfentrazone concentration is 5.5g a.i./ha, where total dosage concentration is 63.8g a.i./ha, shows 80% control at day 15 and about 82% control at day 25 30 post application. This higher efficacy is achieved at about 24% less total concentration of the 3 herbicides when combined at their recommended concentration. This is completely unexpected and surprising.
Unexpectedly and surprisingly, it was found that in the trimix coded as CH 2824 DF, where Clodinafop concentration is 63g a.i./ha, Metsulfuron concentration is 4.5g a.i./ha, 30
17
and Carfentrazone concentration is 9g a.i./ha, where total dosage concentration is 76.5g a.i./ha, shows 96% control at day 15 and about 95% control at day 30 post application. This higher efficacy is achieved at about 9% less total concentration of the 3 herbicides when combined as per individual concentrations. This is completely unexpected and surprising. 5
Therefore, in view of the above, it can be clearly appreciated that formulations clodinafop 25% + metsulfuron 1.6% + carfentrazone 4%; Clodinafop 20% + metsulfuron 1.2% + carfentrazone 2%; or Clodinafop 28% + metsulfuron 2% + carfentrazone 4% shows synergistic effect in control of narrow leaf weeds (Phalaris minor) compared to application of Clodinafop 15% + metsulfuron 20% + carfentrazone 40%. 10
As seen in Table 4(b), Clodinafop treatment alone at 60g a.i./ha shows about 24% control by day 15 and day 30 post application. Metsulfuron treatment alone at 4g a.i./ha shows about 60% control by day 15 and day 30 post application. Carfentrazone treatment alone at 20g a.i./ha shows about 50% control by day 15 and day 30 post application. A person skilled in the art, would reasonably expect to apply Clodinafop, Metsulfuron, and 15 Carfentrazone together at their recommended dosages (total concentration of 84g a.i./ha) to get the desired effect. However, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2414 DF, where Clodinafop concentration is 54g a.i./ha, Metsulfuron concentration is 3.6g a.i./ha, and Carfentrazone concentration is 9g a.i./ha, where total dosage concentration is 66.6g a.i./ha, shows 80% control at day 15 and day 30 post 20 application. This higher efficacy is achieved at 20% less total concentration of the 3 herbicides, and further, the concentration of each active is also less than the individual concentrations. This is completely unexpected and surprising.
Further, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2414 DF, where Clodinafop concentration is 60g a.i./ha, Metsulfuron concentration is 4g 25 a.i./ha, and Carfentrazone concentration is 10g a.i./ha, where total dosage concentration is 74g a.i./ha, shows about 87% control at day 15 and day 30 post application. This higher efficacy is achieved at about 12% less total concentration of the 3 herbicides, and further, the concentration of Carfentrazone is 50% less than the individual concentration. This is completely unexpected and surprising. 30
18
Unexpectedly and surprisingly, it was found in the trimix coded as CH 2842 DF, where Clodinafop concentration is 63g a.i./ha, Metsulfuron concentration is 4.5g a.i./ha, and Carfentrazone concentration is 9g a.i./ha, where total dosage concentration is 76.5g a.i./ha, shows about 77% control at day 15 and day 30 post application. This higher efficacy is achieved at about 9% less total concentration of the 3 herbicides, and further, 5 the concentration of Carfentrazone is more than 50% less than the individual concentration. This is completely unexpected and surprising.
In view of the above, it can be clearly appreciated that formulations clodinafop 25% + metsulfuron 1.6% + carfentrazone 4%; Clodinafop 20% + metsulfuron 1.2% + carfentrazone 2%; or Clodinafop 28% + metsulfuron 2% + carfentrazone 4% shows 10 synergistic effect in control of broad leaf weeds (Solanum nigrum) compared to application of Clodinafop 15% + metsulfuron 20% + carfentrazone 40%.
As seen in Table 4(c), Clodinafop treatment alone at 60g a.i./ha shows about 12% control by day 15 and 19% control by day 30 post application. Metsulfuron treatment alone at 4g a.i./ha shows about 76% control by day 15 and 85% control by day 30 post application. 15 Carfentrazone treatment alone at 20g a.i./ha shows about 64% control by day 15 and 76% control by day 30 post application. A person skilled in the art, would reasonably expect to apply Clodinafop, Metsulfuron, and Carfentrazone together at their recommended dosages (total concentration of 84g a.i./ha) to get the desired effect. However, unexpectedly and surprisingly, it was found that in the trimix coded as CH 2414 DF, 20 where Clodinafop concentration is 60g a.i./ha, Metsulfuron concentration is 4g a.i./ha, and Carfentrazone concentration is 10g a.i./ha, where total dosage concentration is 74g a.i./ha, shows 100% control at day 15 and day 30 post application. This higher efficacy is achieved at 12% less total concentration of the 3 herbicides, and further, the concentration of Carfentrazone si 50% less than the individual concentration. This is completely 25 unexpected and surprising.
These data show that formulations clodinafop 25% + metsulfuron 1.6% + carfentrazone 4%; Clodinafop 20% + metsulfuron 1.2% + carfentrazone 2%; or Clodinafop 28% + metsulfuron 2% + carfentrazone 4% shows synergistic effect in control of broad leaf weeds (Chenopodium album) compared to application of Clodinafop 15% + metsulfuron 30 20% + carfentrazone 40%.

I/We Claim:
1. A herbicidal composition comprising a) Clodinafop propargyl b) Metsulfuron methyl, and c) Carfentrazone ethyl along with at least one agriculturally acceptable excipient.
5
2. The herbicidal composition as claimed in claim 1, wherein said herbicidal composition comprises a) Clodinafop propargyl in an amount ranging from 15-40% w/w; b) Metsulfuron methyl in an amount ranging from 1-5% w/w; and c) Carfentrazone ethyl in an amount ranging from 2-10% w/w.
10
3. The herbicidal composition as claimed in claim 2, wherein said herbicidal composition comprises a) Clodinafop propargyl in an amount of 24% w/w; b) Metsulfuron methyl in an amount of 1.6% w/w; and c) Carfentrazone ethyl in an amount of 4% w/w;
or 15
a) Clodinafop propargyl in an amount of 20% w/w; b) Metsulfuron methyl in an amount of 1.2% w/w; and c) Carfentrazone ethyl in an amount of 2% w/w;
or
a) Clodinafop propargyl in an amount of 28% w/w; b) Metsulfuron methyl in an amount of 2% w/w; and c) Carfentrazone ethyl in an amount of 4% w/w. 20
4. The herbicidal composition as claimed in claim 1, wherein said at least one agriculturally acceptable excipient is selected from the group consisting of at least a dispersing agent, at least a wetting agent, at least a binder, at least a filler, at least a rheology modifier, and combinations thereof. 25
5. The herbicidal composition as claimed in claim 4, wherein said at least a wetting agent is present in an amount ranging from 4-7%w/w, at least a dispersing agent is present in an amount ranging from 8-14%w/w, at least a binder is present in an amount ranging from 11-20% w/w, at least a rheology modifier is present in an 30 amount ranging from 5-9% w/w, and at least a filler is present in an amount ranging from 20-33%w/w.
20
6. The herbicidal composition as claimed in claim 4, wherein said at least awetting agent is selected from the group consisting of a blend of alkyl naphthalene sulfonate, sodium salt, sodium laurel sulphate, and combinations thereof.
5
7. The herbicidal composition as claimed in claim 4, wherein said at least a dispersing agent is selected from the group consisting of sodium lignosulphonates, sodium naphthalene sulphonate- formaldehyde condensates, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylates and esters, ethylene oxide/propylene oxide block copolymers, and combinations thereof. 10
8. The herbicidal composition as claimed in claim 4, wherein said at least a binder is selected from the group consisting of Starch paste, Hydroxypropyl methyl cellulose (HPMC), Polyvinyl Pyrrolidone (PVP), Lactose monohydrate, and combinations thereof. 15
9. The herbicidal composition as claimed in claim 4, wherein said at least a filler is selected from the group comprising the filler is selected from the group consisting of dextrose, lactose, soluble starch, galactose, amylodextrin, ammonium sulfate, maltose, mannitol, sucrose, sorbitol, china clay, and combinations thereof. 20
10. The herbicidal composition as claimed in claim 4, wherein said at least a rheology modifier is selected from the group consisting of Polysaccharides, including xanthan gum, guar gum, and hydroxyethyl cellulose, Clays, including montmorillonite, bentonite, sepeolite, attapulgite, laponite, hectorite, colloidal 25 and previously precipitated silica.
11. The herbicidal composition as claimed in claim 1, wherein said composition is formulated as any one of a water-dispersible granule (WDG or WG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder 30 (WDP), a water-soluble powder (SP), a granule (GR), a dry flowable (DF), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a
21
microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), an oil-based suspension concentrate (OD), a flowable suspension (FS), a suspoemulsion (SE), or a microencapsulated suspension (CS).
5
12. The herbicidal composition as claimed in claim 11, wherein said composition is formulated as a dry flowable (DF).
13. The herbicidal composition as claimed in claim 2, wherein said herbicidal composition is effective in control of undesirable vegetation at a dosage of 250-10 275 ml/hectare.